Hydrogen, Fuel 

Cells and 

Infrastructure 2003 Technologies 

Annual Progress Report Program 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report

President Bush Launches the Hydrogen Fuel Initiative 

"Tonight I am proposing $1.2 billion in research funding so that 

America can lead the world in developing clean, hydrogen-powered 

automobiles." 

"A simple chemical reaction between 

hydrogen and oxygen generates energy, which 

can be used to power a car producing only 

water, not exhaust fumes. With a new national 

commitment, our scientists and engineers will 

overcome obstacles to taking these cars from 

laboratory to showroom so that the first car driven by a child born 

today could be powered by hydrogen, and pollution-free." 

"Join me in this important innovation to make our air significantly 

cleaner, and our country much less dependent on foreign sources 

of energy." 

President George W. Bush 

2003 State of the Union Address 

January 28, 2003 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Benefits of a Hydrogen Economy 

The President's FreedomCAR and Hydrogen Fuel Initiative is designed to reverse America's growing 

dependence on foreign oil by developing the technology to enable production of hydrogen-powered fuel cell 

vehicles and fueling infrastructure to support them. This initiative was chosen not only because of the energy 

security benefits associated with a domestic fuel that can be produced from a wide range of feedstocks, but also 

because of the potential environmental benefits in both transportation and stationary markets. 

Energy Security 

America's transportation sector relies almost 

exclusively on refined petroleum products. More than 

one-half of the petroleum consumed in the United States 

is imported, and that percentage is expected to rise 

steadily for the foreseeable future. Even with the 

significant energy efficiency benefits that gasolineelectric hybrid vehicles and diesels can provide, we 

must ultimately find an alternative fuel that can be 

domestically produced. Hydrogen (along with biofuels) 

is a versatile energy carrier that is environmentally 

clean and could be produced in large quantities entirely 

from domestic sources. Traditional sources of energy -

fossil fuels like natural gas and coal; renewable energy 

sources such as solar radiation, wind and biomass; and 

nuclear energy can all be used to produce hydrogen. Its 

use as a major energy carrier would provide the United 

States with a more diversified energy infrastructure. 

Environmental 

“Hydrogen fuel cells represent one of the 

most encouraging, innovative 

technologies of our era.... One of the 

greatest results of using hydrogen power, 

of course, will be energy independence for 

this nation... think about a legacy here at 

home, about making investments today 

that will make future citizens of our 

country less dependent on foreign sources 

of energy. And so that’s why I’m going to 

work with the Congress to move this 

nation forward on hydrogen fuel cell 

technologies. It is in our national interest 

that we do so.” 

President George W. Bush 

The National Building Museum 

February 6, 2003 

While addressing the energy security issue, we must also address our environmental viability. Air quality 

is a major national concern. It has been estimated that 60% of Americans live in areas where levels of one or 

more air pollutants are high enough to affect public health and/or the environment. Personal vehicles and 

electric power plants are significant 

contributors to the nation's air quality 

problems. Most states are now 

developing strategies for bringing their 

major metropolitan areas into 

compliance with the requirements of the 

Clean Air Act. Widespread use of fuel 

cell vehicles, because they are zeroemission vehicles and have no on-road 

emission deterioration, could have a 

measurable effect on reducing nitrogen 

oxides, volatile organic compounds, and 

particulate matter produced by light-duty 

vehicles. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Emission of greenhouse gases, such as carbon dioxide and methane, has been cited as a major global 

concern. Build-up of these gases in the atmosphere is thought to have detrimental effects on the global climate. 

Although there is not yet agreement on what the exact impact will be, when it will be realized, or how best to 

address the issue, there is agreement that emissions of these gases needs to be reduced. Hydrogen offers a 

unique opportunity to address this problem, since carbon emissions can be decoupled from energy use and 

power generation. When used in a fuel cell, the only emission is water vapor. Efficient hydrogen production 

technologies and the possibility of carbon sequestration make natural gas and coal viable feedstock options, 

even in a carbon-constrained environment. In the case of renewable and nuclear options, greenhouse gases can 

virtually be eliminated. 

Economic Competitiveness 

Abundant, reliable, and affordable energy is an essential component in a healthy economy. When energy 

prices spike, as has occurred several times recently due to supply interruptions and/or high demand, Americans 

suffer, particularly those in lower-income brackets. Hydrogen offers unique opportunities to drastically increase 

the efficiency with which we generate and use energy. And because it can be produced from a wide variety of 

domestically-available resources, we can reduce the impact of externalities on energy prices. 

The technical and economic success of hydrogen-based distributed energy systems will stimulate new 

business ventures. Hydrogen power parks will provide an economic development path for the integrated 

production of energy services such as electricity, transportation fuels, and heating and cooling. This may lead 

to the creation of high-tech jobs to build and maintain these systems. Hydrogen also offers a wide variety of 

opportunities for the development of new centers of economic growth in both rural and urban areas that are 

currently too far off-line to attract investment in our centralized energy system. 

The success of current U.S. industry is also of vital importance to the well-being of our people and of the 

Nation as a whole. For example, the U.S. auto industry is the largest automotive industry in the world, 

producing 30% more vehicles than the second largest producer, Japan. For every worker directly employed by 

an auto manufacturer, there are nearly seven spin-off jobs. America's automakers are among the largest 

purchasers of aluminum, copper, iron, lead, plastics, rubber, textiles, vinyl, steel and computer chips. The auto 

industry is also a major exporter, accounting for 12% of all non-agricultural exports. Remaining competitive in 

the international market is essential to the U.S. economy. 

3 
U.S. Department of Energy 

1000 Independence Avenue, S.W. 

Washington, D.C. 20585-0121 

FY 2003 

Progress Report for Hydrogen, Fuel Cells, and 

Infrastructure Technologies Program 

Energy Efficiency and Renewable Energy 

Office of Hydrogen, Fuel Cells, and Infrastructure Technologies 

Approved by Steven Chalk 

October 2003 
ACKNOWLEDGEMENT 

We would like to express our sincere appreciation to QSS 

Group, Inc., and Argonne National Laboratory for their 

artistic and technical contributions in preparing and 

publishing this report. 

In addition, we would like to thank all our Program 

participants for their contributions and all the authors who 

prepared the project abstracts that comprise this report. 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS
 

I.	 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-1
 

II.	 Distributed Production Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-1
 

A.	 Distributed Production Technologies 

1.	 Novel Catalytic Fuel Reforming, InnovaTek Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-3
 

2.	 Engineering Development of Ceramic Membrane Reactor Systems for Converting 

Natural Gas to Hydrogen and Synthesis Gas for Liquid Transportation Fuels 

(ITM Syngas), Air Products and Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-9
 

3.	 Integrated Ceramic Membrane System for Hydrogen Production, Praxair, Inc. . . . . . . . . . . . II-14
 

4.	 Low Cost Hydrogen Production Platform, Praxair Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-18
 

5.	 Encapsulated Metal Hydride Separation Membrane Development,
 

Westinghouse Savannah River Technology Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-23
 

6.	 Defect-Free Thin Film Membranes for H2 Separation and Isolation, 

Sandia National Laboratories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-28
 

7.	 Autothermal Cyclic Reforming Based Hydrogen Generating and Dispensing System, 

GE Global Research, General Electric Company . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-34
 

8.	 Hydrogen Technical Analysis: Evaluation of Metal Hydride Slurries, TIAX LLC . . . . . . . . . . II-39
 

9.	 Water-Gas Shift Membrane Reactor Studies, National Energy Technology Laboratory . . . . . II-45
 

10. Integrating a Hydrogen Energy Station into a Federal Building, TIAX LLC . . . . . . . . . . . . . . . II-49
 

11. Hydrogen from Renewable Energy Sources: Pathway to 10 Quads for
 

Transportation Uses in 2030 to 2050, Directed Technologies, Inc. . . . . . . . . . . . . . . . . . . . . . . II-53
 

B.	 Production from Biomass 

1.	 Biohydrogen Production from Renewable Organic Wastes, 

Dept. of Civil and Construction Engineering, Iowa State University . . . . . . . . . . . . . . . . . . . . II-57
 

2.	 Biological Water Gas Shift Development, National Renewable Energy Laboratory . . . . . . . . II-62
 

3.	 Supercritical Water Partial Oxidation, General Atomics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-68
 

4.	 Biomass-Derived Hydrogen from a Thermally Ballasted Gasifier, Iowa State University . . . . II-73
 

5.	 Techno-Economic Analysis of Hydrogen Production by Gasification of Biomass,
 

Gas Technology Institute . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-78
 

6.	 Hydrogen from Biomass - Catalytic Reforming of PyrolysisVapors, 

National Renewable Energy Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-82
 

7.	 Production of Hydrogen from Post-Consumer Residues, 

National Renewable Energy Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-86
 

8.	 Fluidizable Catalysts for Hydrogen Production from Biomass Pyrolysis/Steam 

Reforming, National Renewable Energy Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-89
 

9.	 Hydrogen from Biomass for Urban Transportation, Clark Atlanta University . . . . . . . . . . . . . II-93
 

10. Reformer Model Development for Hydrogen Production, Jet Propulsion Laboratory . . . . . . . II-98
 

C.	 Photolysis 

1.	 Maximizing Photosynthetic Efficiencies and Hydrogen Production in
 

Microalgal Cultures, University of California, Berkeley . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-104
 

2. Algal H2-Production Systems: Creation of Designer Alga for Efficient and Robust
 

Production of H2, Oak Ridge National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-108
 

iii 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

II.	 Distributed Production Technologies (Continued) 

C.	 Photolysis (Continued) 

3. Algal Systems for Hydrogen Photoproduction, National Renewable Energy Laboratory . . . . . II-111
 

4.	 Photoelectrochemical Systems for H2 Production, National Renewable Energy Laboratory . II-119
 

5.	 Photoelectrochemical Hydrogen Production, Hawaii Natural Energy Institute, 

University of Hawaii at Manoa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-124
 

6.	 Photoelectrochemical Hydrogen Production Using New Combinatorial Chemistry 

Derived Materials, University of California, Santa Barbara . . . . . . . . . . . . . . . . . . . . . . . . . . II-130
 

7.	 Discovery of Photocatalysts for Hydrogen Production, SRI International . . . . . . . . . . . . . . . II-137
 

D.	 Electrolysis 

1.	 Low Cost, High Efficiency Reversible Fuel Cell Systems, Technology Management, Inc.. . .II-142
 

2.	 High-Efficiency Steam Electrolyzer, Lawrence Livermore National Laboratory . . . . . . . . . . II-146
 

3.	 High-Temperature Solid Oxide Electrolyser System, 

Idaho National Engineering and Environmental Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . II-150
 

E.	 High-Temperature Thermochemical Processes 

1. Thermocatalytic CO2-free Production of Hydrogen from Hydrocarbon Fuels,
 

Florida Solar Energy Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-155
 

2.	 Analysis of Solar Thermochemical Water-Splitting Cycles for Hydrogen Production, 

Florida Solar Energy Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-159
 

III. Hydrogen Storage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-1
 

A.	 Compressed/Liquid H2 Tanks 

1.	 Hydrogen Composite Tank Project, Quantum Fuel System Technologies Worldwide Inc. . . . . III-3
 

2.	 Development of a Compressed Hydrogen Gas Integrated Storage System (CH2-ISS) 

for Fuel Cell Vehicles, Johns Hopkins University Applied Physics Laboratory . . . . . . . . . . . . III-7
 

3.	 Next Generation Hydrogen Storage, Lawrence Livermore National Laboratory . . . . . . . . . . III-11
 

4.	 Hydrogen Storage in Insulated Pressure Vessels, 

Lawrence Livermore National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-15
 

5.	 Low Permeation Liner for Hydrogen Gas Storage Tanks, 

Idaho National Engineering & Environmental Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . III-19
 

6.	 Low Cost, High Efficiency, High Pressure Hydrogen Storage (New FY 2004 Project), 

QUANTUM Technologies, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-24
 

B.	 Hydrides 

1.	 Catalytically Enhanced Hydrogen Storage Systems, University of Hawaii . . . . . . . . . . . . . . . III-26
 

2.	 Hydride Development for Hydrogen Storage, Sandia National Laboratories . . . . . . . . . . . . . III-31
 

3.	 Complex Hydrides for Hydrogen Storage, Florida Solar Energy Center . . . . . . . . . . . . . . . . III-38
 

4.	 High Density Hydrogen Storage System Demonstration Using NaAlH4 Based
 

Complex Compound Hydrides, United Technologies Research Center . . . . . . . . . . . . . . . . . . III-43
 

5.	 Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through 

Molecular Modeling and Combinatorial Methods (New FY 2004 Project), 

UOP Research Department . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-48
 

6.	 Sub-Nanostructured Non-Transition Metal Complex Grids for Hydrogen Storage
 

(New FY 2004 Project), Cleveland State Univercity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-50
 

iv 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

III. Hydrogen Storage (Continued) 

B.	 Hydrides (Continued) 

7.	 Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity
 

(New FY 2004 Project), United Technologies Research Center . . . . . . . . . . . . . . . . . . . . . . .III-52
 

C.	 Carbon Materials 

1.	 Hydrogen Storage in Carbon Single-wall Nanotubes, 

National Renewable Energy Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-54
 

2.	 Doped Carbon Nanotubes for Hydrogen Storage,
 

Westinghouse Savannah River Technology Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-61
 

3.	 Hydrogen Storage in Metal-Modified Single-Walled Carbon Nanotubes,
 

California Institute of Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-65
 

4.	 Carbon-based Sorbent Systems for an Effective Containment of Hydrogen 

(New FY 2004 Project), Air Products and Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . .III-69
 

D.	 Chemical Hybrides 

1.	 Process for the Regeneration of Sodium Borate to Sodium Borohydride for Use
 

as a Hydrogen Storage Source (New FY 2004 Project), Millennium Cell, Inc. . . . . . . . . . . . .III-71
 

2.	 Chemical Hydride Slurry for Hydrogen Production and Storage 

(New FY 2004 Project), Safe Hydrogen, LLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-73
 

E.	 New Materials 

1.	 Novel, Light-Element Nanostructured Materials for Hydrogen Storage 

(New FY 2004 Project), Nanomix, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-75
 

F.	 Testing 

1.	 Standardized Testing Program For Emergent Chemical Hydride And Carbon Storage
 

Technologies, Southwest Research Institute . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .III-77
 

IV. Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-1
 

A.	 Transportation Power Systems 

1.	 Fuel Cell Systems Analysis, Argonne National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-3
 

2.	 Fuel Cell Vehicle Systems Analysis, National Renewable Energy Laboratory . . . . . . . . . . . . . IV-8
 

3.	 Cost Analyses of Fuel Cell Stack/Systems, TIAX LLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-13
 

4.	 Precious Metal Availability and Cost Analysis for PEMFC Commercialization, TIAX LLC. . . . IV-17
 

5.	 DFMA Cost Estimates of Fuel-Cell/Reformer Systems at Low/Medium/High 

Production Rates, Directed Technologies, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-22
 

6.	 Atmospheric Fuel Cell Power System for Transportation, UTC Fuel Cells . . . . . . . . . . . . . . . IV-27
 

7.	 Platinum Recycling Technology Development (New FY 2004 Project), Ion Power, Inc. . . . . IV-31
 

8.	 Platinum Group Metal Recycling Technology Development
 

(New FY 2004 Project), Engelhard Corporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-33
 

B.	 Transportation systems Components 

1.	 Cost and Performance Enhancements for a PEM Fuel Cell System, 

Honeywell Engines, Systems & Services . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-35
 

2.	 Development and Testing of a Toroidal Intersecting Vane Machine (TIVM) 

Air Management System, Mechanology, LLC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-39
 

v 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

IV. Fuel Cells (Continued) 

B.	 Transportation systems Components (Continued) 

3. Motor Blower Technologies for Fuel Cell Automotive Power Systems, UTC Fuel Cells . . . . . IV-44
 

4.	 Hybrid Compressor/Expander Module, TIAX LLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-49
 

5.	 Carbon Foam for Fuel Cell Humidification, Oak Ridge National Laboratory . . . . . . . . . . . . IV-54
 

C.	 Stationary Power Systems 

1.	 Proton Exchange Membrane Fuel Cell Power System on Ethanol, Caterpillar Inc. . . . . . . . . IV-58
 

2.	 New Proton Conducting Solid Sulfide Membranes for Intermediate Temperature
 

Fuel Cells, Iowa State University of Science and Technology . . . . . . . . . . . . . . . . . . . . . . . . . IV-62
 

3.	 Fuel Cell Distributed Power Package Unit: Fuel Processing Based on Autothermal
 

Cyclic Reforming, General Electric Company. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-67
 

4.	 Advanced Buildings PEM Fuel Cell System (New FY 2004 Project), IdaTech, LLC . . . . . . . IV-71
 

5.	 150-kW PEM Fuel Cell Power Plant Verification and Regional Demonstration 

of 150-kW PEM Fuel Cell Power Plant (New FY 2004 Project), UTC Fuel Cells, LLC . . . . IV-73
 

6.	 Backup/Peak Shaving Fuel Cell Systems - Design and Development of the 

GenCoreTM II (New FY 2004 Project), Plug Power Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-75
 

7. Economic Analysis of PEMFC Systems (New FY 2004 Project), Battelle . . . . . . . . . . . . . . IV-77
 

D.	 Fuel Processing Subsystem and Components 

1.	 Water-Gas Shift Catalysis, Argonne National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-79
 

2.	 Catalysts for Autothermal Reforming, Argonne National Laboratory . . . . . . . . . . . . . . . . . . . IV-83
 

3.	 Development of Novel Water-Gas-Shift Membrane Reactor, The Ohio State University . . . . IV-88
 

4.	 On-Board Vehicle, Cost Effective Hydrogen Enhancement Technology for 

Transportation PEM Fuel Cells, United Technologies Research Center . . . . . . . . . . . . . . . . . IV-93
 

5.	 Plate-Based Fuel Processing System, Catalytica Energy Systems . . . . . . . . . . . . . . . . . . . . . . IV-98
 

6.	 Quick-Starting Fuel Processors - A Feasibility Study, Argonne National Laboratory. . . . . . IV-103
 

7.	 Fast Start Reformer Components, Los Alamos National Laboratory . . . . . . . . . . . . . . . . . . . IV-107
 

8.	 Reformate Cleanup: The Case for Microchannel Architecture, 

Pacific Northwest National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-113
 

9.	 Microchannel Steam Reformation of Hydrocarbon Fuels,
 

Pacific Northwest National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-119
 

10. Fuel Processors for PEM Fuel Cells, University of Michigan . . . . . . . . . . . . . . . . . . . . . . . . IV-124
 

11. Sulfur Removal from Reformate, Argonne National Laboratory . . . . . . . . . . . . . . . . . . . . . IV-129
 

12. Selective Catalytic Oxidation of Hydrogen Sulfide, Oak Ridge National Laboratory . . . . . IV-133
 

13. Effects of Fuel Constituents on Fuel Processing Catalysts, Argonne National Laboratory . . . IV-138
 

14. Testing of Fuels in Fuel Cell Reformers, Los Alamos National Laboratory . . . . . . . . . . . . . IV-142
 

15. Development of Reaction Kinetics for Diesel-Based Fuel Cell Reformers, 

National Energy Technology Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-147
 

16. Reforming of Diesel Fuel for Transportation Applications, Argonne National Laboratory . . . IV-153
 

17. Advanced High Efficiency Quick Start Fuel Processor for Transportation
 

Applications, Nuvera Fuel Cells, Inc.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-157
 

18. Development of a 50-kW Fuel Processor for Stationary Fuel Cell Applications Using
 

Revolutionary Materials for Absorption-Enhanced Natural Gas Reforming 

(New FY 2004 Project), ChevronTexaco Technology Ventures . . . . . . . . . . . . . . . . . . . . . . . IV-163
 

vi 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

IV. Fuel Cells (Continued) 

E.	 Fuel Cell Stack Subsystem and Components 

1.	 Integrated Manufacturing for Advanced Membrane Electrode Assemblies, De Nora N.A.. . . . IV-165
 

2.	 Development of High Temperature Membranes and Improved Cathode Catalysts,
 

UTC Fuel Cells IV-171
 

3.	 Advanced MEAs for Enhanced Operating Conditions, 3M Company . . . . . . . . . . . . . . . . . . IV-178
 

4.	 Ultra-Thin Composite Membrane-Electrode Assembly For High-Temperature Proton 

Exchange Membrane Fuel Cells, FuelCell Energy, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-184
 

5.	 Development of High-Performance, Low-Pt Cathodes Containing New Catalysts and 

Layer Structure, Cabot Superior MicroPowders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-188
 

6.	 Design and Installation of a Pilot Plant for High-Volume Electrode Production, 

Southwest Research Institute . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-194
 

7.	 Scale-Up of Carbon/Carbon Composite Bipolar Plates, Porvair Fuel Cell Technology, Inc. .IV-197
 

8.	 Carbon Composite Bipolar Plates, Oak Ridge National Laboratory . . . . . . . . . . . . . . . . . . . IV-202
 

9.	 Cost-Effective Surface Modification for Metallic Bipolar Plates,
 

Oak Ridge National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-206
 

10. High-Performance, Matching, PEM Fuel Cell Components and Integrated Pilot
 

Manufacturing Processes, 3M Company . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-211
 

11. High-Temperature Membranes, Case Western Reserve University . . . . . . . . . . . . . . . . . . . . . IV-217
 

12. Electrodes for Polymer Electrolyte Membrane Operation on Hydrogen/Air and
 

Reformate/Air, Los Alamos National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-221
 

13. New Electrocatalysts for Fuel Cells, Lawrence Berkeley National Laboratory . . . . . . . . . . . IV-226
 

14. Low-Platinum Catalysts for Oxygen Reduction at Proton Exchange Membrane 

Fuel Cell Cathodes, Naval Research Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-231
 

15. Low Platinum Loading Catalysts for Fuel Cells, Brookhaven National Laboratory . . . . . . . IV-236
 

16. Direct Methanol Fuel Cells, Los Alamos National Laboratory. . . . . . . . . . . . . . . . . . . . . . . . IV-241
 

17. Development of Advanced Catalysts for Direct Methanol Fuel Cells, 

California Institute of Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-248
 

18. Novel Approach to Non-Precious Metal Catalysts (New FY 2004 Project), 3M Company. . . . IV-253
 

19. Novel Non-Precious Metals for PEMFC: Catalyst Selection Through Molecular 

Modeling and Durability Studies (New FY 2004 Project), University of South Carolina . . . IV-255
 

20. Development of a Thermal and Water Management System for PEM Fuel Cells
 

(New FY 2004 Project), Honeywell International Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-257
 

21. Development of Polybenzimidazole-based, High-Temperature Membrane and
 

Electrode Assemblies for Stationary and Automotive Applications
 

(New FY 2004 Project), Plug Power, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-259
 

22. Development, Characterization, and Evaluation of Transition Metal/Chalcogen
 

Based Cathode Catalysts for PEM Fuel Cells (New FY 2004 Project),
 

Ballard Power Systems Corporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-261
 

23. PEM Stack Durability (New FY 2004 Project), DuPont Fuel Cells . . . . . . . . . . . . . . . . . . . . IV-262
 

24. MEA and Stack Durability for PEM Fuel Cells (New FY 2004 Project), 3M Company . . . . IV-263
 

25. Development of a Low-Cost, Durable Membrane and Membrane Electrode 

Assembly for Stationary and Mobile Fuel Cell Applications (New FY 2004 Project), 

Atofina Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-265
 

vii 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

IV. Fuel Cells (Continued) 

F.	 Crosscutting Fuel Cell Characterization and Evaluation 

1.	 Neutron Imaging Study Of the Water Transport Mechanism in a Working Fuel Cell, 

National Institute of Standards and Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-267
 

2.	 Low-Friction Coatings and Materials for Fuel Cell Air Compressors, 

Argonne National Laboratory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-271
 

3.	 Bipolar Plate-Supported Solid Oxide Fuel Cell, Argonne National Laboratory . . . . . . . . . . IV-275
 

4.	 Assessment of Fuel Cell Auxiliary Power Systems for On-Road Transportation
 

Applications, TIAX LLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-279
 

5.	 Evaluation of Partial Oxidation Fuel Cell Reformer Emissions, TIAX LLC . . . . . . . . . . . . . IV-284
 

6.	 Modeling and Control of a Solid Oxide Fuel Cell Auxiliary Power Unit, 

Pacific Northwest National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-288
 

7.	 Montana PEM Membrane Degradation Study, Year 1 Report, CTA. . . . . . . . . . . . . . . . . . . . IV-294
 

8.	 Microstructural Characterization of PEM Fuel Cells, Oak Ridge National Laboratory . . . . IV-300
 

V.	 Technology Validation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-1
 

1.	 Validation of an Integrated System for a Hydrogen-Fueled Power Park, 

Air Products and Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-3
 

2.	 Novel Compression and Fueling Apparatus to Meet Hydrogen Vehicle Range 

Requirements, Air Products and Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-6
 

3.	 Hawaii Hydrogen Power Park, State of Hawaii Department of Business . . . . . . . . . . . . . . . . . . V-8
 

4.	 Hydrogen Power Park, DTE Energy Company. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-14
 

5.	 Power Parks System Simulation, Sandia National Laboratories . . . . . . . . . . . . . . . . . . . . . . . . V-18
 

6.	 Filling Up With Hydrogen 2000, Stuart Energy USA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-22
 

7.	 Hydrogen Refueling Technology, HyRadix, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-26
 

8.	 Fuel Cell Installation and Demonstration Project In Gallatin County, Montana,
 

Zoot Enterprises, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-30
 

9.	 Global Assessment of Hydrogen-Based Technologies, 

University of Alabama at Birmingham . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-32
 

10. Advanced Thermal Hydrogen Compression, Ergenics, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . V-36
 

11. Uninterrupted Power Source, Apollo Energy Systems, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-41
 

12. Development of a Hydrogen Fuel Based Power Park (New FY 2004 Project), 

Pinnacle West Capital Corporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-44
 

VI. Integrated Hydrogen and Fuel Cell Demonstration/Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-1
 

A.	 System Analysis 

1.	 Research and Development of a Proton Exchange Membrane Fuel Cell, Hydrogen 

Reformer, and Vehicle Refueling Facility, Air Products and Chemicals Inc. . . . . . . . . . . . . . . VI-3
 

2.	 Fuel Choice for Fuel Cell Vehicles: Stakeholder Risk Analysis, TIAX, LLC . . . . . . . . . . . . . . . VI-8
 

3.	 Hydrogen Commercialization: Transportation Fuel for the 21st Century,
 

SunLine Services Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-12
 

B.	 Demonstration 

1.	 Development of a Turnkey Commercial Hydrogen Fueling Station, 

Air Products and Chemicals, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-17
 

viii 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CONTENTS (Continued)
 

VI. Integrated Hydrogen and Fuel Cell Demonstration/Analysis 

B.	 Demonstration 

2.	 Development of a Natural Gas to Hydrogen Fuel Station, Gas Technology Institute . . . . . . VI-22
 

3.	 Fuel Cell-Powered Front-End Loader Mining Vehicle, Vehicle Projects, LLC . . . . . . . . . . . . VI-27
 

4.	 Advanced Underground Vehicle Power and Control Fuel Cell Mine Locomotive, 

Vehicle Projects, LLC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-31
 

5. UNIGEN® Regenerative Fuel Cell For Uninterruptible Power Supply,
 

Proton Energy Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-35
 

VII. Safety and Codes & Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .VII-1
 

A.	 Safety and Codes & Standards 

1.	 Codes and Standards Analysis, University of Miami. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-3
 

2.	 Hydrogen Codes and Standards, National Renewable Energy Laboratory. . . . . . . . . . . . . . . . VII-6
 

B.	 Sensors for Safety and Performance 

1.	 Carbon Monoxide Sensors For Reformate Powered Fuel Cells, 

Los Alamos National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-11
 

2.	 Electrochemical Sensors for Proton Exchange Membrane Fuel Cell Vehicles, 

Lawrence Livermore National Laboratory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-16
 

3.	 Interfacial Stability of Thin Film Sensors, National Renewable Energy Laboratory . . . . . . . VII-21
 

4.	 Development of Sensors for Automotive Fuel Cell Systems,
 

United Technologies Research Center . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VI-26
 

5.	 Micro-Machined Thin Film H2 Gas Sensors, ATMI, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-30
 

6.	 Sensor Development for Proton Exchange Membrane Fuel Cell Systems, 

Honeywell Sensing and Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-34
 

7.	 Gallium Nitride Integrated Gas/Temperature Sensors for Fuel Cell Systems, Fluence . . . . . VII-39
 

8.	 Fiber Optic Temperature Sensors for PEM Fuel Cells, Oak Ridge National Laboratory . . . . VII-42
 

9.	 Hydrogen Composite Tank Project (New FY 2004 Project), 

University of California, Irvine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-47
 

VIII. Education . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VIII-1
 

1.	 Education Program Element Planning and Multi-Year R,D&D Plan Development, 

U.S. Department of Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VIII-3
 

2.	 Baseline Knowledge Assessment, Oak Ridge National Laboratory . . . . . . . . . . . . . . . . . . . . VIII-6
 

3.	 Database of Existing Hydrogen and Fuel Cell-related Courses and Research Activities
 

at Universities, University of Tennessee . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VIII-8
 

IX. Conversion Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IX-1
 

A.	 Turbines 

1.	 Reduced Turbine Emissions Using Hydrogen-Enriched Fuels, Sandia National Laboratories . . IX-3
 

B.	 Internal Combustion Engines 

1.	 Developing a Thermodynamic Fuel Cell, Sandia National Laboratories. . . . . . . . . . . . . . . . . IX-8
 

2.	 HCNG Heavy Duty Vehicle Prime Mover, Collier Technologies, LLC . . . . . . . . . . . . . . . . . IX-13
 

X.	 Acronyms and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . X-1
 

XI. Primary Contact List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI-1
 

ix 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

x
 
 


 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

I. Introduction
 

Today, after decades of dependence on imported petroleum to fuel the United States' transportation sector, 

there is a new vision for our nation's future — a form of domestically-derived, clean energy to power not only our 

vehicles but our industries, buildings, and homes. This form of energy for the future is hydrogen. The President’s 

Hydrogen Fuel Initiative complements the FreedomCAR initiative to reverse America’s growing dependence on 

foreign oil. Together the FreedomCAR Partnership and Hydrogen Fuel Initiative support the development of 

technology needed for commercially viable hydrogen-powered fuel cells. President Bush committed $1.7 billion 

for the first five years of a long-term research and development effort for hydrogen infrastructure, fuel cells, and 

hybrid vehicle technologies. 

Hydrogen research at the U. S. Department of Energy (DOE) is National Vision being led by the Office of Energy Efficiency and Renewable 

Energy (EERE). Other DOE Offices carrying out portions of the Hydrogen is America’s clean Initiative are Fossil Energy, Nuclear Energy, and Science. Within energy choice. EERE, hydrogen and fuel cell technologies are being managed by 

Hydrogen is flexible, affordable, the Office of Hydrogen, Fuel Cells and Infrastructure 

Technologies. Hybrid and other advanced vehicle technologies are safe, domestically produced, used 

being developed within the Office of FreedomCAR and Vehicle in all sectors of the economy, and 

Technologies. in all regions of the country. 

The Hydrogen, Fuel Cells and Infrastructure Technologies 

Program funds research, development, and validation activities linked to public-private partnerships. The 

government's current role is to concentrate its funding on high-risk, applied research in the early phases of 

development. As activities progress through the stages of developing technology to validating technical 

targets, the government's cost share will diminish. The government's role as co-funder will bring technologies 

to the point where the private sector can make informed decisions on whether or not, and how best to 

commercialize these technologies, and will define any future policies to promote them. 

 Program Mission 

The mission of the Hydrogen, Fuel Cells & Infrastructure Technologies Program 

is to research, develop, and validate fuel cells and hydrogen production, delivery, 

and storage technologies for transportation and stationary applications. 

The Hydrogen, Fuel Cells and Infrastructure Technologies Program responds to recommendations in the 

President's National Energy Policy, the DOE Strategic Plan, and the National Hydrogen Energy Vision and 

Roadmap. The Program works in partnership with industry, academia, and national laboratories, and in close 

coordination with the FreedomCAR and Vehicle Technologies Program and other DOE programs, to achieve 

the four EERE strategic goals: 

• Dramatically reduce dependence on foreign oil 

• Promote the use of diverse, domestic, and sustainable energy resources 

• Reduce carbon emissions from energy production and consumption 

• Increase the reliability and efficiency of electricity generation 

This report presents a brief overview of DOE’s approach to the transition to a hydrogen economy, a 

description of the fuel cell and hydrogen research conducted by the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program in fiscal year 2003 (FY 2003), projects to be implemented in FY 2004, and the research 

priorities for FY 2004. 

I - 1 
 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

The Journey Toward a Hydrogen Economy 

The transition to a hydrogen economy can be compared to a journey to unknown places, with many 

challenges to overcome, similar to those which faced our first manned space explorations. DOE has taken the 

first step toward a hydrogen economy by developing vision, roadmap and long-term 

planning documents. The planning documents are based on the Administration’s 

National Energy Policy and include input from visionary business leaders and policy 

makers. The following is a brief description of these documents and other plans that 

support the President's Hydrogen Fuel Initiative. 

The National Energy Policy, released in May 2001, outlines a long-term strategy 

for developing and using leading-edge technology within the context of an integrated 

national energy, environmental, and economic policy. It specifically highlighted the 

potential of hydrogen with the following recommendations: 

•	 Focus research and development efforts on integrating current programs 

regarding hydrogen, fuel cells, and distributed energy. 

•	 Develop an education campaign that communicates the benefits of alternative 

forms of energy, including hydrogen. 

In November 2001, in response to recommendations within the National Energy 

Policy, DOE organized a meeting of 50 visionary business leaders and policy 

makers to formulate a National Hydrogen Vision. A National Vision of America's 

Transition to a Hydrogen Economy-to 2030 and Beyond was published in 

February 2002 following the Hydrogen Vision Meeting. This document 

summarizes the potential role for hydrogen systems in America's energy future, 

outlining the common vision of the hydrogen economy. 

In January 2002, Secretary of Energy Spencer Abraham announced the 

FreedomCAR Partnership, a cooperative research effort between DOE and USCAR, 

which is composed of DaimlerChrysler Corporation, Ford Motor Company and 

General Motors Corporation. FreedomCAR is based upon the following principles: 

1.	 Freedom from petroleum dependence 

2.	 Freedom from air pollutant and carbon dioxide emissions 

3.	 Freedom for Americans to drive where they want, when they want, in the vehicle of their choice 

4.	 Freedom to obtain fuel more affordably and conveniently 

The companies of the FreedomCAR Partnership will be at the forefront of development of vehicle 

technologies for implementation of the hydrogen economy. 

In April 2002, DOE followed up with a larger group of over 200 technical 

experts from industry, academia, and the national laboratories to develop a National 

Hydrogen Energy Roadmap. This roadmap, unveiled by Secretary Abraham in 

November 2002, describes the principal challenges to be overcome and suggests 

ways we can achieve our National Vision. To realize this vision, the Nation must 

develop and demonstrate advanced hydrogen fuel cell and infrastructure 

technologies. The Roadmap stresses the need for parallel development of model 

building codes and equipment standards to enable technology integration into 

commercial energy systems, and outreach programs to effectively educate local 

government officials and the public, who will determine the long-term acceptance of 

these technologies. 

I - 2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

In February 2003, DOE completed a draft copy of the Hydrogen Posture Plan. 

The Hydrogen Posture Plan describes how DOE will integrate its ongoing and future 

hydrogen R&D activities into a focused Hydrogen Program. It defines four phases of 

transition to a hydrogen economy (see the following subsection titled The Road to a 

Transition for detailed descriptions of each). The Hydrogen Program will integrate 

technology for hydrogen production (from fossil, nuclear, and renewable resources), 

infrastructure development (including delivery and storage), and fuel cells. Successful 

implementation of the Hydrogen Posture Plan and its activities is also critical to 

achieving the goals of the FreedomCAR Partnership. A coordinated DOE Hydrogen 

Program will improve the effectiveness and accountability of DOE’s research, 

development, and demonstration (RD&D) activities and strengthen its contribution to 

achieving the technical milestones on the road to a hydrogen economy. 

The Office of Science hosted a workshop on Hydrogen Production, Storage, and 

Use, on May 13–15, 2003, to identify fundamental research needs and opportunities 

to address the enormous gap between our present capabilities for hydrogen 

production, storage, and use, and those required for a competitive hydrogen 

economy. More than 120 scientists and engineers from academia, industry, and the 

national laboratories attended. Participants also included research leaders from 

abroad and experts from the Offices of Energy Efficiency and Renewable Energy, 

Fossil Energy, and Nuclear Energy within the U.S. Department of Energy. The 

detailed findings and research directions (http://www.sc.doe.gov/bes/hydrogen.pdf) 

address the research challenges for the hydrogen economy. The workshop report 

concludes that simple improvements of today's technologies will not meet the 

requirements. Instead, the significant technical barriers 

need to be overcome with high risk/high payoff basic research that is highly 

interdisciplinary, requiring chemistry, materials science, physics, biology, 

engineering, nanoscience, and computational science. It also calls for the seamless 

integration of basic and applied research to realize the successful transition to a 

hydrogen economy. 

The Hydrogen, Fuel Cells & Infrastructure Technologies Program Multi-Year 

Research, Development and Demonstration Plan was prepared for public review and 

released on June 3, 2003. The Plan describes the planned research, development, 

and validation activities for hydrogen and fuel cell technologies through nine key 

program components through 2010. 

Production Production of hydrogen from domestic resources minimizing environmental impacts 

Delivery Distribution of hydrogen from centralized or from distributed sites of production 

Storage Storage of hydrogen (or its precursors) on vehicles or within the distribution system 

Fuel Cells Provide primary propulsion for fuel cell vehicles, serve as auxiliary power units for 

vehicles, and provide electrical and thermal power in stationary and portable applications. 

Technology Validation Validation of systems in real-world environments 

Safety Safety assurance in DOE-sponsored R&D activities and in the hydrogen systems developed 

Codes and Standards Development of model codes and standards for domestic and international production, 

distribution, storage and utilization of hydrogen 

I - 3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Education Education of key target audiences—including teachers and students, state and local 

governments, safety and code officials, large-scale end users, and the public—about the 

hydrogen economy and how it can affect them 

Systems Integration Understanding the complex interactions between components, system costs, energy 

efficiency, environmental impacts, societal impacts and system trade-offs 

The detailed technical targets and milestones for each element are identified in the Plan. 

The Road to Transition 

Throughout the planning process, DOE has envisioned four phases in the transition to a hydrogen 

economy, each of which requires and builds on the success of its predecessor. The transition to a hydrogen 

economy will take several decades, and this transition will require strong public and private partnerships, 

commitment, and resolve. 

In Phase 1, government and private organizations will research, develop, and demonstrate "critical path" 

technologies and work to establish comprehensive safety guidelines, codes and standards prior to investing 

heavily in infrastructure. This phase is now underway, and it will enable industry to make decisions on 

commercialization by 2015. Following a positive commercialization decision, research will continue on 

advanced technologies for hydrogen production. Throughout the RD&D phase, exploratory research in 

materials sciences and engineering, chemistry, geosciences, and molecular biosciences will be carried out in 

close collaboration with the DOE Office of Science. 

Phase 2 is the Initial Market Penetration Phase. This could begin as early as 2010 using existing natural 

gas and electric grid infrastructure for applications such as portable power and some stationary and 

transportation applications, and continue as hydrogen-related technologies meet or exceed customer 

requirements. 

I - 4 
	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

As markets are established, this leads to Phase 3, or the Infrastructure Investment Phase, in which there is 

expansion of markets and infrastructure. The start of Phase 3 is dependent on a positive commercialization 

decision for fuel cell vehicles in 2015. A positive decision will attract investment in infrastructure for 

manufacturing fuel cells and for producing and distributing hydrogen. Government policies still may be 

required to nurture this infrastructure expansion phase. 

Phase 4, which could begin around 2025, is the Fully Developed Market and Infrastructure Phase. In this 

phase, consumer requirements will be met or exceeded, national benefits in terms of energy security and 

improved environmental quality will be achieved, and industry will receive adequate return on investment and 

compete globally. Phase 4 provides the transition to a full hydrogen economy by 2040. 

Progress Along the Road to Transition 

As discussed, detailed planning for the President's Hydrogen Fuel Initiative was completed during FY 

2003. The following is a brief list of accomplishments achieved: 

•	 The Office of Energy Efficiency and Renewable Energy hosted a hydrogen 

storage "Think Tank" meeting in Washington, D.C., on March 14, 2003, to 

identify new and potentially promising hydrogen storage technologies. Based on 

the Think Tank meeting, which included Nobel Prize Laureates, the DOE issued 

a "Grand Challenge" to the scientific community to solicit applications for 

research and development of hydrogen storage materials and technologies. The 

awards made from this solicitation will establish Centers of Excellence. 

•	 The Office of Fossil Energy launched FutureGen, a $1 billion, 10-year 

verification project that will build the world's first coal-based, near zeroemission electricity and hydrogen plant integrated with carbon sequestration. 

•	 The DOE sponsored a Hydrogen Delivery Workshop in Washington, DC, May 

7-8, 2003. Attendees included researchers, government officials, and industry members. This special 

workshop was held to outline the future technology and research needs for developing cost-effective, 

reliable, and safe hydrogen delivery systems. 

•	 On June 2-3, 2003, DOE held a Hydrogen and Fuel Cells Coordination Meeting to facilitate 

communication and coordination among the DOE programs with key roles in achieving the goals of the 

President's FreedomCAR and Hydrogen Fuel Initiative. The meeting was attended by invited participants 

from programs in DOE's Offices of Energy Efficiency and Renewable Energy, Fossil Energy, Nuclear 

Energy, Science and Technology, Science, and the Office of Management, Budget and Evaluation. 

•	 The world's first hydrogen and electricity co-production facility opened in Las Vegas, Nevada, in 

November 2002. The facility (built by Air Products and Chemicals, Inc., in partnership with Plug Power 

Inc., the DOE, and the City of Las Vegas) will serve as a 

"learning" demonstration of hydrogen as a safe and clean 

energy alternative for vehicle refueling. The facility includes 

small-scale, on-site hydrogen production technologies, a 

hydrogen/compressed natural gas blend refueling facility, 

and a 50-kW PEM fuel cell system that supplies electricity 

to the grid. 

•	 The Office of Energy Efficiency and Renewable Energy 

released a hydrogen production and delivery technologies 

solicitation which includes the following topics: biomass 

gasification and pyrolysis; photolytic processes; 

distributed natural gas reforming technologies; separation 

and purification technologies; advanced electrolysis 

I - 5 

World's First Hydrogen and Electricity 

Co-Production Facility 
 

 

 

 


 


 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

systems; high temperature Stationary/Transportation Awards Announced 

thermochemical water splitting; July 14, 2003 

hydrogen production infrastructure
 

analysis; and advanced hydrogen 

delivery technologies. Pre-proposals 

have been received with proposals due 

in FY 2004.
 

•	 Hosted workshop for education and 

industry experts to launch a new 

education program element, December 4-

5, 2002. 

•	 The Office of Energy Efficiency and 

Renewable Energy issued a solicitation 

for the testing, demonstration, and 

validation of hydrogen fuel cell vehicles 

and infrastructure, and the required 

vehicle and infrastructure interfaces for 

complete system solutions. The awards 

will be cost-shared, and each will include 

a comprehensive safety plan; a program 

that enhances the development of codes 

and standards; and a comprehensive, 

integrated education and training 

campaign. Awards will be made in FY 

2004, and each will be 5 years in length. 

•	 The FreedomCAR Partnership was 

expanded to include energy companies to 

focus on hydrogen infrastructure challenges. 

Company Project Technology 

3M Company MEA and Stack Durability 

IdaTech LLC Stationary Fuel Cell Power System 

UTC Fuel Cells LLC Stationary Fuel Cell Power System 

& Demo 

Plug Power, Inc. Back-up/Peak Shaving Fuel Cells 

Atofina Chemicals, Inc. Low Cost, Durable Membranes 

DuPont MEA Durability 

Plug Power, Inc. High Temperature Membranes 

Texaco Energy Systems Fuel Cell Fuel Processor 

Honeywell International Inc. Thermal and Water Management 

Engelhard Corporation Platinum Recycling 

Ion Power, Inc. Platinum Recycling 

3M Company Non-Precious Metal Catalysts 

Ballard Power Systems Non-Precious Metal Catalysts 

Corp. 

University of South Carolina Non-Precious Metal Catalysts 

Battelle Memorial Institute Economic Analysis 

•	 On March 21-22, 2003, DOE sponsored the Non-Platinum Electrocatalyst Workshop to review and 

identify potential new candidate electrocatalysts that are non-platinum (and non-precious metal). Fiftyfive representatives from universities, government agencies, national laboratories, and private industry 

attended the two-day workshop, held in New Orleans, Louisiana. 

•	 Safety guidelines for DOE Hydrogen Program projects were drafted. 

•	 The Office of Energy Efficiency and Renewable Energy Launched a hydrogen education "campaign" as 

recommended in the President's National Energy Policy. 

A solicitation was released with proposals due in the beginning of FY 2004. 

•	 Initiated a review by The National Academies of DOE's hydrogen research, development, and 

demonstration (RD&D) program. An interim letter report was received April 3, 2003, which provides 

some early feedback and recommendations. A final report is anticipated in FY 2004. 

•	 Energy Efficiency and Renewable Energy conducted a merit review and peer evaluation of all the projects 

in the Hydrogen, Fuel Cells and Infrastructure Technologies Program. The results of this meeting will be 

used to guide research activities during FY 2004. 

•	 DOE Awarded a total of $96 million in 24 new awards in support of the President's FreedomCAR and 

Hydrogen Fuel Initiative. These new projects include research in advanced fuel cell technology for vehicles, 

buildings and other applications. In particular, the projects on hydrogen storage technologies support DOE's 

priority to develop methods to safely store hydrogen to enable at least a 300 mile vehicle range—a critical 

requirement for successful vehicle commercialization. The recipients of these awards have pledged an 

additional $40 million in cost sharing, bringing the total value of these projects to $136 million. 

I - 6 
 

 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Plans for Progress Along the Road to Transition 

The following are the FY 2004 priorities for the FreedomCAR and Hydrogen Fuel Initiative: 

•	 Establish the International Partnership for a Hydrogen Economy (IPHE). The objective of the IPHE is to 

efficiently organize, evaluate and coordinate multinational research, development and deployment 

programs that advance the transition to a global hydrogen economy. 

•	 Establish a fully integrated DOE Hydrogen Program to efficiently manage all DOE hydrogen and fuel cell 

research and include an innovative systems integration capability to cost effectively execute all aspects of 

the President's Hydrogen Fuel Initiative. 

•	 Finalize and publish the 5-year hydrogen RD&D plans of the Offices of Energy Efficiency and Renewable 

Energy, Fossil Energy, and Nuclear Energy based on the peer review by The National Academies. 

•	 Conduct an integrated DOE Hydrogen Program merit review and peer evaluation meeting including the 

Offices of Energy Efficiency and Renewable Energy, Fossil Energy, Nuclear Energy, and Science. 

•	 Establish three to four Hydrogen Storage Centers of Excellence led by DOE national laboratories including 

universities, industry, and/or other federal/national laboratories as partners to address the very pressing needs 

to improve hydrogen storage so that fuel cell vehicles with 300 mile range can become a practical reality. 

•	 Issue solicitation for hydrogen production from coal and award projects. 

•	 Initiate a national Hydrogen Vehicle and Infrastructure Validation Project with three to six consortia (auto/ 

fuel/ supplier teams) to test vehicles and Hydrogen Storage/Sensors Awards infrastructure. Data from these "learning" July 14, 2003 demonstrations will provide feedback to the 

research program. 

•	 Establish an expert panel to analyze the 

merits of whether to continue development 

of on-board fuel processors to reform 

gasoline and alternative fuels such as 

methanol, ethanol, and natural gas to 

produce hydrogen on-board the vehicle. 

•	 Initiate high efficiency polymer electrolyte 

membrane stationary fuel cell power 

system projects that will advance and 

demonstrate the use of fuel cells as an 

alternative power source to grid-based 

electricity for buildings. 

•	 Select up to 32 projects to receive up to $80 

million of federal funding for development 

of hydrogen production and delivery 

technologies. 

Company Project Technology 

Air Products & Chemicals, Inc. 

Cleveland State University 

Intelligent Optical Systems, Inc. 

Iowa State University 

Millennium Cell, Inc. 

Nanomix, Inc. 

QUANTUM Technologies, Inc. 

Safe Hydrogen, LLC 

United Technologies Research Center 

University of California, Irvine 

UOP, LLC 

Hydrogen Storage 

Hydrogen Storage 

Sensors 

Hydrogen Production 

Hydrogen Storage 

Hydrogen Storage 

Hydrogen Storage 

Hydrogen Storage 

Hydrogen Storage 

Sensors 

Hydrogen Storage 

•	 Establish and implement a data 

management plan for the DOE Hydrogen Program. 

•	 Conduct and report on baseline assessment of key target audiences' understanding of hydrogen economy. 

•	 Launch first phase of long-term education strategy by creating hydrogen information clearinghouse to 

serve multiple audiences and initiating specific education activities focused on teachers and students and 

state and local governments. 

•	 Conduct a scoping study for a Programmatic Environmental Impact Statement. 

•	 Initiate worldwide commitment for global hydrogen codes and standards as part of on-going IPHE activities. 

•	 Launch the Office of Nuclear Energy Hydrogen Initiative which will demonstrate the economic 

commercial-scale production of hydrogen using nuclear energy by 2015. 

I - 7 
 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Continue efforts to establish closer relationships with the states through the DOE Regional Offices to 

execute hydrogen and fuel cell RD&D, especially in the areas of education and codes/standards. 

The National Academies Review 

The DOE asked The National Academies in December 2002 to evaluate the cost and status of technologies 

for production, transportation, storage, and end-use of hydrogen and to review DOE's hydrogen research, 

development, and deployment (RD&D) strategy. On April 4, 2003, The National Academies submitted their 

interim report offering four recommendations in the following areas: 

•	 Safety: The Committee recommended that DOE make significant efforts to address safety issues. 

•	 Systems Integration and Analyses: The National Academies recommended that R&D successes & failures 

be analyzed and modeled both as individual technologies and as components of a greater system. 

•	 Exploratory Research: The Committee encouraged DOE to continue funding fundamental, exploratory 

research for promising, high-risk new technologies. 

•	 Organization: The Committee supports the DOE in its efforts to integrate various hydrogen-related RD&D 

programs, the Office of Science, and the private sector. 

A final report will be submitted during FY 2004. FreedomCAR and the Hydrogen Fuel Initiative are 

focused on bringing about significant changes to how the country develops and uses its energy resources. The 

DOE is highly interested in the findings and recommendations of The National Academies so that we can 

guide the program in a way that achieves the best results for the country. Find more information at 

www.nas.edu under BEES-J-02-04-A. 

Technical Challenges and Mileposts Along the Road to Transition 

The EERE Hydrogen, Fuel Cells and Infrastructure 

Technologies Program has set goals and targets for each 

of its technical areas. The "core" activities are hydrogen 

production, delivery, and storage; fuel cell development; 

and validation technology. Cross-cutting activities of 

systems integration/analysis, safety, codes and standards, 

and education are performed in parallel with the 

technology research and development activities. 

Following are brief descriptions of the status of these 

Program activities, the goal for each, pertinent technical 

targets, current status, and anticipated FY 2004 accomplishments. 

Hydrogen Production 

Goal: Research and develop low-cost, highly efficient hydrogen production technologies from diverse, 

domestic sources, including fossil, nuclear, and renewable sources. 

Objectives 

•	 By 2010, reduce the cost of distributed production of hydrogen from natural gas and/or liquid fuels to 

$1.50/kg (delivered, untaxed) at the pump (without carbon sequestration). 

I - 8 
 

 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 By 2010, develop and demonstrate technology to supply purified hydrogen (purity sufficient for PEM fuel 

cells) from biomass at $2.60/kg at the plant gate (projected to a commercial scale 75,000 kg/day).1 The 

objective is to be competitive with gasoline by 2015. 

•	 Develop advanced renewable photolytic hydrogen generation technologies. By 2015, demonstrate an 

engineering-scale biological system that produces hydrogen at a plant-gate cost of $10/kg projected to 

commercial scale. By 2015, demonstrate direct photoelectrochemical water splitting with a plant-gate 

hydrogen production cost of $5/kg projected to commercial scale. The long-term objective for these 

production routes is to be competitive with gasoline. 

•	 By 2010, verify renewable integrated hydrogen production with water electrolysis at a hydrogen cost of 

$2.50/kg (electrolyzer capital cost of $300/kWe for 250 kg/day at 5,000 psi with 73% system efficiency). 

By 2010, verify large-scale central electrolysis at $2.00/kg hydrogen at the plant gate. 

•	 By 2015, research and develop high- and ultra-high-temperature thermochemical/electrical processes to 

convert hydrogen from high temperature heat sources (nuclear or solar) with a projected cost competitive 

with gasoline.2 

•	 Evaluate other new technologies that have the potential for cost-effective sustainable production of 

hydrogen and fund appropriate research and development (R&D) in promising areas. 

FY 2003 Status 

•	 Cost of distributed production of hydrogen from natural gas: $5.00/kg 

•	 Cost of centralized production of hydrogen from biomass: $4.00/kg (at the plant gate) 

Anticipated FY 2004 Accomplishments 

•	 Complete research to enable distributed natural gas reforming technologies delivering 5,000 psi hydrogen 

at $3.00/kg hydrogen – progress toward achieving 2010 goal of $1.50/kg. 

•	 Accelerate and expand research to reduce the cost of electrolysis for hydrogen production, including high 

temperature steam electrolysis, and complete an analysis and research on central, integrated, wind-based 

electrolysis. 

•	 Initiate a geothermal-based electrolysis feasibility study. 

•	 Accelerate and expand research on the production of hydrogen from renewable resources, including 

biomass gasification/pyrolysis, photobiological and photoelectrochemical production. 

•	 Initiate research on high temperature thermochemical water splitting for hydrogen production. 

•	 Complete a comprehensive techno-economic analysis of the major production options for hydrogen on a 

consistent and comparable basis. 

Hydrogen Delivery 

Goal: Develop hydrogen fuel delivery technologies that enable the introduction and long-term viability of 

hydrogen as an energy carrier for transportation and stationary power. 

Objectives 

•	 By 2006, define a cost-effective and energy-efficient hydrogen fuel delivery infrastructure for the 

introduction and long-term use of hydrogen for transportation and stationary power. 

•	 By 2010, develop enabling technologies to reduce the cost of hydrogen fuel delivery from central and 

semi-central production facilities to the gate of refueling stations and other end users to <$0.70/kg. 

•	 By 2010, develop enabling technologies to reduce the cost of moving and handling hydrogen within 

refueling stations and stationary power facilities to a vehicle or stationary power unit to <$0.60/kg. 

1.	 Collaboration with the U.S. Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy 

(EERE) Biomass Program. Offsets for coproducts not included. 

2.	 Collaboration with DOE’s Office of Nuclear Energy. 

I - 9 
 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 By 2015, develop enabling technologies to reduce the cost of hydrogen fuel delivery from the point of 

production to the point of use in vehicles or stationary power units to <$1.00/kg in total. 

FY 2003 Status 

•	 Cost of gaseous hydrogen compression: $0.18/kg; efficiency of 90% 

•	 Cost of hydrogen liquefaction: $1.11/kg; efficiency of 65% 

•	 Cost of hydrogen trunk pipelines: $1.4 million/mile 

•	 Cost of hydrogen distribution lines: $600,000/mile 

•	 Hydrogen carrier storage capacity: 3 wt.%; efficiency of 80% 

Anticipated FY 2004 Accomplishments 

•	 Define and initiate a comprehensive analysis of hydrogen delivery technology and infrastructure options 

and trade-offs. 

•	 Initiate research projects on hydrogen delivery to support the 2005 and 2010 delivery targets, including 

lower cost pipelines, compression and liquefaction technology and novel solid and liquid carrier systems. 

Hydrogen Storage 

Goal: Develop and demonstrate viable hydrogen storage technologies for transportation and stationary 

applications. 

Objectives 

•	 By 2005, develop and verify on-board hydrogen storage systems achieving 1.5 kWh/kg (4.5 wt%), 1.2 

kWh/L, and $6/kWh. 

•	 By 2010, develop and verify on-board hydrogen storage systems achieving 2 k Wh/kg (6 wt%), 1.5 kWh/ 

L, and $4/kWh. 

•	 By 2015, develop and verify on-board hydrogen storage systems achieving 3k Wh/kg (9 wt%), 2.7 kWh/L, 

and $2/kWh. 

•	 By 2015, develop and verify low-cost, off-board hydrogen storage systems, as required for hydrogen 

infrastructure needs to support transportation, stationary and portable power markets. 

FY 2003 Status 

•	 For 10,000 psi tanks: Achieved factor of 10 improvement in cycle life and demonstrated 3-minute fill time. 

•	 For solid state materials: Achieved factor of 10 improvement in kinetics of sodium alanate and identified 

potential pathway to increased storage capacity 

Anticipated FY 2004 Accomplishments 

•	 Demonstrate 10,000 psi tanks achieving 2005 targets of 1.5 kWh/kg and 1.2 kWh/L. 

•	 Complete construction of independent test facility for reversible solid-state storage materials. 

Fuel Cells 

Goal: Develop and demonstrate fuel cell power system technologies for transportation, stationary, and 

portable applications. 

Objectives 

•	 Develop a 60% efficient, durable, direct hydrogen fuel cell power system for transportation at a cost of 

$45/kW (including hydrogen storage) by 2010 and $30/kW by 2015. 

•	 Develop a 45% efficient reformer-based fuel cell power system for transportation operating on clean 

hydrocarbon or alcohol-based fuel that meets emissions standards, a startup time of 30 seconds, and a 

projected manufactured cost of $45/kW by 2010 and $30/kW by 2015. 

I - 10 
	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Develop a distributed generation PEM fuel cell system operating on natural gas or propane that achieves 

40% electrical efficiency and 40,000 hours durability at $400-$750/kW by 2010. 

•	 Develop a fuel cell system for consumer electronics with an energy density of 1,000 Wh/L by 2010. 

•	 Develop a fuel cell system for auxiliary power units (3-30/kW) with a specific power of 150 W/kg and a 

power density of 170 W/L by 2010. 

FY 2003 Status 

•	 Current cost of vehicle fuel cell power systems: $250/kW (at 500,000 units per year) 

Anticipated FY 2004 Accomplishments 

•	 Reduce costs through demonstration of bipolar plate pilot plant production rate of 300 plates/hour. 

•	 Reduce on-board fuel processor start-up time to <1 min. through auto-thermal technology. 

•	 Define requirements and initiate economic analysis/study of stationary fuel cells and their associated 

markets. 

Technology Validation 

Goal: Validate integrated hydrogen and fuel cell technologies for transportation, infrastructure, and electric 

generation in a systems context under real-world operating conditions. 

Objectives 

•	 By 2008, validate an electrolyzer that is powered by a wind turbine at a capital cost of $300/kWe when 

built in quantity. 

•	 By 2008, validate hydrogen vehicles which have greater than a 300-mile range, 2,000-hour fuel cell 

durability, and $3.00/kg hydrogen production cost (untaxed), and which can be safely and conveniently 

refueled by trained drivers. 

•	 By 2008, validate stationary fuel cell and hydrogen internal combustion engine (ICE) systems that 

coproduce hydrogen and electricity from nonrenewable and renewable resources, with a 30,000-hour 

durability, greater than 32% efficiency, and a price of $1,250/kW or less (for volume production). 

•	 By 2010, validate an integrated biomass/wind or geothermal electrolyzer-to-hydrogen system to produce 

hydrogen for $3.30/kg at the plant gate (untaxed and unpressurized). 

•	 By 2015, validate hydrogen PEM fuel cell vehicles achieving 300+ mile range and 5,000 hours fuel cell 

system durability, and which can be safely and conveniently refueled by trained drivers. 

FY 2003 Status 

•	 Cost of hydrogen production from natural gas: $5.00/kg 

•	 Fuel cell durability in a systems context of 1,000 hours 

Anticipated FY 2004 Accomplishments 

•	 Validate $3.60/kg hydrogen from natural gas when co-production of electricity is included 

•	 Initiate “learning” demonstrations that emphasize and integrate hydrogen infrastructure and hydrogen 

powered vehicles to validate technology status and focus future R&D directions. 

Codes and Standards 

Goal: Facilitate the creation and adoption of model building codes and equipment standards for hydrogen 

systems in commercial, residential, and transportation applications. Provide technical resources to harmonize 

the development of international standards among the International Electrotechnical Commission (IEC), the 

International Organization for Standardization (ISO), and the Global Regulation on Pollution and Energy 

(GRPE) Program. 

I - 11 
 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Objectives 

•	 Complete the drafting of hydrogen building codes for the National Fire Protection Association’s (NFPA’s) 

hearing cycle. 

•	 By 2005, facilitate the adoption of the International Code Council (ICC) codes in three key regions: 

Northeast, Mid-Atlantic, and Midwest. 

•	 By 2006, support and facilitate the completion and adoption of the ISO standards for hydrogen refueling 

and storage. 

•	 By 2008, support and facilitate the completion and adoption of the revised NFPA 55 standard for hydrogen 

storage with data from the technology validation program element activities and the experimental project 

for underground bulk storage of hydrogen. 

•	 By 2010, support and facilitate U.S. adoption of a Global Technical Regulation (GTR) for hydrogen fuel cell 

vehicles under the United Nations Economic Commission for Europe World Forum for Harmonization of 

Vehicle Regulations Working Party on Pollution and Energy under the GRPE program (ECE-WP29/GRPE). 

FY 2003 Status 

•	 Developed a plan for international safety standards (currently under review) 

Anticipated FY 2004 Accomplishments 

•	 Collaborate with ICC and NFPA to develop first-order continuing education for code officials. 

•	 Establish a coordination plan with education sub-program activity to run workshops for state and local officials. 

•	 Initiate negotiations with critical standards development organizations and develop draft generic licensing 

agreement and estimate of costs. 

Safety 

Goal: Develop and implement the practices and procedures that will ensure safety in the operation, 

handling, and use of hydrogen and hydrogen systems for all DOE-funded projects. 

Objectives 

•	 Draft a comprehensive safety plan to be completed in collaboration with industry. The plan will initiate the 

research necessary to fill safety information gaps and enable the formation of a Safety Review Panel by 2004. 

•	 Integrate safety procedures into all DOE project funding procurements. This will ensure that all projects 

that involve the production, handling, storage, and use of hydrogen incorporate project safety requirements 

into the procurements by 2005. 

•	 Publish a handbook of Best Management Practices for Safety by 2010. The Handbook will be a “living” 

document that will provide guidance for ensuring safety in future hydrogen endeavors. 

FY 2003 Status 

•	 Completed draft safety guidelines to be used by all DOE Hydrogen Program projects 

•	 Anticipated FY 2004 Accomplishments 

•	 Assemble panel of experts in hydrogen safety to provide expert technical guidance to funded projects. 

•	 Develop in collaboration with NASA, the U.S. Department of Transportation, and the U.S. Department of 

Commerce, a search protocol on component and system safety. 

•	 Identify areas of additional study and research for failure modes scenarios. 

•	 Establish annual review criteria for safety. 

Education 

Goal: Educate key audiences about fuel cell and hydrogen systems to facilitate commercialization and 

market acceptance of these technologies. 

I - 12 
	 

	 

	 

	 

	 

	 

	 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Objectives 

By 2010 – 

•	 Achieve a fourfold increase in the number of students and teachers who understand the concept of a 

hydrogen economy and how it may affect them. 

•	 Achieve a fourfold increase in the number of state and local government representatives who understand 

the concept of a hydrogen economy and how it may affect them. 

•	 Achieve a twofold increase in the number of large-scale end-users who understand the concept of a 

hydrogen economy and how it may affect them. 

•	 Launch a comprehensive and coordinated public education campaign about the hydrogen economy and 

fuel cell technology. 

FY 2003 Status 

•	 Developed a comprehensive, long-term plan to educate multiple audiences. 

Anticipated FY 2004 Accomplishments 

•	 Launch new middle school and high school hydrogen technology curricula and teacher professional 

development program. 

•	 Initiate series of hydrogen technology learning workshops for state and local governments. 

Hydrogen, Fuel Cells, and Infrastructure Technologies Program Management 

This report documents the progress made by the DOE Hydrogen, Fuel Cells, and Infrastructure Technologies 

Program during FY 2003. The following sections of the report contain 161 individual progress reports of projects 

currently being conducted or newly initiated. These reports provide technical details on the progress being made 

to achieve the goals and technical targets of the Hydrogen, Fuel Cells and Infrastructure Technologies Program. 

The following organization chart shows its management structure, and the list of Technology Development 

Managers provides contact information and shows management responsibilities. 

I - 13 
 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Production Team 

Pete Devlin $ Team Leader, Hydrogen Production 

(202) 586-4905 $ Overall Hydrogen Production R&D 

Peter.Devlin@ee.doe.gov $ FreedomCAR and Fuel Partnership Hydrogen Production 

Technical Team 

Roxanne Danz 

(202) 586-7260 

Roxanne.Danz@ee.doe.gov 

$ Hydrogen Production with biomass feedstock and direct 

water splitting using photolytic processes 

$ NAS coordination 

Chris Bordeaux $ Integrated Power Parks 

(202) 586-3070 $ Uninterruptible Power Systems 

Christopher.Bordeaux@ee.doe.gov $ H2 Infrastructure Validation 

$ California Fuel Cell Partnership 

$ International Partnership for H2 Economy (IPHE) 

Matt Kauffman 

(202) 586-5824 

Matthew.Kauffman@ee.doe.gov 

$ Cross-cutting Analyses 

$ Electrolysis and Electricity Infrastructure Integration 

Arlene Anderson 

(202) 586-3818 

Arlene.Anderson@ee.doe.gov 

$ Distributed H2 Production (Natural Gas, Petroleum 

Feedstocks) 

$ Coordinate with Fossil Energy on Coal-Based H2 Production 

(Board of Directors, Pittsburgh Coal Conference) 

$ Multi-Year R,D&D Plan Development (lead) 

$ Platinum Mining & Recovery 

Mark Paster $ FreedomCAR and Fuel Partnership Hydrogen Delivery 

(202) 586-2821 Technical Team 

Mark.Paster@ee.doe.gov $ Overall Feedstock/Production/Delivery Strategy and Analysis 

$ High Temperature Thermochemical Water Splitting for H2 

Production 

Cross-Cutting Functions 

Sig Gronich 

(202) 586-1623 

Sigmund.Gronich@ee.doe.gov 

$ Manager, Technology Validation 

$Overall Technology Validations for Transportation and 

Stationary Applications 

Neil Rossmeissl 

(202) 586-8668 

Neil.Rossmeissl@hq.doe.gov 

$ Manager, H2 Safety, Codes & Standards and Utilization 

$ Hydrogen Technical Advisory Panel 

$ IEA H2 Implementing Agreement Executive Committee 

Christy Cooper 

(202) 586-1885 

christy.cooper@ee.doe.gov 

$ Manager, Hydrogen Education 

$ California Fuel Cell Partnership Communications Team 

$ NextEnergy Educational Working Group 

I - 14 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Storage Team 

JoAnn Milliken $Team Leader, Hydrogen Storage 

(202) 586-2480 $ Hydrogen Storage Budget 

JoAnn.Milliken@ee.doe.gov $ FreedomCAR and Fuel Partnership Hydrogen Storage 

Technical Team 

$ International Hydrogen Storage Activities 

$ BES Liaison 

Lucito Cataquiz 

(202) 586-0729 

Lucito.Cataquiz@ee.doe.gov 

$ Support Service COTR 

$ Costing/Financial Status Reports 

Carole Read $ Metal Hydride Storage Materials 

(202) 586-3152 $ New Materials for Hydrogen Storage 

Carole.Read@ee.doe.gov $ Alanate Working Group 

$ Education Liaison 

Sunita Satyapal $ Carbon-Based Storage Materials 

(202) 586-2336 $ Carbon W orking Group 

sunita.satyapal@ee.doe.gov $ Chemical Hydrogen Storage Materials 

$ Safety Liaison 

$ Fuel Cell Seminar Organizing Committee 

Antonio Bouza 

(202) 586-4563 

antonio.bouza@ee.doe.gov 

$ Compressed and Liquid Hydrogen Storage 

$ Testing and Analysis 

$ Delivery Liaison 

$ Technology Validation Liaison 

$ International Hydrogen Infrastructure Group (IHIG) 

Fuel Cell Team 

Pat Davis 

(202) 586-8061 

Patrick.Davis@ee.doe.gov 

$ Team Leader, Fuel Cell 

$ Overall Fuel Cell Systems 

$ FreedomCAR and Fuel Partnership Fuel Cell Technical Team 

Kathi Epping 

(202) 586-7425 

Kathi.Epping@ee.doe.gov 

$ Stationary Fuel Cells System Development & Demonstration 

$ Back-up power/peak shaving fuel cell systems 

$ Fuel Cell Economic Analysis 

John Garbak $ Fuel Cell Vehicle Demonstration 

(202) 586-1723 $ Liaison with 21st Century Truck 

John.Garbak@ee.doe.gov $ Fuel Cells for APUs, portable power, and off-road application 

$ Compressors/Expanders 

Nancy Garland 

(202) 586-5673 

Nancy.Garland@ee.doe.gov 

$ National Lab Fuel Cell R&D 

$ Sensors 

$ Cost Analyses 

Donna Ho 

(202) 586-8000 

Donna.Ho@ee.doe.gov 

$ Transportation Fuel Cells 

$ Bipolar Plates 

$ SBIR Program 

Valri Lightner $ Fuel Processing 

(202) 586-0937 $ MEA R&D 

Valri.Lightner@ee.doe.gov $ Budget Coordination 

$ Intra-agency Coordination 

I - 15 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Updated Website 

The website for the Hydrogen, Fuel Cells, and Infrastructure Technologies Program has been updated and 

expanded to include not only Program information, but information about hydrogen and hydrogen fuel cell 

vehicles in general. 

The photograph on the next page was taken at the October 8, 2003 DOE program management meeting 

and includes managers from the Offices of Nuclear Energy (NE), Fossil Energy (FE), Science (SC), and 

Energy Efficiency and Renewable Energy (EERE), and personnel providing critical support to the program. 

The Hydrogen Program Merit Review and Peer Evaluation Meeting will be held May 24-27, 2004, in 

Philadelphia. We hope that you will join us there. 

Steven G. Chalk, Hydrogen Program Manager 

Office of Hydrogen, Fuel Cells, and Infrastructure Technologies 

Energy Efficiency and Renewable Energy 

I - 16 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

The Hydrogen Program Team: 1. John Petrovic (LANL); 2. Neil Rossmeissl (EERE); 3. Mark Paster 

(EERE); 4. Tia Alexander (EERE); 5. John Houghton (SC); 6. Ed Schmetz (FE); 7. Valri Lightner (EERE); 

8. Tony Bouza (EERE); 9. David Henderson (NE); 10. Michael Shapiro (TMS); 11. Patrick Davis (EERE); 

12. Art Hartstein (FE); 13. Carole Read (EERE); 14. John Garbak (EERE); 15. Lauren Inouye (Sentech); 

16. Amy Taylor (NE); 17. Steve Chalk (EERE); 18. Lucito Cataquiz (EERE); 19. Roxanne Danz (EERE); 

20. Nancy Garland (EERE); 21. Pete Devlin (EERE); 22. Sunita Satyapal (EERE); 23. Christy Cooper 

(EERE); 24. Donna Ho (EERE); 25. Rich Bechtold (QSS); 26. Bill Cleary (ANL); 27. Larry Blair 

(Consultant); 28. Chris Bordeaux (EERE); 29. Matt Kauffman (EERE); 30. Barbara Wolfe (QSS); 

31. Reeshemiah Schuler (CSMI); 32. Arlene Anderson (EERE); 33. Lowell Miller (FE); 34. Harriet Kung 

(SC); 35. Melissa Lott (QSS); 36. Marsha Quinn (EERE); 37. Kristen Rannels (Sentech); 38. Sigmund 

Gronich (EERE); 39. JoAnn Milliken (EERE); 40. Bobi Garrett (NREL); 41. Kathi Epping (EERE); 

42. Tom Morehouse (ETM Strategic Consulting); 43. Peter Alyanakian (DOE Philadelphia Regional Office) 

I - 17 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

I - 18
 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Novel Catalytic Fuel Reforming 

Patricia Irving (Primary Contact), Quentin Ming, and Andrew Lee 

InnovaTek Inc. 

350 Hills Street, Suite 104 

Richland, WA 99352 

Phone: (509) 375-1093; Fax: (509) 375-5183; E-mail: irving@tekkie.com 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Objectives 

The ultimate goal of this research project is to develop technology that will produce pure hydrogen from 

natural gas and logistical fuels using catalytic steam reforming and membrane hydrogen separation. 

Phase III is intended to advance the state of InnovaGenTM fuel processing technology to the point of alpha 

readiness. This means that the fundamental design of key subsystems will evolve to include: 

• Mature configurations (geometry and component placement defined) 

• Material specifications 

• Value engineering, design for manufacturability 

• Reliability engineering and modeling. 

Phase III includes considerable research, engineering, analysis, design and testing efforts. The result of 

these efforts will be prototypes capable of successfully completing a multi-unit test program representative 

of specified operating conditions. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Fuel Cells 

• J. Durability 

• L Hydrogen Purification/Carbon Monoxide Cleanup 

• M. Fuel Processor System Integration and Efficiency 

Production 

• A. Fuel Processor Capital Costs 

Approach 

• Conduct system analyses and generate design specifications. 

• Design and fabricate components. 

• Test components. 

• Design process configurations. 

• Evaluate configurations with model simulation. 

• Predict component and operational requirements with model simulation. 

• Conduct iterative testing of integrated system. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Concluded testing of the Phase II 1-kW diesel fuel processor platform. 

•	 Concluded testing of the sulfur tolerance of a 100-W palladium/copper (Pd/Cu) membrane assembly. 

•	 Concluded long-term catalyst testing for natural gas reforming. 

•	 Disassembled and inspected 100-W membrane module after testing. 

•	 Disassembled and inspected 1-kW fuel processor after testing. 

•	 Developed new reactor and burner design concepts. Developed a prototype micro-channel cross-flow 

combustor. 

•	 Developed membrane module design concepts. Designed and procured components for a membrane/ 

coupon test fixture. 

•	 Developed improvements to the fuel injector design. Generated an injector nozzle test program. 

Proceeded with the specification and procurement of equipment for testing the fuel injector and mixer. 

•	 Continued work on heat exchanger design concepts. Established final requirements for heat
 

exchangers.
 

•	 Finalized system operating and design parameters. 

Future Directions 

•	 Increase system efficiency and reduce system size and weight. 

•	 Further develop hydrogen purification module. 

•	 Improve system packaging. 

•	 Scale up design to at least 60 LPM hydrogen output; enough for a 5-kWe fuel cell. 

•	 Complete micro-channel implementation. 

•	 Automate start-up, operation, and shut-down. 

•	 Perform more complete thermal integration. 

•	 Focus on manufacturability, cost reduction and high-volume production. 

•	 Fully integrate with at least one fuel cell model. 

•	 Thoroughly test reliability. 

•	 Enhance controls - off-site monitoring, data mining, self-diagnostics. 

•	 Complete documentation - drawings, bills of material, manufacturing routers. 

Introduction 

To be marketable now, fuel cells need to use 

primary fuel sources from existing production and 

distribution networks - i.e. natural gas, gasoline, 

diesel or jet fuels. Fossil fuel-powered fuel cells or 

refueling stations can form the bridge to a future 

when renewable resources power fuel cells. When 

compared to compressed hydrogen, reformed 

hydrocarbon fuels offer a significant cost advantage 

in the delivery of power. The high energy density of 

these fuels will also contribute to increased run times 

per unit of fuel consumed, and size and weight 

reductions associated with fuel storage. 

To meet this need, InnovaTek is integrating 

microreactor technology with advanced sulfur-tolerant 

catalysts and hydrogen membrane technology to 

create a fuel processor for hydrogen generation. The 

ultimate goal of this cooperative project is the 

development of a catalytic reactor heated by the 

combustion of membrane by-products (raffinate) for 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

the production of clean hydrogen by steam reforming 

hydrocarbon fuels. Advanced membrane technology 

is being used to remove CO and CO2 from the 

reformate. The fuel processor being developed will 

provide a pure output stream of hydrogen that can be 

used without further purification for electrical 

generation by a PEM fuel cell. 

Approach 

The ultimate goal of this research program is to 

develop fuel processing technology that makes it 

possible for fuel cells to replace internal combustion 

engines as the power source for electrical generators 

and auxiliary power units in the 1-5 kW range. The 

fuel processor developed will produce pure hydrogen 

from fuels using cost-competitive, highly efficient 

catalytic steam reforming and membrane separation 

technology. 

The design and optimization of a fuel processing 

system is complex because of the number of required 

components and functions (Table 1). 

The following objectives (broken down by key 

subsystems) were identified to achieve our goal. 

Overall System Modeling, Analysis and Design 

•	 update model (optimize efficiency, provide 

design parameters) 

•	 generate and maintain process and 

instrumentation diagram (P&ID) (revision 

control and distribution) 

Table 1. Primary Components of InnovaTek's Fuel Processor 

Reformer 

•	 burner (convert to diesel start-up) 

•	 vaporizer and superheater (micro-channel 

alternatives, integration into reactor) 

•	 catalysts (sulfur tolerance, deposition, 

reforming temperature reduction) 

•	 reformate condensate (recycling, 

evaporation, disposal) 

•	 reactor design (micro-channel 

implementation, catalyst deposition, 

manufacturability) 

Fuel Injector 

•	 mixer (develop next generation diesel 

injector, steam mixer) 

Membrane H2 Purifier 

•	 research contamination causes (investigate 

Zn, Cd and other contaminants) 

•	 membrane material selection (optimize 

material form and composition) 

•	 membrane module design (optimize design 

of membrane module) 

•	 thermal integration (eliminate external 

heating) 

Thermal Management 

•	 condensate cooling/condensing (cooling 

system design, efficiency improvements) 

•	 other heat exchangers (micro-channel 

alternatives, integration into the reactor) 

Component Function Product

Catalytic Reactor Catalytically reforms fossil fuel Reformate (H2, CO2, CO) 

Catalyst Catalyzes the reforming reaction Reformate 

Combustor Burns raffinate to provide heat for the reforming reaction Heat, CO2, H2O 

Fuel injector Injects and mixes fuel and steam into the reactor Vaporized steam/fuel mixture 

Heat exchangers Provides the proper temperature for each component Warmer or cooler gas streams 

H-permeable membrane Converts reformate to pure hydrogen and produces 

raffinate (membrane reject stream) for combustor 

Pure hydrogen, 

raffinate (H2, CO2, CO) 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Sulfur Management 

•	 de-sulfurization of reformate (as necessary, 

preferably re-generative and in-situ) 

•	 desulfurization of fuel (research alternatives) 

•	 thermal integration (eliminate external 

heating) 

Operational Considerations 

•	 safety (failure mode and effect analysis 

[FMEA], hazard analyses, etc.) 

•	 reliability (reliability modeling, test 

programs) 

•	 code requirements (research requirements, 

establish design guidelines) 

•	 manufacturability, maintainability (establish 

targets, schedule design reviews) 

Documentation 

•	 drawings (finalize standards for format, 

archiving etc.) 

•	 product data management (establish data 

master, configuration management and other 

requisite systems) 

Physical Layout and Balance of Plant (BoP), 

including: 

•	 pumping (research and obtain more reliable, 

less expensive alternatives) 

•	 insulation and shrouds (improve 

performance and aesthetics) 

•	 valves, orifices, thermocouples, transducers, 

etc. (integrate control devices) 

Sensors and Controls, including: 

•	 metering and flow measurement (eliminate 

expensive mass flow controllers) 

•	 automation (automated shut-down, start-up 

and operation) 

•	 hardware, software design (establish 

requirements for controllers and software) 

•	 diagnostics (implemented as required for 

troubleshooting) 

•	 data logging (establish requirements, 

minimize excess data collection) 

Results 

Catalyst and Membrane Testing 

Steam Reforming Catalyst Testing. Over 1,000 

hours of catalyst testing was completed using natural 

gas as a feedstock. The reforming occurs at 850°C 

with steam/carbon ratio of approximately 3.5. Figure 

1 shows the product composition for the last half of 

the test. Hydrogen concentration is about 75%; the 

product contains about 1-2% unconverted methane 

due to the pressure (>80 psig) at which the steam 

reforming was conducted. This agrees with 

thermodynamic calculations. The total product flow 

Figure 1.	 Product Gas (H2, CO, CO2, and CH4) 

Composition During Steam Reforming of 

Natural Gas Using InnovaTek’s Proprietary 

Catalyst (ITC #1148); reaction temperature 

850°C, water feed rate 1.0 ml/min, natural gas 

feed rate 380 ml/min, pressure 84.7 psi 

Figure 2. Product Gas (H2, CO, CO2, and CH4) Flow 

Rates During Steam Reforming of Natural Gas 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

rate was measured and is plotted in Figure 2 About 

1.5 SLM product was produced with a natural gas 

feed rate of about 380 mL/min, which corresponds to 

approximately 95% conversion of the natural gas. 

An 80-hour test with ultra-low sulfur (~5 ppm) 

diesel, a developmental product obtained from 

Chevron Phillips Chemical, was also successfully 

completed (Figure 3). 

Membrane Hydrogen Purifier Performance. We 

designed and fabricated a hydrogen-permeable metal 

membrane assembly and tested it with simulated 

reformate with and without sulfur. The 97 ppm 

concentration of sulfur in the sulfur-containing 

reformate represents the result of reforming fuel 

containing approximately 800 ppm sulfur (by 

weight). Tests were conducted at a pressure of 90 

psig. Optimum results were obtained at a membrane 

temperature of 500°C when sulfur was present and at 

400°C without sulfur. Although the sulfur apparently 

causes some degradation of permeation initially, it 

Figure 3. Steam Reforming of Low-Sulfur Diesel Fuel 

Using InnovaTek's Proprietary Catalyst 

 FY 2003 Progress Report 

appears that performance stabilizes after 

approximately one hour of run-time. The ultimate 

recovery with sulfur present is approximately 57% of 

the recovery without sulfur (Figure 4).The results 

show promise that a sulfur-tolerant membrane 

module can be developed but that its surface area will 

need to be about 1.75 times larger to achieve the 

same hydrogen permeation rate that is possible when 

sulfur is not present in the reformate. A visual 

inspection of the module after disassembly showed 

no adverse effects from the testing. 

System Integration 

System components were integrated according to 

the simplified schematic in Figure 5. Table 2 

summarizes the operating parameters and system 

specifications as they currently are defined. We are 

able to achieve a 49% efficiency using a recuperator 

to recapture heat from the exhaust to pre-heat 

combustion air. 

Prototype Operation and Testing 

We performed continuous testing of the 1-kW 

prototype using diesel fuel, logging approximately 

120 hours of run-time. Over the course of operation, 

the sulfur content of the fuel was increased 

incrementally from 50 ppm to 100 and finally to 250 

ppm. During these tests, increased understanding 

was obtained for catalyst and membrane performance 

in an integrated system. The fuel injector was found 

to be a critical component that can help eliminate 

coking, one of the most serious problems associated 

with reforming heavy hydrocarbon fuels. 

Figure 4. Hydrogen Recovery as a Function of Time and 

Sulfur Concentration Figure 5. InnovaTek Fuel Processor System Diagram 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Table 2. 1-kW System Operating Parameters 

Parameter Value

Diesel Flow Rate to Reactor 3.6 gm/min 

Diesel Flow Rate to Burner 2.0 gm/min 

Water Feed Rate 23 gm/min 

Condensate Collected from 

Reformate 

16 gm/min 

Reformer Shell Losses 500 W 

Reformate Condensing Temperature 60°C 

Reforming Temperature 850°C 

Membrane Operating Temperature 400°C 

Membrane Surface Area 524 cm2 

Thermal Efficiency 49% 

Another finding was that as fuel sulfur content 

was increased, more frequent catalyst conditioning 

was required. We also determined that high 

conversion rates are required during steam reforming 

to prevent degradation of the membrane system over 

time. 

Hydrogen production of the 1-kW diesel fuel 

processor was measured over a period of 

approximately 14 hours of continuous operation at 

steady-state operating conditions. When compared 

to the recorded diesel fuel flow rates, an average 

thermal efficiency was calculated to be at least 36 

±3% (based upon the lower heating values of both 

the diesel and the hydrogen). This result is short of 

our target efficiency of 50%, due primarily to higher 

operating temperatures and steam/carbon ratios, and 

non-optimized thermal integration. After testing, the 

prototype fuel processor was disassembled, dissected 

and inspected. The components were found to be 

sound and in overall very good condition. 

Conclusions 

•	 Our process model was very useful in 

contributing to the design and establishing the 

operating parameters of the system. 

•	 Performance tests of InnovaTek's proprietary 

steam reforming catalyst, conducted in a 100-W 

 FY 2003 Progress Report 

test bed and a 1-kW system, indicate that the 

catalyst can be used for multiple fuel types 

without the need for prior sulfur removal, 

although periodic regeneration is required at 

higher sulfur concentrations. 

•	 A scheme for on-line re-generation of the 

reforming catalyst has been developed and will 

be implemented in a modular reactor. 

•	 The hydrogen purification membrane module 

design is improved, and membrane testing on a 

custom test fixture indicated that, although the 

membrane tolerates sulfur, increased surface area 

is required when sulfur is present in the 

reformate. 

•	 The fuel injector design continues to improve 

and is a crucial component to prevent catalyst 

fouling or reactor plugging during operation. 

FY 2003 Publications/Presentations 

1. Irving, P.M., T.M. Moeller, Q. Ming, and A. Lee, 

"Hydrogen Production from Heavy Hydrocarbons 

Using a Fuel Processor with Micro-Structured 

Components", presented at the 2002 Fuel Cell 

Seminar, November 18-21, 2002, Palm Springs, 

CA. 

2. Irving, P.M. "The InnovaGenTM Fuel Processor", 

presented at the SIRTI Technology Showcase, 

November 2002, Spokane, WA. 

3. Irving, P.M., Q. Ming, and D.R. Stephens, 

"Development of a Fuel Processor that Generates 

Hydrogen from Conventional Fuels", In: 

Proceedings of the 14th Annual U.S. Hydrogen 

Meeting, March 4-6, 2003, Washington DC. 

4. Irving, P.M., "Novel Catalytic Fuel Reforming", 

Global Climate Energy Project, April 14-15, 

2003, Stanford University. 

5. Irving, P.M., Q. Ming, T. Dickman, and D.R. 

Stephens, "The InnovaGenTM Diesel Fuel 

Processor with Micro-Channel Components", In: 

Proceedings of the Hydrogen and Fuel Cells 2003 

Conference and Trade Show, June 8-11, 2003, 

Vancouver, BC. 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Engineering Development of Ceramic Membrane Reactor Systems for 

Converting Natural Gas to Hydrogen and Synthesis Gas for Liquid 

Transportation Fuels (ITM Syngas) 

Christopher M. Chen (Primary Contact)
 

Air Products and Chemicals, Inc.
 

7201 Hamilton Boulevard
 

Allentown, PA 18195
 

Phone: (610) 481-3315; Fax: (610) 706-6586; E-mail: chencm@apci.com
 

DOE Technology Development Managers:
 

Daniel C. Cicero - Phone: (304) 285-4826; Fax: (304) 285-4403; E-mail: daniel.cicero@netl.doe.gov
 

Arlene Anderson - Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov
 

Subcontractors:
 

Ceramatec, Inc. (Salt Lake City, UT), ChevronTexaco (Richmond, CA), Eltron Research Inc. (Boulder, CO), McDermott 

Technology Inc. (Alliance, OH), Norsk Hydro (Oslo, Norway), Pennsylvania State University (University Park, PA), 

University of Alaska Fairbanks (Fairbanks, AK), University of Pennsylvania (Philadelphia, PA)
 

Objectives 

•	 Research, develop and demonstrate Ion Transport Membrane (ITM) Syngas ceramic membrane reactor 

system for the low-cost conversion of natural gas to hydrogen and synthesis gas 

•	 Scale-up the ITM Syngas reactor technology through three levels of pilot-scale testing and 

precommercial demonstration
 

•	 Obtain the technical, engineering, operating and economic data necessary for the final step to full 

commercialization of the ITM Syngas technology 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 D. Carbon Dioxide Emissions 

•	 AA.Oxygen Separation Technology 

This project also addresses DOE Office of Fossil Energy objectives to develop lower cost methods to 

produce hydrogen from natural gas. 

Approach 

This project is in Phase 2 of a three-phase program. The approach in Phase 2 includes: 

•	 Task 2.1 Commercial Plant Economic Evaluation 

•	 Task 2.2 Materials and Seals Development and Evaluation 

•	 Task 2.3 ITM Syngas Membrane and Module Design and Fabrication 

•	 Task 2.4 Nominal 24,000 SCFD ITM Syngas Process Development Unit 

•	 Task 2.5 Nominal 330,000 SCFD ITM Syngas Subscale Engineering Prototype 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Process design and economic evaluation of a 150 million SCFD hydrogen plant with CO2 separation to 

provide a carbon-free "clean fuel" showed the potential for 30% capital cost savings in the synthesis 

gas production step 

•	 Projected hydrogen production costs for a distributed-scale hydrogen process (500,000 SCFD 

hydrogen, 100 units/year) are more than 25% below the DOE targets for 2005
 

•	 Demonstrated good performance stability of tubular membranes and seals at 250 psig and 825°C for 6 

month individual test durations 

•	 Achieved the project's Phase 1 oxygen flux targets with catalyzed, supported thin-film planar
 

membranes
 

•	 Achieved a three-fold increase in pilot-scale membrane fabrication yields over one year ago 

•	 Selected catalysts for scale-up testing in the Process Development Unit (PDU) 

•	 Demonstrated leak-tight performance of PDU module seals at 425 psig and 850-900°C under static 

conditions and multiple pressure and thermal cycles 

•	 Tested second-generation pilot-scale membrane modules in the PDU at elevated temperature and 

pressure with a synthesis gas environment 

•	 Fabricated commercial-size ceramic membranes 

Future Directions 

•	 Fabricate multi-wafer membrane module for PDU test 

•	 Test catalyzed planar membranes in PDU 

•	 Fabricate balance of ceramic components for Subscale Engineering Prototype (SEP) module with 

commercial-size membranes 

•	 Initiate tests to validate commercial-size membrane design 

•	 Conduct tests to determine kinetic parameters for membrane and catalysis performance models 

Introduction 

Ion Transport Membranes (ITMs) are a 

revolutionary platform technology for producing 

hydrogen and synthesis gas for applications in power 

generation, transportation fuels, and chemicals. The 

ITM Syngas process provides a lower-cost method for 

converting natural gas to hydrogen and synthesis gas 

by combining air separation and natural gas partial 

oxidation in a single-step ceramic membrane reactor, 

with the potential for capital cost savings of over 30%. 

When successful, this technology will be important to 

emerging hydrogen markets, such as hydrogen-based 

fuel cells for transportation and centralized hydrogen 

production facilities with CO2 capture. 

The new technology utilizes non-porous ceramic 

ITM membranes fabricated from multi-component 

metallic oxides that have both high electronic and 

oxygen ion conductivity at high temperatures 

(greater than approximately 700°C). In operation, 

oxygen from a hot air stream is reduced at one 

surface of the ITM membrane to oxygen ions, which 

diffuse through the membrane under a chemical 

potential gradient. At the opposite surface of the 

membrane, the oxygen partially oxidizes a prereformed mixture of hot natural gas and steam to 

form synthesis gas, a mixture of hydrogen and 

carbon monoxide. The ratio of hydrogen to carbon 

monoxide is in part dependent upon the amount of 

steam. The membrane material must show long-term 

stability in reducing and oxidizing atmospheres, and 

long-term compatibility with any oxygen reduction 

and partial oxidation/reforming catalysts that are in 

contact with its surface. 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

The objective of this program is to research, 

develop and demonstrate a novel ceramic membrane 

reactor system for the low-cost conversion of natural 

gas to hydrogen and synthesis gas: the ITM Syngas 

process. Through a 91⁄2 year, three-phase program, 

the ITM Syngas technology will be developed and 

scaled up to obtain the technical, engineering, and 

operating and economic data necessary for the final 

step to full commercialization of the hydrogen and 

synthesis gas generation technology. Phase 2 of the 

program was initiated in FY 2000 and will extend for 

41⁄2 years. Process concepts and performance will be 

validated in two stages of scale-up in Phase 2: the 

Process Development Unit (PDU), which began 

operation in 2002, and the Subscale Engineering 

Prototype (SEP), which will operate in 2004-2005. 

In Task 2.1, "Commercial Plant Economic 

Evaluation," advanced ITM Syngas processes will be 

developed, and the economics of operation at the 

commercial plant scale will be evaluated based on 

the results of the Phase 2 program. In Task 2.2, 

"Materials and Seals Development and Evaluation," 

membrane materials and seals will be tested at the 

laboratory scale under process conditions to obtain 

statistical performance and lifetime data. In Task 

2.3, "ITM Syngas Membrane and Module Design 

and Fabrication," membrane reactors will be 

designed for the ITM Syngas process at the PDU, 

SEP and commercial scales. Pilot-scale membrane 

modules will be fabricated for testing in the PDU. 

Fabrication of the membrane reactor modules will be 

scaled up in a Production Development Facility 

(PDF) to supply the requirements of the SEP. 

In Task 2.4, "Nominal 24,000 SCFD ITM 

Syngas PDU," the components of the ITM Syngas 

technology will be demonstrated in a laboratory 

Process Development Unit (PDU). The PDU will 

operate at an equivalent of 24,000 SCFD of synthesis 

gas capacity and will performance test pilot-scale 

planar membranes under commercial process 

conditions. In Task 2.5, "Nominal 330,000 SCFD 

ITM Syngas SEP", a Sub-Scale Engineering 

Prototype (SEP) unit will be built to demonstrate the 

ITM Syngas technology using commercial-size 

membranes in sub-scale modules. The SEP will 

demonstrate the operation of the ITM Syngas process 

at up to an equivalent of 330,000 SCFD of synthesis 

gas capacity. 

Results 

Conventional methods for producing hydrogen 

from natural gas typically require external sources of 

heat (e.g. steam methane reformers) or a separate 

pure oxygen stream (e.g. oxygen-fired autothermal 

reformers). Steam methane reformers (SMR) use 

natural gas as fuel in reformer furnaces to generate 

heat, which is transferred to the reforming catalyst 

packed in high-pressure tubes, resulting in a 

significant fraction of the carbon emitted to the 

atmosphere as CO2 in the low-pressure flue gas. 

Oxygen-fired autothermal reformers (ATR) use 

oxygen to partially oxidize natural gas internally in 

the reactor and retain nearly all the carbon in the high 

pressure synthesis gas, thus facilitating removal of 

CO2 for carbon capture. However, the ATR requires 

a separate air separation unit (ASU) to produce high 

purity, high-pressure oxygen - thus adding 

complexity and capital and operating cost to the 

overall process. The ITM Syngas process offers the 

advantages of partial oxidation of the natural gas and 

the concomitant retention of carbon in the highpressure synthesis gas, while simultaneously 

permeating pure oxygen across the ceramic 

membrane from a low-pressure air supply (Figure 1). 

In an evaluation of advanced process concepts, 

an ITM Syngas process was developed for a 

centralized hydrogen production plant with CO2 

removal, producing 150 million SCFD of fuel-grade 

hydrogen. For this application, the ITM Syngas 

process was compared to a conventional oxygenblown ATR with a cryogenic ASU to supply oxygen. 

Economic evaluation of the ITM Syngas process 

showed the potential for 30% capital cost savings in 

Figure 1. ITM Syngas Process to Produce Hydrogen 

and Capture CO2 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

the synthesis gas generation process area and over 

20% capital cost savings for the overall hydrogen and 

CO2 production process. The ITM Syngas process 

also has a higher thermal efficiency of 74% 

compared to 71% for the oxygen-blown ATR 

process. The hydrogen product is a "clean" fuel 

suitable for centralized power generation and for 

distribution to local stationary or mobile 

applications, including fuel cells. 

Tubular membranes and seal assemblies were 

tested in high-pressure, high-temperature lab-scale 

units under commercial process conditions. In these 

tests, pre-reformed natural gas mixtures at process 

pressure were passed over the outer surface of the 

tubular membrane, while air at atmospheric pressure 

was fed to the inner surface of the tube. Multiple 

tests, each operated continuously for over 6 months 

at 250 psig and 825°C under process conditions, 

were completed, and the membranes demonstrated 

good performance stability. A long-term test of a 

tubular membrane at high pressure and temperature 

is shown in Figure 2. 

Sub-scale supported thin-film membranes were 

also tested at atmospheric pressure for periods of 

over 1200 hours. Tests of advanced catalyzed 

membranes demonstrated oxygen fluxes that 

approach the commercial flux target range and meet 

the Phase 1 flux target (Figure 3). 

Rapid progress has been made in scaling up 

ceramic membrane fabrication using conventional 

processing methods (Figure 4). Lab-scale disk 

 FY 2003 Progress Report 

membranes were developed in 1999 in conjunction 

with initial materials development. Pilot-scale 

membranes were developed in 2000-2001 and have a 

30-fold increase in membrane area over the lab-scale 

membranes. The pilot-scale membranes are being 

used to demonstrate membrane performance at 

commercial process conditions in the PDU. 

Fabrication methods that were developed at the pilotscale were scaled up for commercial-size membranes, 

which have a 160-fold increase in membrane area over 

the lab-scale membranes. Fabrication of commercialsize membranes started in 2002. 

Pilot-scale membrane modules have been tested 

in the PDU at elevated temperature and pressure with 

a synthesis gas environment. The PDU integrates the 

various components of the ITM Syngas reactor 

design and is used to confirm the performance of the 

planar membrane modules and seals under 

commercial process conditions. Ceramic-to-metal 

Figure 3. Advanced Catalyzed Membranes Approach 

Commercial Flux Target 

Figure 2. Long-Term High Pressure Test of a Tubular 

Membrane Shows Stable Oxygen Flux 

Figure 4. Achieved Rapid Scale-up of ITM Syngas 

Ceramic Membranes Target 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

seals are used to connect the ceramic membrane 

module to metal air feed and vent piping and are a 

critical element in the membrane reactor system. 

PDU module seals have demonstrated leak tight 

performance at 425 psig and 850-900°C under static 

conditions, and also over 50 thermal cycles and 8 

pressure cycles (Figure 5). 

Conclusions 

Significant progress has been made to develop 

the ITM Syngas technology. A database is being 

built of performance data from several six-month 

duration membrane tests. Membrane modules and 

seal assemblies have also been fabricated and tested 

in the PDU at elevated temperature and pressure 

typical of synthesis gas conditions. Ceramic 

fabrication scale-up has progressed, and commercialsize membranes are being fabricated. Excellent 

progress continues to be made against the remaining 

technical challenges in the demonstration and scaleup of the ITM Syngas technology. 

Figure 5.	 PDU Module Ceramic-To-Metal Seals 

Demonstrate Leak-Tight Performance at 

Steady-State and with Thermal and Pressure 

Cycling 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. "Development of Ceramic to Metal Seals for 

Ceramic Membrane Applications," 57th Annual 

Forum of the Pennsylvania Ceramics Association, 

Sept. 2002 

2. "Ion Transport Membranes for Gas Separation," 

57th Annual Forum of the Pennsylvania Ceramics 

Association, Sept. 2002 

3. "Development of the Ceramic Membrane ITM 

Syngas Process," American Chemical Society 

National Meeting, New Orleans, LA, March 2003 

4. "Development of the Ceramic Membrane ITM 

Syngas Process," American Institute of Chemical 

Engineers Spring Meeting, New Orleans, LA, 

March 2003 

5. "Engineering Development of Ceramic 

Membrane Reactor Systems for Converting 

Natural Gas to Hydrogen and Synthesis Gas for 

Liquid Transportation Fuels," US DOE Hydrogen, 

Fuel Cells and Infrastructure Technologies 

Program Merit Review, Berkeley, CA, May 2003 

6. "Engineering Development of Ceramic 

Membrane Reactor Systems for Converting 

Natural Gas to Hydrogen and Synthesis Gas for 

Liquid Transportation Fuels," US DOE Advanced 

Synthesis Gas and Clean Fuels Program Merit 

Review, Houston, TX, June 2003 

FY2003 Patents Issued or Applications Filed 

1. "Mixed Conducting Membranes for Syngas 

Production", US Pat #6,492,290 

2. Three patent applications filed covering ceramicceramic joining methods and the membrane 

assembly 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Integrated Ceramic Membrane System for Hydrogen Production 

Joseph Schwartz (Primary Contact), Prasad Apte, Raymond Drnevich, Ashok Damle 

Praxair, Inc. 

175 East Park Drive 

Tonawanda, NY 14150 

Phone: (716) 879-7455; Fax: (716) 879-7091; E-mail: Joseph_Schwartz@praxair.com 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov 

Subcontractor: Research Triangle Institute, Research Triangle Park, NC 

Objectives 

•	 Develop an integrated ceramic membrane system using an oxygen transport membrane (OTM) in the 

first stage to produce syngas and a hydrogen transport membrane (HTM) in the second stage to 

produce hydrogen at a low cost on a scale of 1000-5000 SCFH 

•	 Develop a palladium-based HTM that can meet performance goals for flux, selectivity, life, and 

cycling on a bench scale 

•	 Develop the substrate materials, coating materials, and appropriate manufacturing technology 

•	 Confirm membrane performance under simulated reactor conditions 

•	 Confirm that the process is cost competitive for distributed hydrogen production 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 E. Control and Safety 

•	 Z. Catalysts 

•	 AA.Oxygen Separation Technology 

•	 AB.Hydrogen Separation and Purification 

Approach 

•	 Update literature review 

•	 Develop substrate 

•	 Develop membrane 

•	 Confirm membrane performance through tube testing 

•	 Update process economics 

Accomplishments 

•	 Completed Phase I 

•	 Determined that the two-stage integrated ceramic membrane process could be cost competitive if the 

membranes can be developed 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Identified alloy compositions with suitable resistance to contaminants 

• Identified substrate compositions with suitable thermal expansion properties 

• Fabricated porous ceramic support tubes 

• Coated the porous ceramic support tubes with palladium alloy 

Future Directions 

• Produce leak-free composite palladium alloy membranes 

• Demonstrate membrane performance in simulated reactor conditions 

• Determine the cost of hydrogen production using palladium alloy membranes 

• Decide whether to continue the project based on membrane performance and projected costs 

Introduction 

Hydrogen can be produced from natural gas by 

mixing it with steam, oxygen, air, or a combination 

of these to produce syngas, which contains hydrogen. 

One potentially low cost, efficient way to produce 

syngas is to use a ceramic membrane to separate 

oxygen from air. The separated oxygen reacts with 

natural gas and steam over a catalyst to produce 

syngas. The membrane, which can be integrated into 

the syngas generator, eliminates the need for a large, 

expensive air separation plant. (The work on oxygen 

membranes is being done in a different project.) 

Implementing those membranes to produce hydrogen 

is one of the goals of this project. To produce 

hydrogen, the product syngas is typically sent to 

another reactor where most of the CO and some of 

the steam in the syngas react to produce additional 

hydrogen. Using conventional existing technology, 

the hydrogen in the product stream from the second 

reactor must be purified using additional large, 

expensive equipment. The goal of the current phase 

of this project is to simplify hydrogen production by 

combining the second reactor and the hydrogen 

purification into a single step in a single vessel, 

which could significantly reduce the cost of 

producing hydrogen, and consequently, reduce the 

price of hydrogen to the consumer. Because of the 

way that the reaction and separation are combined, it 

is also possible to produce more hydrogen than 

would be possible using the conventional two-step 

approach, providing additional benefit to the 

consumer. 

Phase I of this project analyzed and compared 

several different processes. Based on projected cost, 

efficiency, and likelihood of success, a two-stage 

process wherein each stage was comprised of a 

membrane reactor was selected. The analysis 

indicated that this process has the potential to be the 

least expensive hydrogen production method of those 

evaluated. Phase II, which began earlier this year, 

has focused on developing the hydrogen purifier to 

put this process into practice. Potential materials 

have been identified, and several attempts have been 

made toward fabricating the hydrogen purifier. 

These attempts have shown continuous improvement 

and provided essential information about what 

remains to be done to produce an effective purifier. 

Approach 

The first step in developing the hydrogen purifier 

was to determine possible materials for the 

membrane based on available results in the technical 

literature. Some membrane compositions examined 

in the past have been unable to resist contamination 

caused by other materials in the syngas, such as CO 

or sulfur. Other compositions have failed because 

they were made of materials with different thermal 

expansion characteristics so that when the final 

membrane was heated, the layers separated, 

destroying the membrane. Possible membrane 

compositions that are expected to be sufficiently 

resistant to contaminants and not separate when 

heated were identified. 

The next step in the project is to make and test 

the membrane to confirm its performance. Porous 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

substrates using ceramic materials have been made 

based on our expertise in producing ceramic 

membranes for other applications. These substrates 

have been coated with palladium, and the resulting 

membranes have been analyzed. Controlling the 

pore size and porosity of the ceramic substrate is 

critical to ensuring that the coating will be leak free 

and uniform while being sufficiently thin to provide 

adequate performance at a reasonable cost. The 

porous substrates have shown continuous 

improvement because of improved techniques 

designed to control the pore size and porosity of the 

substrates. Once sufficient membranes have been 

produced, they will be tested in a demonstration 

reactor using simulated syngas. 

Provided that the membrane development is 

successful, the economic assessment performed in 

Phase I will be revised using the test data. If the 

integrated ceramic membrane process still appears to 

be a low-cost hydrogen generation process, we will 

advance to the next part of the project, which is 

testing the membrane in an integrated reactor. 

Results 

In the initial trial, eight porous ceramic tubes 

were fabricated by isostatic pressing. One of the 

tubes was activated and plated with palladium alloy 

layers. The tube was then thermally annealed in 

argon. Samples of the tube that were analyzed by 

scanning electron microscope (SEM) before and after 

annealing indicated the metal film thickness was 

about 4 μm. SEM analysis indicated that the top 

surface of this substrate tube was rough with up to 

40-50 micron size holes on the surface. Although the 

plating appeared to go on well and seemed to follow 

contours into the large holes, it did not appear to 

bridge the gap at all of the large openings on the 

surface. A nitrogen leak test confirmed the presence 

of through holes throughout the surface, as indicated 

by the SEM analysis of the top surface of annealed 

films. Figures 1 and 2 show the top of the substrate 

surface before and after heating, respectively. These 

pictures clearly show the surface roughness and the 

size of large 40-50 μm size openings on the surface. 

Because of the problems with these tubes, the 

next group of tubes was made with smaller pores, 

and thicker plating was used, as shown in Figures 3 

and 4. Each of these steps was expected to improve 

the tube and make it less likely to leak. Tube # 

030327-0 was activated and plated with palladium 

Figure 1. Schematic of Fabricated Tri-layer 

Figure 2. Top of Surface after Annealing 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

alloy. However, permeation analysis indicated a 

substantial leak of nitrogen through pinholes 

throughout the surface. Although the average pore 

size of the openings on the surface of this tube was 

smaller than the pores in the first batch, with a finer 

surface texture, large openings of the order of 50 μm 

were still evident on the surface (Figure 3). 

Although the plating appeared to go on the surface 

well and followed the contours into the large holes, it 

still did not bridge the gap at all of the large openings 

on the surface, as seen in Figure 4. 

This batch of tubes showed improvement over 

the first batch, but the substrate surface needs to be 

smoother with smaller, more uniform openings to 

obtain a leak-tight metal film. Work on developing 

improved substrates continues. 

Conclusions 

•	 Palladium alloy compositions exist that have 

sufficient hydrogen flux and resistance to possible contaminants, such as sulfur and CO. 

•	 Low-cost substrate materials exist with proper 

thermal expansion properties so that thermal 

cycling of the final membrane is likely to be 

possible. 

•	 These substrate materials can be fabricated into 

porous tubes and coated with palladium alloy. 

•	 Control of substrate pore size and porosity is 

critical. 

FY 2003 Publications/Presentations 

1. Presentation at the DOE Annual Merit Review 

Meeting 

2. Semi-Annual Progress Report submitted to DOE 

 FY 2003 Progress Report 

Figure 3. Top of Zirconia Substrate 

Figure 4. Top of Surface After Plating 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low Cost Hydrogen Production Platform 

Timothy M. Aaron 

Praxair Inc. 

175 East Park Drive 

P.O. Box 44 

Tonawanda, NY 14051 

Phone: (716) 879-2615; Fax: (716) 879-7567; E-mail: tim_aaron@praxair.com 

DOE Program Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-1637; E-mail: Arlene.Anderson@ee.doe.gov 

Subcontractors: 

Boothroyd-Dewhurst Inc, Wakefield RI 

Diversified Manufacturing Inc, Lockport, NY 

Objectives 

•	 Examine opportunities for on-site production of hydrogen at low cost using existing technologies 

(steam methane reforming, pressure swing adsorption), with the following parameters: 

- 1,000 - 5,000 scfh 

- Small, compact, single skid system 

- 10-15 year system life 

•	 Establish a benchmark for current technology 

•	 Design and fabricate a prototype on-site hydrogen production system 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells, and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance (O&M) 

•	 C. Feedstock and Water Issues 

•	 E. Control and Safety 

Approach 

•	 Conduct review of existing technologies 

•	 Develop preliminary design and engineering models 

•	 Assess economics versus current and potential future supply options 

•	 Develop and test component prototypes 

•	 Develop final design and verify economics 

•	 Build, install and test complete prototype system 

Accomplishments 

•	 Preliminary detail and process design completed 

•	 3D computer models of components and system completed 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Design for Manufacture and Assembly (DFMA) preliminary analysis completed 

• System economic model completed 

• Significant hydrogen cost reductions determined to be achievable 

Future Directions 

• Complete preliminary detail design and engineering models 

• Complete DFMA analysis on total system 

• Design, construct and test system components 

• Verify component performance and overall system life 

• Complete final detail design 

• Develop, install and test prototype system 

• Continue to update business and economic models 

Introduction 

Steam methane reformer (SMR)-based hydrogen 

production facilities are highly capital intensive 

because they are custom-designed and are built using 

one-at-a-time design and fabrication techniques. 

Capital costs account for 70-85% of the total per unit 

hydrogen costs for on-site systems in the 20,000 scfh 

and below capacity range. As a result, the 

opportunity exists for very substantial reductions in 

product hydrogen costs by introducing advanced 

design optimization technology. The focus of this 

project is to develop an integrated system for the 

turnkey production of hydrogen at 1,000 - 5,000 scfh 

(28-140 Nm3/hr). The design is based on existing 

SMR technology and existing chemical processes or 

technologies to meet the design objectives. 

Consequently, the system baseline design consists of 

a steam methane reformer, a pressure swing 

adsorption (PSA) system for hydrogen purification, 

natural gas compression, steam generation and all 

components and heat exchangers required for the 

production of hydrogen. A process flow diagram of 

the system is shown in Figure 1. The scope of this 

project does not include hydrogen compression, 

storage or fueling station components. 

The focus of the project emphasizes packaging, 

system integration and an overall step change in the 

cost of capital required for the production of 

hydrogen at low volumes. To assist in this effort, 

subcontractors were brought in to evaluate the design 

concepts and to assist in meeting the overall goals of 

Figure 1. Low-Cost Hydrogen Production Platform 

Process Flow Diagram 

the project. Praxair supplied the overall system and 

process design for the concepts and the 

subcontractors were used to evaluate the designs 

from a manufacturing and overall design 

optimization viewpoint. Design for manufacturing 

and assembly (DFMA) techniques and computer 

models were utilized to optimize the concepts during 

all phases of the design development. 

Approach 

The means for achieving low hydrogen costs 

from small systems is through capital cost 

reductions, integrating components and reducing 

2 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

the number of parts required for an SMR-based 

hydrogen production system. For conventional 

small plant designs, more than 75% of the cost of 

hydrogen is associated with capital costs. The 

project approach is to apply DFMA design 

techniques to the component and system designs 

from the early concept phase of design to the 

completion of the design effort. The reduction in 

number of parts and the resulting integration and 

simplification of the plant layout significantly 

reduces the capital cost and the overall plant size. 

Praxair has defined concepts that involve 

integration of steam generation, reforming, shift 

reaction and all high temperature components into a 

single highly integrated package. The PSA 

purification system as well as the overall skid 

layout and integration have also been designed 

using the DFMA approach. This effort shows the 

potential to significantly reduce the capital cost 

required for a small hydrogen system and thereby 

greatly reduce the overall cost to produce hydrogen. 

A risk analysis was conducted to identify any 

design deficiencies related to the potential concepts. 

The analysis showed that no fundamental design flaw 

exists with the concepts, but additional simulations 

and prototypes would be required to verify the 

design(s) prior to fabricating a production unit. 

These identified risks will be addressed in detail 

during Phase II of the development project. 

Along with the models of the high-temperature 

components, a detailed process and 3D design model 

of the remainder of system, including PSA, 

compression, controls, water treatment and 

instrumentation was developed and evaluated. The 

overall design and specifications were then used to 

develop accurate hydrogen costs for the optimized 

system. Potential areas for further cost reductions 

were also identified and will be investigated in future 

phases of the program. 

A market and business analysis was also 

conducted as part of Phase I. A study of the current 

available and potential future hydrogen production 

technologies was compared with the design concepts 

developed in this project. An analysis of the 

potential market, with respect to number of units, 

feedstocks and capacity was also conducted. 

Results 

The capital and product costs were estimated 

for 1,000, 2,000 and 5,000 scfh plants at production 

rates of 1, 10, 100 and 1,000 units built per year. 

With the low cost SMR approach, the product 

hydrogen costs for 1,000 and 2,000 scfh plants at 

100 units produced per year were approximately 

$24/MMBtu and $19/MMBtu (HHV), respectively. 

With increased volume production to 1,000 units 

per year, the hydrogen costs are reduced by about 

12% to $21/MMBtu for the 1,000 scfh unit and $17/ 

MMBtu (HHV) for the 2,000 scfh unit. For the 

5,000 scfh plant, the cost of hydrogen ranged from 

$14 to $17/MMBtu (HHV) depending on number of 

units built per year. These costs represent a 

significant improvement and a new benchmark in 

the cost to produce small volume on-site hydrogen 

using existing process technologies. The cost 

models also show that the utility costs (natural gas 

@ $4/MMBtu (HHV), electricity and water) total 

$7.50/MMBtu (HHV). 

The capital and product costs are based on a 

skid package designed to be a complete, 

operationally verified system prior to being shipped 

to the site for installation. Computer models of the 

completed system skid assembly are shown in the 

Figures 2 and 3. 

The skid has been designed to easily fit within a 

standard parking space. All mechanical devices such 

as valves, pumps, compressors, motors, and controls 

are located on the periphery of the skid with doors 

providing easy access to these items. The skid is also 

designed to be ventilated during operation by using 

the cooling system fan to provide the required air 

changes. The electrical enclosure is designed to be 

isolated from the machinery portion of the skid. 

Atmospheric analysis for combustible and/or 

hazardous gases has not been designed into the 

system. It has been calculated that with sufficient air 

changes, there is no potential of creating a hazardous 

or explosive environment within, or in the immediate 

vicinity of, the skid. The predicted cost to produce 

hydrogen from this system is shown in Figure 4. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Low-Cost Hydrogen Production Platform 

Skid Design. (All components and controls 

necessary for the production of hydrogen 

using natural gas, city water and electricity as 

utilities.) 

Figure 3. Low-Cost Hydrogen Production Platform - 

Skid Cover Off 

Figure 4. Unit Hydrogen Cost Versus Units Produced 

and System Capacity 

A comparison of fuel costs between internal 

combustion engine vehicles (ICEVs) and fuel cell 

vehicles (FCVs) shows that if there is no tax on 

hydrogen, then the hydrogen must be produced at 

about $19/MMBtu (HHV) (before compression) to 

be competitive with fully-taxed gasoline at $1.60/gal. 

If hydrogen is to be competitive with untaxed 

gasoline ($1.20/gal), then the cost of uncompressed 

hydrogen should be $12/MMBtu (HHV). Thus, with 

a cost of $19/MMBtu (HHV) for 2,000 scfh 

uncompressed hydrogen with production of 

hydrogen plants at 100 units/year, FCV hydrogen 

costs will be nearly equal to ICEV hydrogen costs in 

early years if there is no tax on hydrogen. With the 

mass production of hydrogen plants as the FCV 

market grows throughout the U.S., hydrogen cost 

will need to decrease to $13/MMBtu (HHV) to make 

it possible to support a fuel tax. Cost models indicate 

that $13 to $16/MMBtu hydrogen is not achievable 

with 1,000 scfh plants, but with production plants of 

2,000 scfh and higher, these targets are achievable. 

The design concepts developed in Phase I of this 

project show significant progress in decreasing the 

cost to produce hydrogen in production plants of 

<5,000 scfh. As the demand for hydrogen increases, 

the capacity required at each site will grow and units 

in the production range of 5,000 scfh will be more 

cost effective. Significant effort will be required to 

validate the design concepts in the subsequent phases 

of the project and to develop a working prototype of 

the system. The total remaining duration of the 

project is estimated to be three to four years. 

4 
 

 

 

 

 

Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

The transportation sector is likely to continue to 

be a primary source for the demand of small-scale 

hydrogen production systems in the future. Our 

baseline projections for the number of 2,000-5,000 

scfh hydrogen plants that Praxair will have 

opportunity to build are 30 plants/yr in 2010 and 130 

plants/yr in 2020. With the recent modifications to 

California's zero emission vehicle mandate, the 

market for FCVs will be slow to develop. The cost 

of fuel cells also remains a significant barrier for the 

viability of FCVs. Therefore, this project is 

structured to develop an optimized SMR-based 

system and thoroughly test all aspects of the design 

prior to entering into a production run. Phase I work 

has demonstrated that significant improvements in 

cost, plant layout, system integration and overall 

system optimization are achievable. Therefore, 

further development efforts will focus on system and 

component computer modeling and prototype 

testing. Phase II of the project will focus on 

demonstrating both the design component testing and 

economic viability of the concepts developed in 

Phase I. 

Conclusions 

1. Applying DFMA principles to the overall design 

significantly lowered the cost to produce 

hydrogen at volumes of 1,000 to 5,000 scfh. 

2. A complete hydrogen generating system 

producing up to 5,000 scfh can be packaged in a 

single skid that is small enough to easily fit into a 

typical parking space. 

3. A new benchmark appears possible for the cost of 

hydrogen produced from current process 

technologies (i.e. SMR with PSA purification). 

4. Preliminary results from the Phase I study will 

need to be verified in subsequent phases of the 

project to ensure that the system is safe, robust 

and meets the overall project goals. 

FY 2003 Publications/Presentations 

1. Presentation at the DOE Annual Merit Review 

Meeting (May 2003) 

2. Phase I Final Report (submitted to DOE - June 

2003) 

5 
Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

6
 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Encapsulated Metal Hydride Separation Membrane Development 

Kit Heung (Primary Contact), James Congdon 

Westinghouse Savannah River Technology Center 

773-A, Savannah River Site 

Aiken, South Carolina 

Phone: (803) 725-3161; Fax: (803) 725-2756; E-mail: leung.heung@srs.gov 

DOE Technology Development Manager: Peter Devlin 

Phone: (202) 586-4905; Fax: (202) 586-9811; E-mail: Peter.Devlin@ee.doe.gov 

Objectives 

•	 Produce a sol-gel encapsulated metal hydride packing material that will absorb hyrogen selectively, 

will not break down to fines, and will tolerate reactive impurities. 

•	 Evaluate the packing material for hydogen absorption from low concentration streams. 

•	 Develop separation process with the new packing material. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 AB.Hydrogen Separation and Purification 

Approach 

•	 Develop formulations and procedures to make silica encapsulated metal hydride composite material. 

•	 Design and install gas manifold for testing encapsulated packing materials for hydrogen absorption 

from streams of gas mixtures. The tests will generate hydrogen capacity and absorption kinetic data. 

•	 Analyze the encapsulated packing materials before and after repeated hydrogen absorption and 

desorption to evaluate their physical stability. 

•	 Develop process to use this new hydrogen absorption packing material for efficient hydrogen 

separation from low concentration gas streams. 

Accomplishments 

•	 Produced five variations of encapsulated samples for hydrogen absorption test. 

•	 Conducted hydrogen absorption tests with various samples from gas mixtures that contain nitrogen, 

methane and carbon monoxide. 

•	 Developed new encapsulation technique that significantly improved the physical stability of the 

product. 

Future Directions 

•	 Increase metal hydride content in the encapsulated product to maximize hydrogen capacity. 

•	 Investigate the encapsulation of metal hydrides of higher equilibrium hydrogen pressure so that the 

product is better suited for use in pressure swing absorption separation processes. 

•	 Optimize the porosity of the encapsulating matrix to increase the product's resistance to reactive 

impurities. 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Design and fabricate a pressure swing absorption experimental apparatus to test the encapsulated metal 

hydride for hydrogen separation. 

•	 Conduct cost analysis. 

Introduction 

Hydrogen is certainly a clean fuel, but there is no 

significant quantity of naturally free hydrogen 

anywhere on earth. Hydrogen exists mostly in 

combined form with other elements, such as in water 

and hydrocarbons. Energy is required to free 

hydrogen from these compounds before it can be 

used as a fuel. This energy requirement must be 

minimized to maximize the net useful energy carried 

by hydrogen. Hydrogen demand today is mostly 

from the chemical industry and the petroleum 

refinery industry. This demand for hydrogen is met 

by steam reforming of natural gas and partial 

oxidation of hydrocarbon liquids and coal. The cost 

of hydrogen produced in this way is very low 

compared to the value of the products made. Many 

off-gas streams containing up to 50% hydrogen are 

discarded for economic reasons. Besides, hydrogen 

produced today is only a few percent of overall 

energy demand. 

A hydrogen economy will bring many changes. 

First, hydrogen demand will increase many fold. 

Second, hydrogen will be produced from multiple 

sources that include renewable and non-renewable. 

Third, low hydrogen content streams will not be 

discarded, and the hydrogen must be recovered using 

cost-effective recovery techniques. 

Present technologies for hydrogen separation 

include pressure swing adsorption (PSA), 

liquefaction, and membranes. All three processes are 

efficient for high hydrogen contents and highpressure feeds but are not efficient for low hydrogen 

contents and low-pressure feeds. For PSA, the 

inefficiency is partly due to the fact that the 

absorbents, including molecular sieves and activated 

carbons, preferentially absorb the heavy impurities. 

This is good if the heavy impurities are less than 

50%, but is not as good otherwise. When hydrogen 

content in a gas mixture is less than about 50%, it is 

more efficient to use an absorbent that absorbs 

hydrogen instead of the heavier components. A 

hydrogen absorbent that can be used in a practical 

separation process is not available today. The 

objective of this project is to develop such an 

absorbent and the process to use it. 

Approach 

Metal hydrides are a very well known group of 

materials that absorb hydrogen reversibly at 

moderate conditions. One example is 

LaNi4.25Al0.75: 

2 LaNi4.25Al0.75 + 5 H2 ↔ 2 LaNi4.25Al0.75H5 

Each bulk liter of this material can absorb up to 

18 moles of hydrogen reversibly. The hydrogen can 

be absorbed and desorbed by changing the hydrogen 

pressure, the temperature or both. This group of 

materials would have been well suited for hydrogen 

recovery from low concentration streams if not for 

two practical problems. First, metal hydrides in 

general break down to fines after repeated hydrogen 

absorption and desorption. The fines are in the 

micron range that makes them very difficult to use in 

separation columns. Second, metal hydrides are 

sensitive to reactive impurities like oxygen and 

carbon monoxide. Low levels of these impurities can 

render metal hydrides inactive toward hydrogen. 

Past efforts to deal with these problems are described 

by the works of Sandrock et al [1] and Suda et al [2]. 

In this work, a metal hydride is first broken down 

to fine particles. The fine particles are then 

encapsulated in a porous silica matrix to form a 

composite material. The composite is made in the 

form of granules or beads for packing separation 

columns. Each granule is a matrix of porous silica 

with metal hydride particles uniformly distributed in 

it. The porosity of the matrix permits hydrogen to 

reach the metal hydride particles but prevents the 

larger impurity molecules from penetrating. The 

porous matrix is strong and has void space for the 

metal hydride particles to expand and contract so that 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

hydrogen absorption and desorption do not cause 

breakage of the granules. The composite granules 

can therefore withstand hydrogen absorption/ 

desorption without generating fines and have good 

tolerance to reactive impurities. 

The encapsulated metal hydride samples are 

tested for hydrogen absorption first in a batch mode, 

then in a flow-through mode. In the flow-through 

mode, a small column is packed with the 

encapsulated metal hydride granules. Gas mixtures 

of hydrogen in nitrogen containing methane or 

carbon monoxide are fed into the column. Hydrogen 

concentration at the column exit is measured so that 

breakthrough curves are generated. The 

breakthrough curves give the capacity and kinetic 

information of the absorbent at the experimental 

conditions. The column is regenerated by heat and 

purging with nitrogen after hydrogen breaks through. 

After repeated absorption and desorption, the 

encapsulated granules are inspected for their physical 

conditions visually and microscopically. Success of 

a sample is defined by its ability to maintain its 

hydrogen capacity, absorption kinetics, and physical 

integrity after repeated cycling. Longer term, a 

pressure swing separation process using the 

encapsulated metal hydride (MH) as a packing 

material will be developed and demonstrated. 

Results 

Five different encapsulation methods were 

investigated that generated samples for hydrogen 

absorption tests: (1) Fumed silica was used for the 

porous matrix that encapsulated the fine particles of 

lanthanum-nickel-aluminum (LaNi4.25Al0.75); (2) 

Tetraethyl orthosilicate (TEOS) sol-gel was used as 

the source of silica for the matrix; (3) Sample in (1) 

was further treated with TEOS; (4) Method was the 

same as in (1) except that the La-Ni-Al particles were 

fluorinated [2] before encapsulation; (5) A method 

called external gelation that combined fumed silica, 

TEOS, and pore former to encapsulate the La-Ni-Al 

powder was used. The samples were tested for 

hydrogen absorption from different mixtures. Their 

hydrogen capacities and ability to withstand repeated 

absorption/desorption cycles are summarized in 

Table 1. The results show that good resistance to 

attrition is achieved by most of the samples. The 

presence of methane does not reduce the hydrogen 

capacity. The presence of carbon monoxide reduces 

the capacity significantly. One of the future efforts 

will be to improve the resistance toward CO. 

Figures 1 to 4 show photographs of encapsulated 

metal hydride samples and the original metal hydride 

particles before and after hydrogen absorption/ 

desorption cycling. The granules and beads of 

Table 1: Summary of Test Results 

Method Resistance to 

attrition 

H2 capacity from 

N2 stream 

mmol/g MH 

H2 capacity from 

(N2+10% CH4) 

mmol/g MH 

H2 capacity from 

(N2+1% CO) 

mmol/g MH 

Fume silica + LaNi4.25Al0.75 good 5 to be tested to be tested 

TEOS sol-gel + LaNi4.25Al0.75 poor 2 to be tested 0.45 

Fume silica + LaNi4.25Al0.75 + 

TEOS 

good 4.5 4.5 1.7 

Fumed silica + fluorinated 

LaNi4.25Al0.75 

good 4 to be tested 0.45 

External gelation + pore former + 

LaNi4.25Al0.75 

very good 4 to be tested to be tested 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

encapsulated metal hydride stay intact after repeated 

hydrogen absorption/desorption cycling. On the 

contrary, metal hydride particles by themselves break 

down to a fine power after a few cycles. 

In flow-through tests, a 40-cc sample is loaded in 

a 3⁄4-inch diameter, 6-inch long column that is 

installed on a gas manifold. A feed stream of low 

concentration hydrogen in nitrogen is delivered to the 

column. Methane or carbon monoxide is added to 

the feed depending on the test plan. Hydrogen is 

absorbed by the encapsulated metal hydride. 

Nitrogen and other impurities just pass through the 

column. Hydrogen concentration measured at the 

exit of the column is very low at the beginning and 

 FY 2003 Progress Report 

increases gradually when the metal hydride becomes 

saturated, producing a breakthrough curve. The 

breakthrough curve provides information on the 

performance of the sample. To regenerate, the 

column is heated to 120oC and purged with nitrogen. 

From the hydrogen concentration measured at the 

exit, the partial pressure and quantity of hydrogen 

recovered can be calculated. A typical set of 

breakthrough curve and regeneration results are 

shown in Figure 5. The feed gas contained 12% 

hydrogen in nitrogen. The feed flow rate was 34 

standard cc per minute. The pressure was 1500 torr 

(29 psia), and the temperature was 22o

C. The 

column absorbed more than about 90% of the 

hydrogen for about 300 minutes before the hydrogen 

Figure 1. Encapsulated La-Ni-Al after 100 Cycles 

Figure 3. Metal Hydride Particles before Cycling 

Figure 2. Encapsulated La-Ni-Al by External Gelation 

Method Figure 4. Metal Hydride Particles after 10 Cycles 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 5.	 Breakthrough Curve (Top) and Regeneration 

Results (Bottom) of Hydrogen Absorption by 

Encapsulated Metal Hydride 

broke through rapidly at about 400 minutes into the 

run. During regeneration, the partial pressure of 

hydrogen increased with temperature until it reached 

a maximum of 700 torr. The total hydrogen 

recovered was about 4 mmol/g of metal hydride 

compared to a maximum of about 6 at equilibrium. 

Conclusions 

•	 Metal hydride powder can be encapsulated in a 

porous silica matrix using a variety of techniques 

to produce stable granules suitable for hydrogen 

separation. 

•	 The encapsulated metal hydride retains its ability 

to absorb hydrogen readily and has better 

resistance to reactive impurities. 

•	 The external gelation technique combining the 

use of a pore former produces the strongest 

granules. The resistance of these granules to 

reactive impurities needs to be tested. 

•	 Breakthrough curve data show that an effective 

pressure swing, temperature swing, or 

combination swing process for hydrogen 

recovery from low concentration streams can be 

developed. 

References 

1. J. J. Sheridan III et al, Journal of the LessCommon Metals, 89 (1983) 447-455 

2. X.-L. Wang et al, Journal of Alloys and 

Compounds, 231 (1995) 860-864 

FY 2003 Publications/Presentations 

1. Paper titled "Hydrogen Absorption Property of 

Encapsulated LaNi4.25Al0.75" was accepted for 

presentation at HYPOTHESIS V (Hydrogen 

Power - Theoretical and Engineering Solutions 

International Symposium) to be held 7-10 

September, 2003. 

Special Recognitions & Awards/Patents 

Issued 

1. U.S. patent number 6,528,441 was issued on 

March 4, 2003. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Defect-Free Thin Film Membranes for H2 Separation and Isolation 

Tina M. Nenoff 

Sandia National Laboratories 

PO Box 5800, MS 0734 

Albuquerque, NM 87185-0734 

Phone: (505) 844-0340; Fax: (505) 844-1480; E-mail: tmnenof@sandia.gov 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811, E-mail: arlene.anderson@ee.doe.gov 

Objectives 

•	 Synthesize defect-free thin film zeolite membranes for H2 isolation and purification. 

•	 Use these as water management membranes in proton exchange membranes (PEMs). 

•	 Replace existing expensive and fragile Pt catalysts. 

•	 Test the separations of light gases (pure and mixtures) through the membranes. 

•	 Demonstrate effective light gas separations and commericalization potential of zeolite membranes. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 	 

•	 B. Weight and Volume 

•	 D. Durability 

•	 E. Refueling Time 

•	 H. Sufficient Fuel Storage for Acceptable Vehicle Range 

•	 K. Balance-of-Plant (BOP) Components 

Approach 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance (O&M) 

•	 C. Feedstock and Water Issues 

•	 E. Control and Safety 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

•	 AB.Hydrogen Separation and Purification 

Accomplishments 

•	 Synthesize defect-free thin film zeolite membranes and microporous bulk phases for future membrane 

applications. 

•	 Model/simulate permeation of light gases through various frameworks/pores for optimized
 

performance.
 

•	 Analyze flux and permeation of gases through membranes on unique in-house permeation unit. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Validate modeling/simulation with actual permeation data to optimize membranes synthesized. 

•	 Foster industrial contacts and collaborations. 

Future Directions 

•	 Synthesize and characterize thin films and bulk novel microporous phases including aluminosilicate 

(Al/Si) zeolite thin films doped and/or ion exchanged with other elements, unsupported 

aluminosilicate zeolite membranes, and silicotitanate phases (Si/Ti). 

•	 Attempt use of atomic layer deposition of catalytic metals on top of zeolite membrane. 

•	 Synthesize membranes on oxide-coated porous stainless steel (commerically viable) supports 

•	 Model separation values by molecular dynamics calculations for pure and mixed light gases 

interacting with differing zeolite type membranes (i.e., comparing ZSM-5 to ZSM-W). 

•	 Perform permeation and flux studies of pure and mixed gases through membranes (H2, CO, CO2, CH4, 

N2, and SF6); proceed with unit alterations for H2S testing. 

•	 Build a partnership with a membrane company. Initiate an agreement for product development with an 

industrial partner. 

Introduction 

There is a great need for robust, defect-free, 

highly selective molecular sieve (zeolite) thin film 

membranes for light gas molecule separations in 

hydrogen fuel production from CH4 or H2O sources. 

In particular, we are interested in (1) separating and 

isolating H2 from H2O and CH4, CO, CO2, O2, N2 

gases; (2) water management in PEMs; and (3) 

replacing expensive Pt catalysts needed for PEMs. 

Current hydrogen separation membranes are based 

on Pd alloys or on chemically and mechanically 

unstable organic polymer membranes. The use of 

molecular sieves brings a chemically and 

mechanically stable inorganic matrix to the 

membrane. The crystalline frameworks have 

“tunable” pores that are capable of size exclusion 

separations. The frameworks are made of inorganic 

oxides (e.g., silicates, aluminosilicates, phosphates) 

that bring different charge and electrostatic attraction 

forces to the separation media. The result is 

materials with high separation abilities plus inherent 

thermal stability over 600°C and chemical stability. 

Furthermore, the pore sizes and shapes are defined 

crystallographically (<1 Å deviation), which allows 

for size exclusion of very similarly sized molecules. 

In comparison, organic polymer membranes are 

successful based on diffusion separations, not size 

exclusion. We envision impact of positive results 

from this project in the near term with hydrocarbon 

fuels, and in the long term with biomass fuels. 

Approach 

The approach for this project in FY 2003 is the 

development of defect-free thin film zeolite 

membranes and new bulk microporous phases for the 

selective separation of light gases. The development 

of these membranes includes the synthesis, 

modeling/simulation, permeation studies, and 

validation for the separation and isolation of H2. The 

permeation studies are of pure and mixed gases 

through membranes, studied at room temperature and 

80°C. The modeling and simulation work helps 

determine improved pore size and composition for 

sieving. The validation is the iteration of modeling/ 

simulation data with actual permeation values to 

improve upon the membranes synthesized. 

Previous work at Sandia has successfully shown 

the ability to grow defect-free aluminosilicate and 

phosphate-based molecular sieve membranes. The 

continued focus now is on the enhancement and 

optimization of the type of molecular sieve for 

separation, the methodology of film growth, the type 

of supports upon which to grow membranes (and 

remain commercially viable). We are studying 

aluminosilicate frameworks and metal doped 

frameworks to better determine the relationship 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

between adsorption, sieving and then permeation. To 

study the effect and preferability of support types, we 

are studying and comparing unsupported film growth 

versus film growth on ceramic supports. We are also 

beginning our studies on newly available ceramic 

coated stainless steel supports (allowing for phase 

match on the ceramic, but enhancing durability of 

stainless steel). With all materials synthesized, we 

perform characterization in-house to better understand 

structure-permeability relationships. Characterization 

methods include X-ray diffraction, thermal analyses, 

elemental analysis and permeation studies. Our inhouse permeation unit is capable of fitting both disk 

and tubular membrane supports, either of ceramic 

oxide or stainless steel materials. This unique unit can 

be run from room temperature to elevated 

temperatures (= 500°C), though we only plan to go to 

approximately 80°C. The unit also contains a residual 

gas analyzer, enabling us to monitor and identify ratios 

of the permeate mixtures. We are able to leverage end 

sealant technology we have patented through Sandia. 

The gases we plan to test for this project include H2, 

He, CH4, CO, CO2, CH4, O2, N2, H2S and SF6, plus 

mixtures of these gases. 

Results 

In the area of thin film membranes, we have 

successfully synthesized micron thick 

aluminosilicate zeolite membranes on alumina disks 

(see Figure 1). Our permeation testing (see Figure 2) 

of the material shows that these membranes are 

defect-free. Defect free is denoted by permeation 

selectivity due to size exclusion by molecular sieving 

through the zeolite pores, and not through crystalline 

defect sites, pin holes, or crystallite mismatches

(pores of this Zeolite are 5.5 Å). Molecules used for 

this test are He (kinetic diameter = 2.6 Å) and SF6

(kinetic diameter = 5.5 Å). Pure gas studies are run 

at room temperature. The only consistent problem 

has been that our membranes have grown on both 

sides of the disk support, even when seeding occurs 

on one side. As a result, our flux through the 

membrane/support is slightly diminished from what 

it would be with only one side membranes. 

Once the membrane is determined to be defectfree, testing on pure gases vital to the steam 

reforming cycle for natural gas to hydrogen fuels can 

 FY 2003 Progress Report 

begin. In the past years we have shown that the 

Sandia aluminosilicate membranes have fluxes on 

the order of 10-6 mole/(m2

Pa sec) and separations of 

H2/N2 61, H2/CO2 80, H2/CH4 = 7, CH4/CO2 11 

[3]. Also, the all-silica Zeolite membranes have 

superior CO2 separation from smaller light gases 

(such as H2) [3,4]. Lifetime stabilities of the 

membranes have been undertaken in this project. In 

over a year of exposure to water vapor, the all silica 

membranes can be recalcined (to clear the pores of 

the zeolites) and retested for light gas selectivities. 

Our studies show good consistency in permeation 

data plus long-term durability in the actual integrity 

of the membrane. Furthermore, we have shown a 

high reproducibility in membrane synthesis 

procedure yielding consistent permeabilities. (See 

Figure 1 and Table 1.) 

We have expanded our research to include 

silicotitanate membrane synthesis. In attempts to 

synthesize ETS-4 and ETS-10 as membranes, we have 

successfully synthesized both ETS-10 and a 

completely novel silicotitanate phase. This new phase 

exhibits initial selectivity toward H2 and good flux 

(10-8 mole/(m2Pa sec)), though complete removal of 

pore-blocking template molecules has not yet been 

achieved through initial calcination procedures. 

Further optimization of the calcination procedure will 

lead to improved results. (See Figure 2.) 

Figure 1.	 Cross Section View by Scanning Electron 

Microscope of a 10 Micron Thick Silicalite 

Zeolite Membrane on an Oxide Coated 

Stainless Steel Porous Support 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

We are also studying zeolite W (a 12-ring, 3D 

pore system) to compare it to the ZSM-5 sinusoidal 

pathway zeolite. We have successfully synthesized 

zeolite W crystals on a membrane. However, it is not 

yet a continuous film. Experiments continue to 

improve this membrane. (See Figure 3.) 

Though not completely understood, these 

results indicate that we can tune the membrane 

materials to have selectivity for various light 

gases. This is even more valuable given that 

crystalline inorganic zeolite membranes are 

FY 2003 Progress Report 

chemically, thermally and mechanically robust 

and stable. In comparison to Pd alloy films, the 

zeolite membranes perform well. According to 

the literature [5], Pd on alumina had relative 

ratios of light gas separations of H2/N2 = 110 at 

elevated temperature of 350C. The flux was also 

low (2 x 10-7 mole/m2Pa sec). Furthermore, we 

have synthesized defect-free aluminosilicate 

zeolite thin films supported on commercially 

available oxide coated stainless-steel supports 

(SS316); industry needs stainless steel to make 

membranes an economically viable technology. 

Figure 2.	 Cross Section of Novel Silicotitanate 

Crystalline Membrane on an Alumina 

Support 

Figure 3. Cross Section of Zeolite W Crystals Grown 

on an Alumina Support 

Table 1. Permeation values for pure gases at room temperature on various silicalite membranes; "regenerated" is 

calcined after one year exposure to water vapor. Flux = 10-7 mole/m2 s Pa); Trans-membrane pressure = 

16 psi. 

Gas / (Kinetic i (Å)) 

Membrane 

He 

(2.6) 

SF6 

(5.5) 

H2 

(2.8) 

CO2 

(3.3) 

O2 

(3.5) 

CH4 

(3.8) 

N2 

(3.6) 

CO 

(3.7) 

18A 1.8 < 0.05 2.4 2.9 1.4 - - 1.6 

21A 1.2 < 0.04 1.6 3.0 1.3 1.7 1.1 -

22A 1.5 < 0.02 2.0 5.9 1.2 3.2 1.4 1.4 

22B 1.5 < 0 .03 2.9 4.9 - - - -

22B regenerated" 1.1 - 1.4 2.9 - - - -

28A 0.8 < 0.03 1.9 5.1 1.3 2.6 1.6 1.6 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

There is a great need for robust, defect-free, 

highly selective molecular sieve (zeolite) thin film 

membranes for light gas molecule separations in 

hydrogen fuel production from CH4 or H2O sources. 

They contain an inherent chemical, thermal and 

mechanical stability not found in conventional 

membrane materials. Our goal is to utilize those 

zeolitic qualities in membranes for the separation of 

light gases, and to eventually partner with industry to 

commercialize the membranes. To date, we have 

successfully: 

•	 Demonstrated (through synthesis, 

characterization and permeation testing) both the 

ability to synthesize defect-free zeolitic 

membranes and use them as size selective gas 

separation membranes; these include 

aluminosilicates, silicates, silicotitanates, and 

phosphate-based phases. 

•	 Built and operated our in-house light gas 

permeation unit; we have amended it to enable 

testing of CO gases, mixed gases, and at high 

temperatures. We are initiating further 

modification for H2S permeation studies. 

•	 Synthesized membranes on commercially 

available oxide and composite disks (this is in 

addition to successes we have had in 

synthesizing zeolitic membranes to tubular 

supports [6]). 

•	 Synthesized a number of novel bulk and 

membrane silicotitanate and aluminosilicate 

phases, including the Si/Ti membrane that 

exhibits selectivity for H2. 

References 

1. Tavolaro, A.; Julbe, A.; Guizard, C.; Basile, A.; 

Cot, L.; Drioli, E. "Synthesis and 

characterization of a mordenite membrane on an 

?-Al2O3 tubular support." J. Mater. Chem. 2000, 

10, 1131. 

2. Lai, R.; Gavalas, G. R. "ZSM-5 membrane 

synthesis with organic-free mixtures." 

Microporous and Mesoporous Materials, 2000, 

38, 239. 

 FY 2003 Progress Report 

3. Nenoff, T. M.; Bonhomme, F. "Defect-free thin 

film membranes for hydrogen separation and 

isolation." 14th World Hydrogen Energy 

Conference Proceedings, Montreal, Canada, 

2002, in press. 

4. Bonhomme, F.; Welk, M. E.; Nenoff, T. M. "CO2 

selectivity and lifetimes of high silica ZSM-5 

membranes". Micro. & Meso. Materials, 2003, in 

press. 

5. Chou, K. S.; Wang, S. M. "Studies on the 

preparation of Pd/alumina/porous stainless steel 

membranes for hydrogen separation." J. Chinese 

Inst. Chem. Eng., 2000, 31, 499. 

6. Thoma, S. G.; Nenoff, T. M. "A New Method for 

Synthesizing Defect-Free Thin Film Membranes: 

Composite Zeolite/Sol-gel Membranes" SD6222, US Patent Submission, 2000. 

FY 2003 Presentations 

M. E. Welk, T. M. Nenoff, F. Bonhomme, "DefectFree Thin Film Membranes for H2 and CO2 

Separation and Isolation", Hydrogen and Fuel 

Cells 2003 Conference and Trade Show, 

Vancouver, BC, Canada, June 2003. 

2. T. M. Nenoff, M. E. Welk, F. Bonhomme, 

"Defect-Free Thin Film Membranes for H2 and 

CO2 Separation and Isolation", Spring National 

ACS meeting, New Orleans, LA, March 2003. 

Invited Lecture. 

3. T. M. Nenoff, M. E. Welk, F. Bonhomme, 

"Defect-Free Thin Film Membranes for H2 

Separation and Isolation", National Hydrogen 

Association Meeting, Washington, DC, March 

2003. 

4. T. M. Nenoff, F. Bonhomme, "Defect-Free Thin 

Film Membranes for H2 Separation and 

Isolation", 14th World Hydrogen Energy 

Conference, Montreal, Canada, June 10, 2002. 

FY 2003 Publications 

1. Mitchell, M.; Gallo, M.; Nenoff, T. M. "Molecular 

dynamics simulations of binary mixtures of 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

methane and hydrogen in titanosilicates." J. Phys. 

Chem., 2003, submitted. 

2. Bonhomme, F.; Welk, M. E.; Nenoff, T. M. "CO2 

selectivity and lifetimes of high silica ZSM-5 

membranes." Micro. & Meso. Materials, 2003, in 

press. 

3. Bonhomme, F.; Thoma, S. T.; Nenoff, T. M. "Two 

ammonium templated gallophosphates: Synthesis 

and structure determination from powder 

diffraction data of 2D and 3D-GAPON." Micro. & 

Meso. Materials, 2002, 53, 87. 

4. Nenoff, T. M.; Bonhomme, F. "Defect-free thin 

film membranes for hydrogen separation and 

isolation." 14th World Hydrogen Energy 

Conference Proceedings, Montreal, Canada, 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. Attended HyTeP as SNL speaker/representative in 

Santa Fe, NM, 4/23/03 

2. Invited by Senator Jeff Bingaman (D-NM) for H2 

and Fuel Cell Economic Development discussions 

(included national lab & industry attendees), 

Albuquerque, NM, 4/25/03 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Autothermal Cyclic Reforming Based Hydrogen Generating and 

Dispensing System 

Ravi Kumar (Primary Contact), Shawn Barge, Parag Kulkarni, Court Moorefield, and Vladimir 

Zamansky 

GE Global Research 

General Electric Company 

18 Mason 

Irvine, CA 92618 

Phone: (949) 859-8851 (ext. 159); Fax: (949) 859-3194; E-mail: kumarr@research.ge.com 

James Smolarek, Michael S. Manning, Safdar A. Baksh, and Joseph M. Schwartz 

Praxair Inc. 

175 East Park Drive 

Tonawanda, NY 14151 

Phone: (716) 879-2761; Fax: (716) 879-7218 

Michael Jones 

BP 

Chertsey Road, Sunbury on Thames 

Middlesex, TW16 7LN 

United Kingdom 

Phone: (011) 44 -1932 768265; E-mail: JonesMID@bp.com 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811, E-mail: Mark.Paster@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: Benjamin@cmt.anl.gov 

Objectives 

The overall objective of the project is to develop a reformer-based hydrogen refueling station capable of 

delivering at least 40 kg/day of hydrogen. The specific performance objectives of the refueling system are 

as follows: 

• Produce proton exchange membrane (PEM) fuel cell grade hydrogen (99.99+% purity); 

• Achieve fully automated operation during normal, start-up, shut-down and stand-by modes; and 

• Achieve 75% hydrogen generator efficiency (HHV - higher heating value basis). 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Fuel Processor Capital Costs 

• B. Operation and Maintenance (O&M) 

• C. Feedstock and Water Issues 

• E. Control and Safety 

• Z. Catalysts 

• AB.Hydrogen Separation and Purification 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

•	 Design a pre-commercial 40 kg/day hydrogen generating and refueling system to produce fuel cell 

grade hydrogen from natural gas (NG) based on GE's Autothermal Cyclic Reforming (ACR) process; 

•	 Analyze several process configurations that include ACR reactor, shift reactor, pressure swing 

adsorber (PSA), and heat exchangers and select the best configuration that has high efficiency, high 

reliability and lower capital cost; 

•	 Fabricate and operate the ACR-based hydrogen generator; 

•	 Develop a control system for safe operation of the hydrogen generator with low operation and 

maintenance (O&M) cost; and 

•	 Develop tools to quantify the efficiency, cost and reliability of the system. 

Accomplishments 

•	 Assessed the technical feasibility of the design; 

•	 Defined system layout; 

•	 Designed ACR reactors, shift reactors and PSA; 

•	 Operated low-pressure ACR and shift reactors for extended periods of time; 

•	 Operated PSA on simulated reformate; 

•	 Determined the delivered cost of hydrogen based on ACR technology; and 

•	 Determined the competitiveness of the design relative to alternative concepts. 

Future Directions 

•	 Modify low-pressure reformer design to operate at high pressure; 

•	 Integrate high-pressure ACR system with Praxair's PSA, hydrogen compressor, and storage system; 

and 

•	 Safely install and operate the refueling system at a demonstration site. 

Introduction 

GE is developing a hydrogen generation system 

designed for vehicle refueling. The hydrogen 

generation system uses a proprietary reformer to 

convert hydrocarbon fuels to a hydrogen-rich gas that 

is purified downstream. The ACR process is a 

unique technology that can be applied for the 

production of hydrogen or syngas from different 

fuels, including natural gas, diesel fuel, and 

renewable feed-stocks, such as bio-derived fuels. 

The refueling system also includes a PSA unit to 

purify the hydrogen, a hydrogen compressor, highpressure storage tanks, and a dispensing unit to safely 

deliver the hydrogen from the storage tanks to the 

vehicle. Praxair will develop the PSA unit. They 

will also procure the hydrogen compressor, hydrogen 

storage tanks, and hydrogen dispenser. BP will 

analyze the refueling station logistics and safety. 

ACR is an autothermal cyclic catalytic steam 

reforming technology for converting hydrocarbons to 

a hydrogen-rich stream. The ACR process operates 

in a three-step cycle that involves steam reforming of 

the fuel in a Ni catalyst bed (Step 1 - Reforming), 

heating the catalyst bed through oxidation of the Ni 

catalyst (Step 2 - Air Regeneration), and finally 

reducing the catalyst to the metallic state (Step 3 - 

Fuel Regeneration). The heat required for the 

endothermic reforming step is provided during the 

exothermic air regeneration step. The ACR process 

consists of two reactors cycling between the 

reforming and regeneration (air and fuel) steps to 

produce a continuous stream of hydrogen. The 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

reformer produces a 70% hydrogen stream that is Results 

purified downstream to achieve PEM fuel cell 

quality. The ACR process represents a significant 

technological advancement in comparison with 

autothermal reforming (ATR) and partial oxidation 

(POX), as the ACR-produced syngas is not diluted 

with nitrogen and the overall efficiency of the ACR 

process is higher than that of ATR and POX. When 

compared to conventional steam methane reforming 

(SMR), the ACR process has significantly lower 

capital costs and lower emissions. In addition, the 

ACR process is fuel flexible and has been 

successfully demonstrated using high-sulfur fuels. 

Approach 

The major goal of the ACR-based hydrogen 

generation and dispensing system project is to deliver 

PEM fuel cell grade hydrogen for vehicle refueling at 

the hydrogen cost target of $2.50/kg. The ACR 

technology promises to reduce the capital cost and 

improve the efficiency and reliability of the reformer 

when compared to other reforming technologies 

(SMR, ATR and POX). The project is broken down 

into three phases: Phase I - Conceptual Design and 

Analysis, Phase II - Sub-System Development, and 

Phase III - Prototype Design, Fabrication, and 

Operation. 

In Phase I, a conceptual design of the entire 

ACR-based refueling system was developed. The 

mass and energy balances, process flow diagrams 

and systems design for the ACR reactors and other 

components were completed. A market analysis was 

performed to determine the competitiveness of the 

design relative to alternative concepts. Finally, an 

economic analysis of the system was performed to 

determine if the DOE targets are attainable using 

ACR technology. 

Phase II is sub-system development. The major 

task in this phase is ACR reactor and catalyst 

development. The ACR catalyst will be subject to 

detailed evaluation for fuel conversion efficiency and 

reliability under different operating conditions. 

Phase III is prototype design, fabrication and system 

operation. In this phase, the entire system, including 

the reformer, PSA, hydrogen compressor, and storage 

tanks, will be integrated, installed and operated at a 

demonstration site. 

The conceptual design of the ACR system has 

been finalized. Multiple configurations were 

evaluated from a standpoint of efficiency, reliability, 

and capital cost. One major design issue was 

whether to use high-pressure reforming (150 psig) or 

low-pressure reforming (5 psig) with a syngas 

compressor. It was determined that high-pressure 

reforming was both more efficient and cost effective 

than low-pressure reforming, as shown in Table 1. 

Table 1. Comparison of High-Pressure Reforming and 

Low-Pressure Reforming 

High-Pressure 

Reforming 

(150 psig) 

Low-Pressure 

Reforming 

(5 psig) 

Efficiency (LHV) 75% 71% 

Capital Cost Lower Higher 

Reliability Higher Lower, 

due to syngas 

compressor 

The layout of the selected system is shown in 

Figure 1. The major subsystems of the refueling 

system are reformer, shift reactor, PSA, hydrogen 

compressor, storage tanks, and dispenser. The station 

will be capable of refueling three vehicles 

consecutively. The footprint of the refueling system 

was evaluated. The largest components in terms of 

size are the storage tanks. 

Figure 1. Refueling System Layout 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

A low-pressure pilot-scale reformer was tested 

for extended periods of time. The reformer was 

subjected to several start-stop cycles and operated 

using automated controls. Figure 2 shows that the 

reformer operates in a stable manner, and the 

reformate has about 70% hydrogen. 

Praxair has determined the optimal configuration 

of the PSA for the ACR cyclic process. The PSA 

will be a 3-bed system designed for low capital cost 

as well as easy valve maintenance. Praxair 

performed an extensive evaluation of hydrogen 

compressors based on capital cost, reliability, and the 

ability to meet the performance targets. They chose a 

hydraulically driven compressor. One of the main 

factors for this choice was its oil-free design that will 

help prevent contamination of the hydrogen. The 

compressor has a long, slow stroke that will result in 

higher reliability. The design allows for quick 

maintenance that will decrease O&M cost for the 

system. Praxair is considering both steel and 

composite tanks for the hydrogen storage system. 

The major factors in this selection are safety and 

codes. Multiple methods to fill the vehicle were 

evaluated, and it was concluded that a cascade 

system was optimal. 

A detailed cost analysis of the entire refueling 

station was performed to estimate the cost of 

delivered hydrogen. The model takes into account 

the system capital cost, O&M cost, and fuel and 

consumables costs. Figure 3 shows the cost of 

delivered hydrogen at different system capacities and 

mass production rates. The plot shows that the 

refueling system can meet the DOE target at higher 

capacities (>20,000 scfh) and when mass-produced 

(>500 units/year). 

A sensitivity analysis was performed on the 

factors that affect the cost of delivered hydrogen (see 

Figure 4). The factors that were varied were: NG 

cost, O&M cost, capital cost, efficiency, and 

availability. Each of these factors were varied one at 

a time. Figure 4 shows the cost of delivered H2 at 

the mean value for each of the factors (center points), 

as well as the variability in the cost of H2 due to the 

variability in each of the factors. For example, as 

shown in Figure 4, the cost of NG has a mean of $4/ 

Figure 3. Cost of Hydrogen Estimated for Various 

System Sizes and Mass Production Rates 

Figure 2. Performance of ACR Figure 4. Sensitivity Analysis of Cost of Hydrogen 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

MMBtu and a variability of $3.50-$5.00/MMBtu. 

This results in a delivered cost of H2 with a mean of 

$2.65/kg and a variability of $2.47-$2.92/kg. The 

analysis determined that the variability in cost of 

hydrogen will be primarily due to variability in NG 

cost, capital cost, and availability. 

Conclusions 

The process design of the reformer, shift reactor, 

and PSA has been completed. The design was 

optimized to increase efficiency, decrease capital 

costs, and improve reliability. 

The process and economic analysis determined 

that high-pressure reforming is better than lowpressure reforming for the ACR-based hydrogen 

generator. A low-pressure reformer was operated for 

extended periods using automated controls. The 

reformer operated in a stable manner and delivered a 

70% hydrogen stream to the shift reactor. The design 

of the low-pressure reformer is being modified to 

allow the reformer to operate at high pressure. The 

design of the shift reactor has been completed. 

After extensive analysis, a three-bed PSA design 

was chosen over other bed designs in order to reduce 

capital costs as well as to reduce operation and 

maintenance costs. Vendors for hydrogen 

compressor, storage tanks, and dispenser have been 

 FY 2003 Progress Report 

identified. Hydro-Pac was chosen for the hydrogen 

compressor because of their unique slower speed 

hydraulic drive unit and successful prior experience 

with Praxair in high-pressure gaseous nitrogen and 

argon compression. Praxair is considering both steel 

and composite tanks for the hydrogen storage 

system. Fueling Technologies Incorporated has been 

chosen as the vendor for the dispenser. Multiple 

methods to fill the vehicle were evaluated, and it was 

concluded that a cascade system is optimal. 

The economic analysis indicated that the 

refueling system will meet the hydrogen cost target 

of $2.50/kg at capacities greater than 20,000 scfh and 

when mass-produced in greater than 500 units/year. 

FY 2003 Publications/Presentations 

1. Hydrogen Refueling System Based on 

Autothermal Cyclic Reforming, Kumar, R., 

International Energy Agency Annexe XV 

Meeting, Palm Springs, CA, November 17-18, 

2002. 

2. Hydrogen Refueling Station Based on 

Autothermal Cyclic Reforming, Kumar, R., 

Barge, S., Kulkarni, P, Moorefield, C, Zamansky, 

V., Fuel Cell Seminar, Palm Springs, CA, 

November 18-22, 2002. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Technical Analysis: Evaluation of Metal Hydride Slurries 

Stephen Lasher (Primary Contact) and Peter Teagan 

TIAX LLC 

Acorn Park 

Cambridge MA, 02140 

Phone: (617) 498-6108; Fax: (617) 498-7054; E-mail: lasher.stephen@tiax.biz 

DOE Technology Development Manager: Peter Devlin 

Phone: (202) 586-4905; Fax: (202) 586-9811; E-mail: Peter.Devlin@ee.doe.gov 

Objectives 

•	 Assess the potential economic, environmental, and other benefits of using metal hydride slurries in a 

small-scale hydrogen distribution system (H2 mini-grid) for both hydrogen vehicle fueling (H2 station) 

and proton exchange membrane (PEM) fuel cell power systems (FCPSs) for combined building heat 

and power (cogen). 

•	 Assess the viability of using fluorinated (or otherwise treated) metal hydrides for the purification of 

carbon monoxide (CO)-containing hydrogen streams. 

•	 Establish R&D objectives for the development of hydrogen purification and H2 mini-grids using metal 

hydride slurries. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Production 

•	 AB.Hydrogen Separation and Purification 

•	 AD.Market and Delivery 

Delivery 

•	 A. Lack of Hydrogen/Carrier and Infrastructure Options Analysis 

•	 E. Solid and Liquid Hydrogen Carrier Transport 

Storage 

•	 V. Life Cycle and Efficiency Analysis 

Approach 

•	 Develop conceptual designs and evaluate the cost and efficiency of metal hydride slurry-based 

purification, storage, and delivery for H2 stations and direct hydrogen FCPSs and compare to 

conventional systems (i.e. pressure swing adsorption purification, compressed hydrogen storage/ 

delivery, and reformate-based FCPSs). 

•	 Determine cost of electricity (COE), hydrogen costs, energy use, greenhouse gas (GHG) emissions, 

and other emissions for FCPSs and H2 stations utilizing both conventional and metal hydride slurry 

technology. 

•	 Perform a molecular-level theoretical evaluation of the long-term feasibility of fluorinated metal 

hydride purification. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Search for alternative protection methods or compounds that are even more effective in a practical 

application. 

Accomplishments 

•	 Developed conceptual designs and estimated capital costs for compressed hydrogen (cH2)-based minigrids and FCPSs. 

•	 Constructed FCPS performance model with various building load profiles and FCPS efficiency 

calculations as inputs. 

•	 Developed overall cost assessment and determined preliminary annual costs for reformate and direct 

hydrogen FCPSs. 

•	 Integrated Phase I conceptual designs and capital costs for cH2- and metal hydride slurry-based H2 

stations into FCPS performance model and overall cost assessment. 

Future Directions 

•	 Develop conceptual designs, evaluate efficiency, and estimate capital costs for metal hydride slurrybased mini-grids and FCPSs. 

•	 Update FCPS performance model for metal hydride slurry-based systems. 

•	 Refine capital cost estimates and evaluate hydrogen distribution costs for both cH2- and metal hydride 

slurry-based mini-grids on a $/kg basis. 

•	 Refine capital cost estimates and evaluate COE for cH2-, reformate-, and metal hydride slurry-based 

FCPSs. 

•	 Compare hydrogen costs, energy use, GHGs, and other emissions for the FCPS, H2 mini-grid, and H2 

station utilizing both conventional and metal hydride slurry technologies. 

•	 Evaluate other benefits of distributed generation and H2 mini-grids. 

•	 Use molecular modeling to describe a fluorinated layer of metal hydride on top of the virgin hydride. 

•	 Establish selectivity of CO/H2 separation based on energy surface calculation for transport through the 

fluorinated layer. 

•	 Use the results to determine viability of fluorinated hydrides and develop and test hypothesis for 

optimization of the barrier layer. 

Introduction 

In Phase I, completed last year, the professionals 

at TIAX evaluated the potential cost and 

performance improvements that alternative and 

incipient hydrogen purification technologies could 

have over conventional pressure swing adsorption 

(PSA). The analysis indicated that the use of 

fluorinated metal hydrides in slurry form could 

reduce hydrogen cost and improve safety over 

conventional PSA purification with compressed 

hydrogen (cH2) storage (Lasher et al 2002). In 

addition, if waste heat could be used to provide the 

heat for hydrogen desorption, metal hydride slurries 

could result in efficiency benefits. However, current 

metal hydrides have low tolerance to impurities 

typically found in reformate streams, especially 

oxygen and carbon monoxide. In Phase I, based on 

research results from Japan (Wang et al 1995a,b), we 

assumed that fluorinated (or in some other way 

protected) metal hydrides would be able to 

demonstrate high tolerance to impurities. However, 

significant additional research is required to verify 

these results and develop a stable and effective 

protective layer on the metal hydride. 

Metal hydride slurry is a suspension of a metal 

hydride in an inert liquid, such as a light mineral oil 

or liquid alkane. The slurry is assumed to have no 

impact on the intrinsic hydride performance (e.g. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

hydrogen capacity, hydrogen uptake kinetics, 

thermodynamics), but can result in overall systemlevel improvements such as higher heat transfer 

rates, easier transport (i.e. pump-able), and lower risk 

of impurities poisoning due to the liquid/gas 

equilibrium constant. A promising application 

identified for metal hydride slurries was combined 

purification, storage, and distribution in a small-scale 

hydrogen distribution system (H2 mini-grid). Direct 

hydrogen PEM fuel cell power systems (FCPSs) 

utilizing H2 mini-grids could improve reliability, 

cost, start-up time, emissions, and noise compared to 

reformate-based systems. In addition, producing 

hydrogen centrally for both vehicle fueling and 

FCPSs via a H2 mini-grid provides an early market 

and fuel infrastructure for direct hydrogen vehicles. 

In the metal hydride slurry mini-grid concept, 

reformate would be produced at a H2 station, and 

hydrogen would be absorbed into the metal hydride 

slurry while impurities would be stripped out. Then, 

some of the metal hydride slurry would be pumped 

through pipelines to local buildings, where pure 

hydrogen would be desorbed and used to generate 

power in distributed FCPSs. The spent hydride 

slurry would then be pumped back to the H2 station 

through a separate pipeline (perhaps concentric 

pipelines) for regeneration. Additional hydrogen 

capacity would be required at the H2 station to meet 

vehicle fueling demands. This application has the 

potential advantages of being safer and requiring 

smaller pipe diameters than low pressure (~ 10 atm) 

cH2 distribution. In addition, overall system 

efficiency could be improved provided the FCPSs 

supply some or all of the heat necessary to desorb 

hydrogen from the metal hydride. 

Approach 

In this phase of work, started in June 2002, we 

are evaluating the feasibility of using metal hydride 

slurries for purification and the potential benefits of 

using metal hydride slurries for hydrogen delivery 

via a H2 mini-grid. 

In order to assess the potential economic, 

environmental, and other benefits of using metal 

hydride slurries in the H2 mini-grid application, we 

have constructed a FCPS performance model. 

Annual hourly building load profiles and fuel cell 

 FY 2003 Progress Report 

system efficiencies are used in the model to 

determine hydrogen requirements from the H2 minigrid and to optimize fuel cell size. In utilityconnected buildings, grid power and natural gas 

demands are also determined, and annual energy 

costs are calculated based on utility rates and the cost 

of hydrogen from the H2 mini-grid. Annual costs to 

the building owner and the cost of electricity (COE) 

are calculated based on the annual energy, 

maintenance, and capital costs of the FCPSs. Annual 

greenhouse gas and other emissions can also be 

determined based on the annual energy demand (i.e. 

hydrogen, natural gas, and grid electricity). The cost 

of hydrogen is calculated based on the capital cost of 

the H2 mini-grid (i.e. distribution cost) plus the 

marginal cost of producing hydrogen at the H2 

station (i.e. marginal production cost). Alternatively, 

hydrogen can be priced at a premium to subsidize 

hydrogen sales to vehicles. 

In order to evaluate the long-term feasibility of 

fluorinated metal hydride purification, we will 

perform molecular-level theoretical calculations 

using first principles and quantum modeling to 

understand the underlying microscopic mechanism 

of a fluorinated metal alloy (e.g. La-Ni-Al). 

We will test two main hypotheses: (1) 

fluorination reduces the binding energy of undesired 

molecular species (e.g. O2 and CO), and (2) the 

diffusion barrier created by the fluorinated surface is 

much lower for hydrogen molecules than for 

undesired molecules. Based on the calculations, we 

will generate a general model for surface protection 

of metal hydrides and formulate general principles 

for protection techniques. resis. 

Results 

A summary of our work in progress and some 

preliminary results and conclusions are presented 

here. The final results and conclusions will be 

detailed in a final report, expected to be completed in 

late fall 2003. 

The National Fire Protection Agency (NFPA), 

the American Society of Mechanical Engineers 

(ASME), the Compressed Gas Association (CGA), 

the Code of Federal Regulations (CFR), the U.S. 

Department of Transportation (DOT), and industry 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

experts were consulted for the design of the cH2 

mini-grid. We assume a delivery pressure equivalent 

to the output of the PSA (~ 10 atm) can be tolerated 

in most applications and no boost compressors are 

required over the short distribution distance (< 2 

miles) of the H2 mini-grid. We have estimated 

material, construction, “right-of-way”, and “right of 

eminent domain” costs based on vendor quotes and 

additional cost assessments. Total capital cost for 4-

inch pipe is estimated to vary between $250,000 and 

$600,000 per mile depending on location (rural, 

suburban, or urban). Right-of-way costs dominate in 

most cases. 

Hourly electric and heat (space and water 

heating) load profiles for residential and commercial 

buildings in various locations have been generated 

for a typical meteorological year (TMY) using DOE 

EnergyPlus software. The load profiles are used in 

the FCPS performance model to calculate FCPS 

power demand (FCPS turns on when the building 

demand exceeds design power), cogen use (only 

when fuel cell is on and building heat is needed), and 

monthly utility demands. Example load profiles are 

shown in Figures 1 and 2. Note that the electric and 

space heating demands vary significantly from the 

winter to summer. 

We constructed FCPS models using HYSYS 

process modeling software to evaluate system 

parameters that can affect system efficiency and 

cogen potential. The efficiency and cogen results are 

Figure 1.	 24-Hour New York City Fast Food 

Restaurant Load Profile - Winter Day 

Example 

used in the FCPS performance model to calculate 

hydrogen (or natural gas) demand and actual cogen 

utilization. An example of a system level parametric 

analysis is shown in Figure 3. Note that low 

temperature and high pressure FCPS operation 

increases cogen capabilities because less heat is 

required for anode and cathode humidification. 

HYSYS models for the H2 stations were developed 

in Phase I. 

A FCPS performance model has been 

constructed using the building load profiles and 

FCPS efficiency and cogen calculations. The model 

calculates the FCPS and utility energy demands for 

every hour of a TMY for various building types. We 

have estimated preliminary annual costs for direct 

hydrogen and reformate-based FCPSs using the 

FCPS performance model with typical utility rates 

and estimates for hydrogen, FCPS capital, and 

maintenance costs. Examples of the annual cost 

Figure 2.	 24-Hour New York City Fast Food 

Restaurant Load Profile - Summer Day 

Example 

Figure 3. Parametric Analysis using HYSYS Models - 

Direct Hydrogen FCPS Example
 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

estimates are shown in Figures 4 and 5. Note that in 

Figure 4, smaller FCPSs suffer from poor economies 

of scale (more expensive capital on a $/kWe basis) 

and larger FCPSs suffer from low utilization. 

The examples in Figures 4 and 5 assume the 

following: 

•	 FCPS operates only when the building demand 

for power meets or exceeds the FCPS design 

power. 

•	 Low-temperature cogen assumes the FCPS waste 

heat (i.e. cogen potential) can be used to meet 

some or all of the building hot water demand 

(61-74°C) when the FCPS is operating. 

Figure 4. Preliminary FCPS Annual Costs with and 

without Cogen - Direct Hydrogen Example 

Figure 5. Preliminary FCPS Annual Cost Breakdown - 

50 kWe with High-temp Cogen Example 

 FY 2003 Progress Report 

•	 High-temperature cogen assumes some or all of 

the hot water and space heating demands (74-

94°C) can be met when the FCPS is operating. 

•	 Utility stand-by charges are zero. 

•	 The installed capital costs for 50-kWe direct 

hydrogen and reformate-based FCPSs are 

$24,500 and $44,500, respectively (assuming 

high volume manufacturing). 

•	 FCPS stack and fuel processor catalyst bed lives 

are 40,000 hours. 

•	 Hydrogen is sold to the building owner for just 

$1.00/kg, representing the marginal cost to produce hydrogen at the H2 station. This does not 

include the cost of distribution through the H2 

mini-grid (work in progress). 

Conclusions 

Based on the preliminary results, a few 

observations can be made: 

•	 There is an optimum FCPS size that will depend 

on the building load profile (i.e. utilization) and 

assumed economies of scale (see Figure 4). 

•	 It is not clear whether cogen (high- or low-temperature) will be attractive for distributed FCPSs 

under the assumed mode of operation and load 

profiles used in this analysis to date (see Figure 

4). The relatively small annual cost savings will 

have to be weighted against additional system 

complexity and reliability concerns. 

•	 Fuel costs (hydrogen or natural gas) dominate 

the annual cost of the FCPSs, assuming capital 

and maintenance cost estimates for high volume 

manufacturing (see Figure 5). 

•	 Hydrogen delivery will have to be relatively 

cheap to maintain competitiveness with reformate-based systems (see Figure 5). However, 

other benefits of the direct hydrogen FCPSs, 

such as improved reliability, quick start-up, and 

quiet and emissions free operation, have not been 

incorporated into the economic analysis to date. 

•	 In the near-term, when capital and maintenance 

costs will be high, both direct hydrogen and 

reformate-based FCPSs will have difficulty competing with the utilities based on energy savings 

alone. Other benefits of FCPS distributed generation will have to be valued (e.g. power quality, 

reliability). 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

References 

1. Lasher, S., M. Stratonova, and J. Thijssen, 

“Hydrogen Technical Analysis”, 2002 Annual 

Progress Report – Hydrogen, Fuel Cells, and 

Infrastructure Technologies Program, DOE, 

EERE, November 2002 

2. Wang, X.L., K. Iwata, and S. Suda, “Hydrogen 

Purification using Fluorinated LaNi4.7Al0.3 

Alloy”, Journal of Alloys and Compounds, 

231:860-864, 1995a 

3. Wang, X.L., and S. Suda, “Stability and Tolerance 

to Impurities of the Fluorinated Surface of 

Hydrogen-Absorbing Alloys”, Journal of Alloys 

and Compounds, 227:58-62, 1995b 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Water-Gas Shift Membrane Reactor Studies 

Richard Killmeyer (Primary Contact), Kurt Rothenberger, Bret Howard, Michael Ciocco, Bryan 

Morreale, Robert Enick, Felipe Bustamante 

National Energy Technology Laboratory 

P.O. Box 10940 

Pittsburgh, PA 15236 

Phone: (412) 386-6409; Fax: (412) 386-5920; E-mail: richard.killmeyer@netl.doe.gov 

DOE Program Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov 

Objectives 

•	 Evaluate water-gas shift (WGS) reaction kinetics and membrane flux using industrial gas mixtures and 

conditions 

•	 Test the feasibility of enhancing the WGS reaction at high temperature without added catalysts by 

using a membrane reactor 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 M. Fuel Processor System Integration and Efficiency 

• N. Cost 	 

Approach 

•	 Complete reverse kinetics and Computational Fluid Dynamics (CFD) modeling to optimize reactor 

geometry for forward reactions 

•	 Measure forward kinetics in quartz & Inconel reactors to determine reactor wall catalysis 

•	 Measure forward kinetics in reactor packed with membrane material to determine catalytic activity 

•	 Measure membrane H2 permeability in presence of clean syngas components 

•	 Conduct forward water-gas shift using a membrane reactor at favorable conditions 

Accomplishments 

•	 Conducted first-ever high temperature and high pressure reverse WGS reaction kinetics study 

•	 Determined catalytic effect of reactor shell material on WGS reaction 

•	 Conducted CFD simulations to determine effect of reactor geometry on kinetics 

•	 Completed intrinsic kinetics testing of the forward WGS reaction 

•	 Designed and constructed a new hydrogen membrane testing unit with enhanced features for 

membrane reactor testing
 

Future Directions 

•	 Evaluate forward WGS reaction kinetics and the catalytic effect of membrane materials 

•	 Design, construct, and test a Pd-Cu alloy membrane reactor to enhance the WGS 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Determine the effect of sulfur poisoning on catalytic reactor materials, membrane materials, and 

heterogeneous catalyst particles 

•	 Incorporate reaction kinetics results and permeability results into a high temperature, high pressure 

WGS membrane reactor model 

Introduction 

The use of coal as a transition feedstock for a 

hydrogen economy is likely to be accomplished via 

gasification, i.e. the conversion of solid coal into a 

gaseous mixture of CO, CO2, H2O, and H2. The 

hydrogen yield of such gasifier effluent may be 

increased by reacting the CO with additional 

amounts of water, using the so-called water-gas shift 

(WGS) reaction. Although the WGS reaction is 

customarily used in industry, the reaction has not 

been explored at the conditions (temperature, 

pressure) envisioned in the gasification process, 

primarily due to non-favorable thermodynamics at 

those conditions. However, high temperature and 

high pressure provide a unique scenario to increase 

the hydrogen yield without the need for an external 

catalyst, while favoring the overall heat-efficiency of 

the coal gasification plant. Moreover, the 

thermodynamics may be enhanced by the use of a 

membrane reactor, which will allow for continual 

removal of pure hydrogen through the walls of the 

reactor (Figure 1). The final products of such a 

reactor would be a high-pressure, pure CO2 stream 

and a pure H2 stream. This project deals with the 

study of the membrane reactor in conditions similar 

to those of a gasifier stream. 

Approach 

The success of a membrane reactor in increasing 

the yield of hydrogen will ultimately depend both on 

a high production rate of hydrogen inside the reactor 

Figure 1. Schematic of a Membrane Reactor for the 

WGS Reaction 

(fast kinetics) and a high rate of flow of hydrogen 

through the membrane (fast permeation rate). The 

knowledge of the reaction kinetics and membrane 

permeation is then required to evaluate the suitability 

of the membrane reactor. 

The reaction kinetics of both the reverse and 

forward WGS reactions were studied in an inert 

environment (non-membrane, quartz reactor) to 

determine the intrinsic kinetics. The effects of high 

pressure and high temperature were addressed. The 

influence of the reactor walls was investigated for a 

high-performance alloy (e.g., Inconel 600®); this is 

important in order to model the behavior of the 

reaction in an actual industrial setting. 

Pd-Cu alloys, known for their sulfur tolerance 

(sulfur being one of the main contaminants in the 

gasifier stream), their good mechanical performance, 

and their infinite selectivity towards hydrogen, were 

selected as membrane materials. The membranes 

were characterized in regard to hydrogen permeance 

both with sulfur-free and sulfur-laden gases. Current 

research efforts are focused on the performance of 

the high-temperature, high-pressure water-gas shift 

reaction in a Pd-Cu membrane reactor. 

Results 

The high-pressure, high-temperature reverse 

WGS reaction can be described using an expression 

of the form 

1/ 2 r = k [H ] [CO ] r 2 2 

where [H2] and [CO2] are the concentrations of 

hydrogen and carbon dioxide respectively. This 

suggests that the reaction behaves in a similar way as 

the low-pressure gas-phase reaction. However, the 

values for the rate constant (kr), Figure 2, are 

somewhat larger for the high-pressure reaction. 

Figure 2 also presents the experimental and 

simulation results for the low-pressure reaction. The 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

differences can be explained by considering the 

chemistry of the reaction, which requires an initial 

induction period before reaching steady state. 

The high-pressure, high-temperature forward 

WGS was then studied. The form of the rate 

expression, was similar to that predicted from the 

1/ 2 r = k f [CO] [H 2

O] 

low-pressure mechanism. In this case, both the lowpressure and high-pressure values of the rate constant 

(kf

), Figure 3, are in good agreement, as a result of a 

much shorter induction period. 

There is a dramatic increase in the rate of 

reaction when the reaction is carried out in a metallic 

 FY 2003 Progress Report 

(Inconel 600) reactor. Figure 4 indicates that the 

reaction is 100-fold faster when it takes place in a 

metallic reactor. This behavior is valid for the lowpressure (Figure 4) and high-pressure (Figure 5) 

reactions. As a result, the reaction is fast enough that 

no external addition of catalyst is needed. Surface 

analysis of the Inconel 600 showed a change in the 

chemical composition of the alloy in the surface, 

confirming the catalytic effect brought about by the 

reactor walls. A long-term study of the 

consequences of the stability of Inconel 600 under 

the reaction conditions is required. 

Conclusions 

•	 Reaction kinetics of the high-temperature, highpressure WGS reaction follow the same reaction 

mechanism as the high-temperature, low-presFigure 2.	 Rate Constant as a Function of Temperature Figure 4. Reactor Wall Effects for the Highfor the Reverse WGS Reaction (Experiments Temperature, Low-Pressure Reverse WGS 

were carried out in a quartz reactor) Reaction as a Function of Residence Time 

Figure 3.	 Rate Constant as a Function of Temperature Figure 5. Reactor Wall Effects in the Highfor the Forward WGS Reaction (Experiments Temperature, High-Pressure Reverse WGS 

were carried out in the quartz reactor) Reaction as a Function of Temperature 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

sure reaction. No significant effect of high pressure in the rate constant was observed. 

•	 Inconel 600 is a strong enhancer of the WGS 

reaction. As a result, the reaction achieves 

equilibrium conversions at relatively low temperature. 

FY 2003 Publications/Presentations 

1. F. Bustamante et al., “Reverse WGS Reaction 

Kinetics at Elevated Temperature and Pressure in 

Quartz and Inconel Reactors,” AIChE Meeting, 

Indianapolis IN, November 2002. 

2. F. Bustamante et al., “Kinetics of the 

Homogeneous WGS Reverse Reaction at 

Elevated Temperature,” AIChE Journal, in press 

summer 2003. 

3. M. Ciocco et al., “Hydrogen from Coal: WGS 

Membrane Reactor Studies,” International Coal 

Utilization Conference, Clearwater FL, March 

2003. 

4. R. Killmeyer et al., “WGS Membrane Reactor 

Studies,” EE HFCIT Annual Merit Review 

Meeting, Berkeley CA, May 2003. 

References 

1. Graven, W., Long, J. J. Am. Chem. Soc. 1954, 76, 

2602, 6421. 

2. Tingey, J. J. Phys. Chem. 1966, 70, 1406. 

 FY 2003 Progress Report 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Integrating a Hydrogen Energy Station into a Federal Building 

Stefan Unnasch (Primary Contact), Scott Fable 

TIAX LLC 

1601 S. De Anza Blvd., Suite 100 

Cupertino, CA 95014 

Phone: (408) 517-1563; Fax: (408) 517-1553; E-mail: unnasch.stefan@tiax.biz 

DOE Technology Development Manager: Sigmond Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmond.Gronich@ee.doe.gov 

Subcontractors: Bevilacqua-Knight, Inc., Sacramento, CA 

Objectives 

• Evaluate combined fuel cell power/hydrogen production systems (Energy Stations): 

- Analyze energy station systems with 50-kW proton exchange membrane fuel cells (PEMFCs) that 

are suitable for installation in Federal buildings 

- Analyze options for system components, including direct hydrogen and reformate fuel cells and 

various storage, power production, and hydrogen usage configurations 

- Determine costs and energy efficiency for different system configurations 

• Assess integration with buildings and potential for cogeneration: 

- Analyze potential for heat recovery from fuel cell/hydrogen production systems 

- Identify potential for cogeneration in Federal building applications 

• Identify potential fleets for vehicle operation 

• Establish partnerships for hydrogen fueling and power sales 

• Identify barriers to hydrogen use 

• Make recommendations for future development 

• Identify potential opportunities to develop fuel cell energy stations 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• Hydrogen Production 

- B. Operation and Maintenance (O&M) 

- E. Control and Safety 

• Hydrogen Storage 

- V. Life Cycle and Efficiency Analyses 

• Fuel Cells 

- F. Heat Utilization 

• Technology Validation 

- C. Hydrogen Refueling Infrastructure 

- I. Hydrogen and Electricity Coproduction 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Education 

- B. Lack of Demonstrations or Examples of Real World Use 

Approach 

•	 Analyze integrated power and fueling system 

•	 Explore private and public partnerships 

•	 Identify barriers to hydrogen use 

Accomplishments 

•	 Developed list of possible components that will comprise hydrogen generation and dispensing stations 

•	 Developed list of relevant system configurations from possible components, with detailed description 

and schematics of proposed system configurations 

•	 Selected a baseline system configuration, and initiated a detailed system cost and performance analysis 

•	 Prepared comprehensive list of potential operating configurations 

•	 Surveyed potential public/private fleets and Federal buildings for siting a hydrogen energy station 

•	 Initiated evaluation of building integration and prepared comprehensive list of potential building 

interfaces 

•	 Determined and contacted sites best suited for hydrogen energy station 

•	 Created general process flow diagram (PFD) representing potential hydrogen energy station fluid/ 

energy flows for target site system 

•	 Evaluated emissions benefits for hydrogen energy station operation relative to conventional energy 

sources 

Future Directions 

•	 Continue the analysis and identification of energy station applications at target sites 

•	 Analyze the cost, emissions, and energy utilization benefits of integrated power and fueling for 

specified site 

•	 Identify the key technology, cost, and public perception barriers to hydrogen use 

•	 Make recommendations for future development 

Introduction 

The purpose of this technical analysis is to 

evaluate potential synergies between transportation 

and stationary applications to accelerate development 

of a hydrogen infrastructure through the installation 

of 50-75 kW stationary fuel cell-based energy 

stations at Federal building sites. The various 

scenarios, costs, designs and impacts of such a 

station are quantified in a cost-shared project that 

utilizes a natural gas reformer to provide hydrogen 

fuel for both the stack(s) and a limited number of fuel 

cell powered vehicles, with the possibility of using 

cogeneration to support the building heat load. 

Approach 

To carry out this analysis project as effectively as 

possible, TIAX structured it to consist of six major 

tasks. During the first phase of the project (FY 

2002), TIAX completed the first three tasks. During 

the second phase of the project, TIAX will use the 

results from the first phase to complete the following 

three tasks. 

Task 4 — Analyze Integrated Power and Fueling. 

This task involves a more detailed analysis and 

modeling of the technologies and system designs that 

were selected in Task 1. This analysis will evaluate 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

and quantify the costs, emissions, energy flows, 

number of vehicles to be fueled, and optimal fueling 

and storage time for each of the selected systems and 

technologies. 

Task 5 — Explore Private and Public 

Partnerships. This task involves contacting potential 

public/private partnerships to determine their 

interest/plans to engage in such ventures. Part of this 

investigative process will be to determine existing 

and planned public/private partnerships and 

undertakings related to the development of a 

hydrogen fueling infrastructure, and to evaluate their 

success. 

Task 6 — Identify Barriers to Hydrogen Use. 

TIAX will make an assessment and analysis of the 

different types of barriers and obstacles with which 

the development of a hydrogen infrastructure will be 

faced, including: key technological hurdles, cost 

obstacles, policy barriers and needed changes, and 

public perception issues. 

Results 

During FY 2003, the following items were 

accomplished under Task 4: Analyze Integrated 

Power and Fueling Systems. We began to evaluate 

and quantify the emissions, costs, and energy flows 

for each of the selected systems and technologies. 

Figure 1 shows a projection of annual greenhouse gas 

(GHG) emissions for a hydrogen energy station 

supporting passenger vehicles and providing 

electricity and heat for a building. As indicated, the 

GHG emissions associated with supporting a 

comparable gasoline vehicle and the equivalent heat 

and electricity demand for the building using utility 

gas and electricity are twice that of the emissions 

from a hydrogen energy station supporting the same 

energy demand. Figure 2 shows a projection of 

annual criteria pollutant emissions (i.e., NOx, CO, 

and hydrocarbons) for the same cases. Under this 

comparison, operating a comparable gasoline vehicle 

and producing the same level of building energy 

from utility gas and electricity generates 20 times the 

criteria pollutant emissions generated by a hydrogen 

energy station. 

Figure 3 shows a sample cost curve for fuel cell 

stacks. These curves indicate the relationship 

between stack production volume and cost per 

kilowatt. This and similar cost profiles are being 

developed to facilitate an overall cost projection of 

energy stations infrastructure under both small and 

large volume production scenarios. 

Figure 4 provides a sample PFD. PFDs are being 

generated for the target energy station configurations 

to model energy flows between major system 

components. This modeling process facilitates 

system optimization by indicating component 

Figure 1. Annual Greenhouse Gas Emissions Figure 2. Annual Criteria Pollutant Emissions 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Example Fuel Cell Stack Cost Curves 

Conclusions 

•	 TIAX has identified a set of representative technologies and representative operational scenarios 

that are being analyzed to estimate the size, 

power output, and cost of a hydrogen energy station at a target site. 

•	 Hydrogen energy stations provide significantly 

lower GHG and criteria pollutant emissions compared to equivalent conventional vehicle and 

building operation. 

•	 System optimization of an integrated hydrogen 

energy station will take into account system 

operation, capacity, and cost. 

Figure 4. Example Process Flow Diagram 

capacity requirements under a desired energy output. 

Once the system component sizing has been 

determined, the cost of particular components and of 

the overall system can be determined. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen from Renewable Energy Sources: Pathway to 10 Quads For 

Transportation Uses in 2030 to 2050 

Duane B. Myers (Primary Contact), Gregory D. Ariff, Reed C. Kuhn, and Brian D. James 

Directed Technologies, Inc. 

3601 Wilson Boulevard, Suite 650 

Arlington, VA 22201 

Phone: (703) 243-3383; Fax: (703) 243-2724; E-mail: Duane_Myers@DirectedTechnologies.com 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Objectives 

•	 Identify a pathway for producing 10 quads of hydrogen per year for transportation uses from
 

renewable sources in the years 2030 to 2050 (1 quad = 1015 Btu).
 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 T. Renewable Integration 

•	 AD.Market and Delivery 

Approach 

•	 Determine the total potential hydrogen generation from renewable resources in the U.S. in 2030-2050 

to ensure that the production of 10 quads of hydrogen is possible. 

•	 Only the resources that could make a contribution of at least 0.1 quads per year were included: 

biomass, solar, wind, and geothermal. 

•	 The potential hydrogen generation from each of the four resources was determined on a state-by-state 

basis. 

•	 The hydrogen demand for a given state in the year 2040 was estimated by assuming that the per capita 

demand for hydrogen would be proportional to the per capita gasoline usage in that state. 

•	 The cost for hydrogen from each resource was calculated by applying discounted cash flow (DCF) 

analysis for each step along the hydrogen pathway from production to dispensing into vehicles. 

•	 A simulation was created to generate a hydrogen production scenario for the continental U.S. based on 

resource availability, cost, and hydrogen demand. 

Accomplishments 

•	 Determined that the generation of 10 quads of H2 from renewable sources is theoretically feasible in 

2030-2050. 

•	 Estimated the average cost of the 10 quads of hydrogen in the continental U.S. 

•	 Issued Draft report for review (February 2003). 

Future Directions 

•	 Finalize report based on reviewer comments (expected July-August 2003). 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

This report is the final in a series of studies by 

Directed Technologies, Inc. of the cost and 

infrastructure requirements to supply hydrogen for 

fuel cell vehicles (FCVs). The previous studies have 

concentrated on the early development of the 

hydrogen infrastructure to supply a limited number 

of FCVs. In this study, the focus shifts to future 

years in which a significant fraction of passenger cars 

and trucks are FCVs. The goal of the current 

analysis was to develop a technically feasible 

pathway to supply 10 quads (one quad = 1015 Btu) 

per year of hydrogen fuel from renewable energy 

sources for transportation uses in the years 2030 to 

2050. [In this report, the lower heating value (LHV) 

is used when referring to the energy content of a 

fuel.] The midpoint year 2040 was used for 

calculations of resource availability and demand that 

may change over the 20-year period. To put 10 

quads of hydrogen energy in perspective, if the 

passenger vehicles currently on the road were 

converted to FCVs, 10 quads of hydrogen would be 

sufficient to fuel all of those vehicles (based on an 

average 2.2X efficiency gain for FCVs over 

conventional internal combustion engines). 

Approach 

We first determined the total potential hydrogen 

generation from renewable resources in the U.S. in 

2030-2050 to ensure that the production of 10 quads 

of hydrogen is possible. All renewable resources 

were considered; however, only the resources that 

could make a contribution of at least 0.1 quads per 

year were included: biomass, solar, wind, and 

geothermal. Hydrogen from the biomass resources 

was assumed to be produced through gasification and 

steam reforming, and hydrogen from the electricitygenerating resources by water electrolysis. 

(Alternate hydrogen production methods were 

considered, but the lowest-cost routes to hydrogen 

were gasification/reforming from biomass and 

electrolysis from wind, solar, and geothermal 

electricity.) 

The potential hydrogen generation from each of 

the four resources was determined on a state-by-state 

basis. The U.S. totals for hydrogen potential in 2040 

are listed in Figure 1. The hydrogen potential 

 FY 2003 Progress Report 

Figure 1.	 Summary of Hydrogen Availability and 

Usage for each Resource Predicted by the 

Model 

includes the effect of conversion efficiencies 

(gasifier or electrolyzer) and line losses in 

transmission. 

The hydrogen demand for a given state in the 

year 2040 was estimated by assuming that the per 

capita demand for hydrogen would be proportional to 

the per capita gasoline usage in that state (the per 

capita gasoline consumption varies considerably 

from state to state). To calculate the gasoline need 

for a state in 2040, we multiplied the predicted 

population by the current per capita gasoline usage, 

assuming that the relative gasoline use per capita 

remains the same for each state in the future. The 10 

quads of hydrogen was then divided among the states 

in the same proportion as the projected gasoline 

consumption. 

The cost for hydrogen from each resource was 

calculated by applying discounted cash flow (DCF) 

analysis for each step along the hydrogen pathway 

from production to dispensing into vehicles. The 

capital costs for equipment were taken from the 

literature or from projections for future costs for 

renewable technologies. 

A simulation was created to generate a hydrogen 

production scenario for the continental U.S. based on 

resource availability and cost. The model strives to 

simulate an unregulated hydrogen market in which 

consumers in each state buy hydrogen generated 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

from the least expensive available resource from any 

other state. In the simulation, hydrogen is purchased 

in small units (0.0001 quads), with each state 

purchasing the cheapest available hydrogen in each 

buying round until all of that state's hydrogen needs 

are met or the resources are consumed. 

Results 

The resulting costs of hydrogen at the 

dispensing site from the various pathways are 

shown in Figure 2. The hydrogen costs listed on 

Figure 2 include for comparison purposes the cost 

for 500 miles of transmission, although the 

distribution system described below accounts for 

actual transmission miles. 

Figure 2.	 Cost of Hydrogen from Renewable 

Resources, Including 500 Miles 

Transmission from Source to Vehicle 

Dispensing for Reformation Production (top) 

and Electrolysis (bottom) Methods 

Figure 1 shows the simulation results for the 

annual resource availability and consumption. 

Consumption of each resource depends both on its 

availability and on the cost of hydrogen from that 

resource relative to all other resources. While 

biomass and geothermal resources represent a small 

hydrogen potential relative to solar and wind energy, 

these resources make significant contributions to the 

national hydrogen demand due to their relatively low 

cost compared to other renewable resources. Solar 

energy, however, makes no contribution since it is 

considerably more costly than the abundant Class 4 

wind energy with which it must compete. Of 

particular note is that 3.34 quads of the 4.8 quads of 

potential hydrogen from wind classes 5 and 6 goes 

untapped. Much of this unused wind potential is in 

the Midwest and Rocky Mountains, where the high 

transmission cost to the population centers on the 

coasts prohibits higher-class wind from being cost 

competitive with Class 4 wind resources at shorter 

transmission distances. 

The distribution of cost of hydrogen in all states is 

shown in Figure 3, with an average cost of $3.98/kg. 

Generally, the least expensive hydrogen initially 

available to all states is from in-state biomass 

resources, followed by the biomass in neighboring 

states. Nearly half of all hydrogen from biomass is 

consumed in-state, with the amount transported out of 

state (via pipeline) decreasing with increasing interstate distance. The average inter-state pipeline 

distance is 259 miles. As states consume their 

Figure 3. National Hydrogen Cost Histogram (Average 

is $3.98/kg) 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

surrounding biomass resources, they are forced to 

purchase electricity for hydrogen generation, which 

may be transmitted over longer distances. Only 24% 

of renewable electricity is used in-state for hydrogen 

production, and no obvious trend exists for quantity of 

hydrogen transmitted as a function of transmission 

distance. The mean distance for renewable electricity 

transmission is 540 miles. It is interesting to note that 

no resource is transmitted (via electrical lines or 

pipelines) more than 1,500 miles, indicating that 

coastal states reach no further than the middle of the 

country to meet their hydrogen demand. The resulting 

state-by-state cost of hydrogen is shown in Figure 4. 

Conclusions 

The annual generation of 10 quads of hydrogen 

in the years 2030-2050 from renewable sources for 

transportation uses in the U.S. is technically 

achievable and, according to our model, leads to a 

national average hydrogen cost of $3.98/kg ($33.24/ 

GJ, LHV basis), excluding profits. Wind and 

biomass are the most significant resources (on an 

energy supplied basis) for hydrogen production, 

with geothermal playing a small role due to its 

limited potential. 

Hydrogen from renewable electricity is 

expensive compared to that from the reformation of 

biomass for three important reasons. First, most 

renewable electricity, especially wind and solar, is 

expensive compared to electricity from fossil fuels 

due primarily to high capital costs for the wind and 

solar installations with relatively low capacity factors 

 FY 2003 Progress Report 

(all <50%). Secondly, electrolysis incurs large 

capital expenses and additional inefficiencies. 

Lastly, transmission of energy as electricity via 

transmission lines is more costly than hydrogen 

pipelines. 

FY 2003 Publications/Presentations 

1. Duane B. Myers at the National Hydrogen 

Association annual U.S. Hydrogen Conference on 

March 5, 2003. 

2. Duane B. Myers to the DOE H2 Analysis Working 

Group on April 23, 2003. 

Figure 4. Average Delivered Cost of Hydrogen by 

State 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Biohydrogen Production from Renewable Organic Wastes 

Shihwu Sung (Primary Contact), Dennis A. Bazylinski, Lutgarde Raskin 

Dept. of Civil and Construction Engineering 

Iowa State University, Ames IA 50011 

Phone : (515) 294-3896; Fax: (515) 294-8216; E-mail: sung@iastate.edu 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Investigate different strategies for selective growth of hydrogen-producing bacteria (e.g., heat
 

selection and pH control, hydraulic loading) in a mixed culture environment.
 

•	 Determine the biokinetics parameters of hydrogen-producing microorganisms. 

•	 Identify and quantify hydrogen-producing bacterial population in a complex microbial community 

background using nucleic acid based technique - terminal restriction fragment length polymorphism 

(T-RFLP). 

•	 Design and develop improved bioreactor system to favor the growth of hydrogen-producing bacteria. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 H. Fermentative Micro-organisms 

Approach 

•	 Develop batch scale and continuous reactor system to evaluate technical and practical feasibility of 

hydrogen production from synthetic and real waste streams. 

•	 Study the effect of heat treatment of sludge on hydrogen production in a continuous experiment. 

•	 Apply Monod equation to estimate kinetic constants for different types of waste streams. 

•	 Apply nucleic acid based techniques for microbial community identification and quantification. 

•	 Find the correlation between hydrogen yield and the Clostridium sp. in the continuous bioreactor. 

Accomplishments 

•	 Successfully enriched naturally available mixed seed (e.g. compost, soybean soils, anaerobic digester 

sludge, etc.) to microbial culture rich in hydrogen-producing bacteria. 

•	 Accomplished a hydrogen yield of 2.2 mole/mole of sucrose by using mixed microbial culture with 

hydrogen conversion efficiency of 27.5%. 

•	 Developed heat treatment strategy for selective growth of hydrogen producers. 

•	 Evaluated the effect of preheat treatment of seed inoculum at 70-90o

C for 15-20 minutes followed by 

repeat heat treatment of settled sludge on hydrogen yield. 

•	 Determined biokinetics parameters [e.g. specific growth rates (m), half saturation constant (Ks), 

growth yield (Y)] of hydrogen producers using different substrates. 

•	 Identified and quantified the hydrogen-producing bacteria in a mixed culture environment using 

nucleic acid based technique known as terminal restriction fragment length polymorphism (T-RFLP). 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Evaluate different reactor configurations and control parameters to obtain higher hydrogen conversion 

efficiency using real waste streams, e.g. high fructose corn syrup, molasses, food waste, corn 

processing waste, etc. 

•	 Develop pilot-scale hydrogen production demonstration project using real wastes. 

•	 Continue identification and quantification of hydrogen-producing bacterial population in a complex 

microbial community background using nucleic acid based techniques. 

Introduction 

The environmental consequences of extensive 

use of fossil fuels have already begun to surface. The 

excessive use of fossil fuels is one of the primary 

causes of global warming and acid rain, which have 

started to affect the earth’s climate, weather, 

vegetation and aquatic ecosystems (Hansen et al., 

1981). Moreover, the U.S. relies heavily on imported 

petroleum from nations which are politically 

unstable. Due to global environment and national 

energy security considerations, a non-polluting and 

renewable energy source needs to be developed. 

Hydrogen is a clean energy source, producing water 

as its only by-product when it burns. Besides, 

hydrogen can be produced from renewable raw 

materials such as organic wastes. Therefore, 

hydrogen is a potential clean energy substitute for 

fossil fuels. 

A new fermentation process that converts 

negative-value organic waste streams into hydrogenrich gas has been developed by the Biotechnology 

Research Group at Iowa State University (Van 

Ginkel et al., 2001). The process employs mixed 

microbial cultures readily available in nature, such as 

compost, anaerobic digester sludge, soil, etc., to 

convert organic wastes into hydrogen-rich gas. An 

enriched culture of hydrogen-producing bacteria 

such as Clostridia was obtained by heat treatment, 

pH control and hydraulic retention time (HRT) 

control of the treatment system. The process not 

only generates environmentally clean energy -

hydrogen, but also stabilizes the waste. Thus, the 

newly explored hydrogen fermentation technology 

could curtail the growing energy insecurity and 

eliminate the global and local pollution problems 

resulting from excessive use of fossil fuels. The 

biohydrogen fermentation technology could enhance 

the economic viability of many processes utilizing 

hydrogen as a fuel source or as a raw material. 

Approach 

A series of serum bottle tests were conducted to 

evaluate the environmental factors (e.g. pH and heat 

treatment) affecting biological hydrogen production 

and to investigate the feasibility of biohydrogen 

production from different substrates. Serum bottle 

tests were also conducted to determine the biokinetic 

parameters (e.g. specific growth rate, half velocity 

constant and growth yield) of hydrogen-producing 

bacteria for different substrates. Following the batch 

studies, completely mixed bioreactors were operated 

for continuous hydrogen production using 

anaerobically digested sludge that had been heat 

treated at 100°C for 15 minutes as microbial seed. 

The experimental set-up employed in this study is 

shown in Figure 1. Upon successful start-up, the 

operation of the bioreactor was optimized to 

maximize hydrogen production. The process 

Figure 1. Experimental Setup of Continuous 

Bioreactor 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

optimization included determination of optimum 

operating pH, combination of temperature and 

duration of heating of settled biomass, frequency of 

heat treatment, chemical oxygen demand (COD) 

loading rate and HRT. 

A nucleic acid based technique – DNA 

fingerprinting called terminal restriction fragment 

length polymorphism (T-RFLP) – was used to 

identify the abundant populations in a complex 

microbial community background. This method 

involves the extraction of DNA from the biomass 

samples and the amplification of the 16S ribosomal 

DNA (16S rDNA) gene using the polymerase chain 

reaction (PCR) with appropriate primers. The 

forward primer was labeled with fluorescein. The 

fluorescently labeled PCR products were digested 

with restriction enzymes HaeIII, MspI, and RsaI. 

The fluorescently labeled terminal restriction 

fragments obtained in this manner were separated by 

gel electrophoresis. 

Results 

A series of batch test results showed that a pH of 

5.5 was optimum for hydrogen production without 

any detection of methane as evident from the highest 

hydrogen conversion efficiency as indicated in 

Figure 2. This pH was therefore selected for the 

continuous phase testing. Batch tests also showed 

that heat treatment of seed inocula at 70-90o

C for 15-

20 minutes enhanced the hydrogen production by 

more than five times with respect to control (without 

heat treatment). Such an increase was likely due to 

more favorable conditions to spore-forming 

hydrogen producers by reducing nonspore-forming 

hydrogen consumers. 

Based on biokinetic studies, the specific growth 

rates (μ) of hydrogen-producing bacteria were found 

to be 0.10 hr-1, 0.176 hr-1 and 0.215hr-1 respectively 

for sucrose, non-fat dried milk (NFDM) and food 

waste (produce + deli). These values were 

significantly higher than that for hydrogen-oxidizing 

bacteria (0.055 hr-1) [Rittmann and McCarty, 2001]. 

This suggests that a hydrogen-producing bioreactor 

could be operated at much shorter HRT than the 

conventional methanogenic reactor. Thus, HRT 

could be one of the important factors to select the 

predominance of hydrogen producers in anaerobic 

reactor. The biohydrogen production rates at various 

initial substrate concentrations for different 

substrates are shown in Figure 3. 

Figure 2. Effect of Ph on Hydrogen Production in 

Batch Studies 

Figure 3.	 Biohydrogen Production Rates at Various 

Initial Substrate Concentrations (A) Sucrose; 

(B) Non-Fat Dry Milk; (C) Food Waste 

3 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

A continuous bioreactor was operated for about 

140 days at a substrate concentration of 20 g/L 

(sucrose) in a semi-batch feed at an HRT of 24 hr. 

The seed sludge was preheat-treated at 100°C for 15 

minutes followed by a series of heat treatment at 

70o

C for 20 minutes on day 29 (Phase I), day 113 and 

day 129 (Phase III). The result is presented in Figure 

4. In Phase I, heat treatment was applied to only onethird of total biomass and the reactor showed no 

significant improvement in hydrogen yield. In Phase 

III, when all of the biomass was heat treated, the 

hydrogen production rates increased from 5.0 L/day 

to 8.3 and 13.0 L/day, respectively on day 113 and 

day 129. The corresponding hydrogen yields 

increased from 0.85 mole H2/mole sucrose to 1.42 

and 2.2 mole H2/mole sucrose, respectively on day 

112 and day 130. Thus, the repeated heat treatment 

was effective in selecting hydrogen producers and 

activating spore germination. 

The microbial community analysis conducted at 

University of Illinois Urbana-Champaign during the 

experimental run time is presented in Figure 5. The 

studies showed that the highest level of H2 was 

observed when the populations of Clostridium clusters 

I and II were active in Phases I and III. Thus, repeat 

Figure 4. Biohydrogen Production Rate With Periodic 

Heat Treatment Bioreactor 

Figure 5.	 Dominant Microbial Populations in the 

Reactor as Indicated by T-RFLP Analysis 

With Restriction Enzyme Msei 

 FY 2003 Progress Report 

heat treatment of all biomass was necessary to achieve 

sustainable hydrogen production. Clostridia are 

obligate anaerobic acidogenic bacteria that can form 

spores (endospores) to protect themselves against 

unfavorable environmental conditions, such as high 

temperature; however, when the favorable conditions 

return, they can geminate and become vegetative cells. 

A two-stage reactor with the first stage for 

hydrogen production and the second stage for 

culturing hydrogen producers is currently being 

investigated in our laboratory. 

Conclusions 

•	 An operational pH of 5.5 was shown to be optimal for hydrogen production. 

•	 Hydrogen-producing bacteria have specific 

growth rates 2 to 4 times higher than the hydrogen-oxidizing methanogens. 

•	 Both initial heat treatment of the seed inoculum 

and repeat heat treatments of the biomass during 

the reactor operation promoted hydrogen production by eliminating non-spore forming hydrogenconsuming microorganisms and by activating 

spore germination. 

•	 Sustainable hydrogen production was possible 

with pH control and repeat heat treatment of settled sludge at 70o

C for 20 minutes. 

•	 Terminal restriction fragment length polymorphism (T-RFLP) analysis showed that Clostridium clusters I and II and Bacillus species were 

dominant populations in the bioreactors. 

References 

1. Hansen J, Johnson D, Lacis A, Lebedeff S, Lee P, 

Rind D and Russell G (1981). Climate impact of 

increasing atmospheric carbon dioxide. Science. 

213(4511). 

2. Rittmann B E and McCarty P L (2001). 

Environmental Biotechnology: Principles and 

Application. McGraw-Hill Companies Inc., New 

York. 

3. Van Ginkel S, Sung S and Lay J J (2001). 

Biohydrogen production as a function of pH and 

substrate concentration. Environ. Sci. Technol. 35 

(24): 4726-4730. 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2002 Publications/Presentations 

1. Duangmanee T, Padmasiri S, Simmons J J, Raskin 

L and Sung S. Hydrogen production by anaerobic 

communities exposed to repeated heat treatment. 

In CD-ROM Proceedings of Water Environment 

Federation 75th Annual Conference & Exposition, 

September 28-October 2, 2002, Chicago, IL. 

2. Padmasiri S, Simmons J J, Duangmanee T, Sung S 

and Raskin L. Microbial community analysis in 

hydrogen producing continuous flow bioreactors, 

The 103rd Meeting of the American Society for 

Microbiology, May 19-22, 2003, Washington DC. 

3. Simmons J J, Padmasiri S, Duangmanee T, Sung 

S and Raskin L. Microbial study during hydrogen 

fermentation in continuous flow bioreactors. 

Annual Meeting of the Society for Industrial 

Microbiology, August 10-14, 2003, Minneapolis, 

MN. 

 FY 2003 Progress Report 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Supercritical Water Partial Oxidation 

Michael H. Spritzer (Primary Contact) and Glenn T. Hong 

General Atomics 

3550 General Atomics Court 

San Diego, California 92121 

Phone: (858) 455-2337, Fax: (858) 455-4111, E-mail: michael.spritzer@gat.com 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260, Fax: (202) 586-9811, E- mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Develop a gasification technology that can convert biomass wastes of all types into hydrogen and other 

high-value products. 

•	 Verify that high-pressure supercritical water is an ideal medium for gasification of biomass. 

•	 Show that high hydrogen yields and gasification efficiencies can be reliably achieved with
 

supercritical water partial oxidation (SWPO).
 

•	 Confirm competitive hydrogen production costs of ~$3/GJ (~$0.35/kg) can be achieved with smallsize SWPO gasifiers. 

•	 Demonstrate a 5-ton per day (tpd) reduced-scale gasifier at a small publicly-owned treatment works 

(POTW). 

•	 Construct a 40-tpd commercial biomass gasifier at a large POTW. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

Approach 

•	 Build on 20 years experience with supercritical water oxidation (SCWO) of hazardous wastes. 

•	 Exploit the inherent characteristics of supercritical water (SCW) to convert wet biomass into
 

hydrogen:
 

- SCW quickly gasifies all organics with minimum char 

- Water-gas shift contributes significantly to hydrogen yields 

- SCW scrubs particulates and acids from hydrogen-rich gaseous products 

- High pressures aid in separation/storage of hydrogen 

•	 Develop supercritical water gasification system in a four-step program: 

- Phase I: Pilot scale testing/feasibility studies (complete) 

- Phase II: Technology development (expect recompete/award in 2003) 

- Phase III: System integration and design 

- Phase IV: Reduced scale demonstration of 5-tpd system 

- Design and construct 40-tpd commercial demonstration system 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Performed economic analysis showing that competitive hydrogen production costs of ~$3/GJ (~$0.35/ 

kg) can be achieved with small-size SWPO gasifiers. 

•	 Performed pilot-scale conceptual design of SWPO system for Phase II development. 

•	 Prepared a SWPO development plan, including cost and schedule estimates. 

•	 Prepared a business plan to identify SWPO market potential. 

•	 Carried out SWPO market survey in collaboration with San Diego State University (SDSU). 

•	 Defined follow-on activities from preliminary testing through pilot-scale demonstration of an 

integrated SWPO system. 

•	 Identified improvements to reactor design. 

•	 Submitted Phase I final report in December 2002. 

Future Directions 

Phase II: Technology Development: (2004) 

•	 Design, fabricate and test advanced pilot-scale SWPO reactor. 

•	 Optimize SWPO operating parameters and H2 yields during extended-duration tests. 

•	 Revise market, economic and life cycle cost assessments and define scale-up requirements. 

Phase III: System Integration & Design: (2005) 

•	 Perform safety, reliability and maintenance, and permitting studies. 

•	 Perform process design and long-lead procurement for Phase IV. 

•	 Update development plan for Phase IV. 

Phase IV: Reduced-Scale Demonstration of 5-tpd System: (2006-2007) 

•	 Implement requirements defined during Phase III studies. 

•	 Match reduced-scale SWPO system to industrial H2 separation and storage systems. 

Introduction 

General Atomics (GA) is developing 

supercritical water partial oxidation (SWPO) for the 

efficient and environmentally advantageous 

gasification and hydrogen production from lowgrade fuels such as municipal wastes, biomass, and 

high-sulfur coal. 

SWPO involves carrying out oxidative reactions 

in a supercritical water environment - akin to highpressure steam - in the presence of limited quantities 

of oxidant, typically pure oxygen or air. Partial 

oxidation in-situ rapidly heats the gasification 

medium, resulting in less char formation and 

improved hydrogen yield. The high-pressure, highdensity aqueous environment is ideal for reacting and 

gasifying organics. The high water content of the 

medium encourages formation of hydrogen and 

hydrogen-rich products and is compatible with high 

water content feeds such as sludges and biomass, and 

eliminates the need for feedstock drying. The high 

water content of the medium is also effective for 

gasification of hydrogen-poor materials such as coal. 

Approach 

Figure 1 provides a simplified process flow 

diagram (PFD) for the GA SWPO pilot plant. 

Pressurized slurry is fed to the preheater, where it is 

preheated to a temperature of 250°C or other suitable 

temperature depending on the feed material. It was 

found during testing that slurry preheating had to be 

limited to avoid char formation and plugging of the 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

preheater. In addition, the pumpable concentration of 

biomass slurry was limited, for example to about 10­

15 wt% for wood flour. To overcome these 

limitations, a high organic feed (designated auxiliary 

fuel in Figure 1) is coprocessed with the slurry. As 

shown in Figure 1, the high organic feed and oxygen 

are combined with the preheated slurry at the reactor 

inlet. The reactor has a volume of about 10 liters and 

provides a residence time of 60-75 seconds at an 

operating pressure of 3400 psi and operating 

temperatures of 650 to 800°C. In the reactor, the 

feed is converted primarily to CO2, H2O, H2, CH4 

and CO. The gasifier products are cooled after 

leaving the gasifier and the liquid and gaseous 

products may then be separated at either high or low 

pressure. Figure 2 shows a photograph of the SWPO 

system gasifier skid. 

Results for the SWPO pilot-scale testing were 

reported last year. In the latter half of 2002, the 

Phase I results were analyzed and used to identify 

favorable applications for the SWPO technology. An 

economic analysis was carried out, supported by a 

market survey of municipal sewage treatment plants 

in the U.S. All results were then documented in the 

Phase I Final Report issued in December, 2002. 

Results 

The major results for Phase I are as follows: 

1. Based on successful Phase I testing, the SWPO 

pilot-scale conceptual design for Phase II 

development shall be based on the following: 

•	 Pumping tests indicate that a biomass slurry 

feed concentration of about 12 wt% solids is 

a practical maximum. 

•	 Feed preheat is typically limited to 260°C to 

avoid char formation and plugging. 

•	 A high heating value waste is coprocessed 

with biomass in order to attain the desired 

gasifier temperature and still have sufficient 

feedstock for gasification. Suitable high 

heating value wastes are trap grease, plastics, 

rubber, or coal. 

•	 A vessel-type gasifier rather than a pipe-type 

gasifier is used to achieve higher gasifier 

operating temperatures and minimize heat 

losses. 

•	 A catalyst-free gasifier is used to enable 

long-term operation with dirty feed materials 

without plugging. 

•	 A high-energy nozzle is used for high 

dispersion of the incoming feed to improve 

mixing and attain high gasification yields. 

•	 A methane-steam reformer is used on the 

clean SWPO product gas to reform the 

methane-rich gas to hydrogen. 

Figure 1. Process Flow Diagram for the SWPO System Figure 2. SWPO System Gasifier Skid 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

•	 Due to the low level of CO produced in the 

gasifier, water-gas shift reactors are not 

necessary. 

2. A nationwide web-based survey of municipal 

sewage treatment plants received over 100 

responses. The survey indicates that sludge solids 

disposal costs are usually above $100 per dry ton 

and range up to $500 per dry ton. 

3. An economic analysis for coprocessing of sewage 

sludge and waste grease was performed. Results 

show that competitive hydrogen production costs 

of ~$3/GJ (~$0.35/kg) can be achieved with 

small-size SWPO gasifiers. Table 1 shows the 

key parameters of the analysis. Figure 3 shows 

how the hydrogen production cost varies with 

financing terms and revenue received for 

accepting sludge solids. 

Conclusions 

The Phase I results indicate that a practical 

means to overcome limitations on biomass slurry 

feed concentration and preheat temperature is to 

coprocess an auxiliary high- heating value material. 

SWPO coprocessing of two high-water content 

Table 1. SWPO Economic Analysis Basis 

 FY 2003 Progress Report 

wastes, partially dewatered sewage sludge and trap 

grease, yields a scenario for the production of 

hydrogen at highly competitive prices. It is 

estimated that there are hundreds if not thousands of 

potential sites for this technology across the U.S. and 

worldwide. 

The economics for 40 tpd sewage sludge plants 

augmented with grease trap waste are favorable over 

a significant range of cost parameters such as sludge 

revenue and capital financing. Hydrogen production 

costs for SWPO plants of this size are projected to be 

about $3/GJ (~$0.35/kg) or less. Economics may be 

further improved by future developments such as 

pumping of higher solids content sludges and 

improved gasifier nozzle designs to reduce char and 

improve hydrogen yields. The easiest market entry 

for SWPO is expected to be sales to municipal 

wastewater treatment plants for use with sewage 

sludge in conjunction with trap grease, as both of 

these wastes are ubiquitous and have reasonably 

well-defined negative value (i.e., the process will 

receive revenue to accept the feed). Additionally, 

waste grease is frequently recovered at municipal 

wastewater treatment plants where it is already 

contaminated with sewage. 

Description Assumption Reference 

Plant size 40 tpd total solids, 30 tpd organic 

sludge solids (not grease) 

Numerous plants of this size in the US and 

worldwide 

Sludge solids 

revenue $0-300 per dry ton SDSU survey 

Gasifier residence 

time 20 seconds 15 seconds for UHM, 1998 

Trap grease 

revenue $0.08 per gallon Darling/Al Max telecons 

Steam revenue $3.50 per MMBtu (? 1000 lb) Yeboah et al., 2002 

Cost of liquid 

oxygen (LOX) $0.04 per pound Vendor discussions 

Hydrogen purity 99.99% Typical purity level with pressure swing 

adsorption 

Financing rate 6 to 12% Current prime interest rate is below 5% 

Financing period Up to 20 years City of San Diego methane contract is a 20-yr 

term 

4 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Hydrogen production cost for sewage sludge 

with trap grease. Solid lines show cases 

where the amount of grease supplied equals 

the amount necessary to raise the combined 

feeds to the final gasifier temperature of 

650°C and all of the grease or its equivalent 

is completely oxidized to H2O and CO2. The 

dashed lines show cases where the amount of 

grease has been doubled. The dotted lines 

show cases where the amount of grease has 

been tripled. For each grease ratio, six 

different financing arrangements are shown. 

From left to right, these are 20 years at 6%, 

20 years at 12%, 10 years at 6%, 10 years at 

12%, 5 years at 6%, and 5 years at 12%. 

SWPO should also be favorable to other market 

applications in which low or negative value, high 

water content biomass is available in conjunction 

with a low or negative value fuel material. For 

biomass slurries, primary candidates are sewage 

sludge, manure sludge, and shredded and/or 

composted organic municipal solid waste (MSW) 

slurries. For the high heating value stream, primary 

candidates are trap grease, waste plastic or rubber 

slurries, and coal or coke slurries. 

The next phase of the SWPO program will be 

focused on verifying process improvements 

identified during the preliminary pilot-scale testing, 

and then performing extended duration testing with 

the GA pilot plant. Tests of at least 100 hours 

duration using sewage sludge and trap grease as 

simultaneous feedstocks are a primary objective. 

Follow-on Phases III and IV of the SWPO program 

will develop and demonstrate a dedicated 5-tpd 

reduced-scale SWPO facility at a location such as the 

Encina municipal wastewater treatment plant. 

Subsequent to this demonstration, the technology 

will be ready for a commercial-scale demonstration. 

While there are clearly technical challenges that 

must still be addressed, such as demonstration and 

scale-up of the technology, SWPO represents an 

outstanding opportunity to further the dual goals of 

developing a hydrogen economy and practicing 

environmentally friendly waste disposal. It may well 

represent one of the few scenarios in which hydrogen 

may be produced economically from biomass at a 

relatively small scale. SWPO could thus play a 

pivotal role in the proliferation of distributed 

hydrogen generation. As an additional benefit, the 

high operating pressure of the process presents 

opportunities for the recovery of high pressure 

hydrogen product without the high cost of 

compression. 

References 

1. University of Hawaii at Manoa, "Hydrogen 

Production from High Moisture Content Biomass 

in Supercritical Water", M.J. Antal Jr. and X. Xu, 

Proceedings of the U.S. DOE Hydrogen Program 

Review, Alexandria, VA, April 28-30, 1998a. 

2. Yeboah, Y.D. et al., "Hydrogen from Biomass for 

Urban Transportation", Proceedings of the U.S. 

DOE Hydrogen Program Review, Golden, CO, 

May 6-8, 2002. 

FY 2003 Publications/Presentations 

1. Spritzer , M.H. and G.T. Hong, "Supercritical 

Water Partial Oxidation", poster paper at the 

Annual Peer Review Meeting, U.S. DOE 

Hydrogen Program, Berkeley, CA, May 2003. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Biological Water Gas Shift Development 

Edward J. Wolfrum (Primary Contact), Gary Vanzin, Jie Huang, Andrew S. Watt, Sharon Smolinski, 

and Pin-Ching Maness 

National Renewable Energy Laboratory 

1617 Cole Blvd. 

Golden, CO 80401 

Phone: (303) 384-7705; Fax: (303) 384-6363; E-mail: Ed_Wolfrum@nrel.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Improve biological water-gas shift (WGS) reaction for producing biomass-derived hydrogen, using the 

photosynthetic bacterium Rubrivivax gelatinosus CBS as the biological catalyst. 

•	 Understand the biological machineries governing the CO-shift process in order to improve both COshift rates and durability. 

•	 Understand high pressure bioreactor dynamics. 

•	 Design, construct, and operate bioreactor capable of operating at elevated pressure. 

•	 Elucidate CO pressure effects on biological CO-shift reaction. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

Approach 

•	 Physiology study to determine energy generation during CO shift. If verified, this would assure 

sustained hydrogen production in darkness. 

•	 Molecular study to clone and characterize genes involved in CO-shift reaction. This would enable us 

to optimize the CO-shift process. 

•	 Integrated bioreactor engineering and operation to understand high-pressure bioreactor dynamics. 

Accomplishments 

•	 Physiological studies have confirmed that adenosine triphosphate (ATP) is generated dur-ing CO shift, 

which simplifies dark bioreactor operation and maintenance while improv-ing its durability. 

•	 Molecular biology studies have identified 16 genes involved in CO shift, which enables us to
 

manipulate them for over-expression of CO-shift activity.
 

•	 Developed a novel recirculating bubble-column reactor which provides good gas-liquid mass transfer. 

•	 Obtained intrinsic CO-shift kinetics of Rubrivivax gelatinosus at various CO concentrations. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Understand the biochemistry of the hydrogenase enzyme in the CO-shift pathway. The CO-shift 

hydrogenase is durable and more tolerant to oxygen, unlike most hydrogenases reported in literature. 

An in-depth investigation could result in insight regarding a structure-function relationship. 

•	 Continue to understand the genetic system of the CO-shift hydrogenase. This knowledge would allow 

its genetic transfer to other microbial systems for fermentative and photo-lytic hydrogen production. 

•	 Elevated-pressure bioreactor operation with gaseous substrates is a unique research area. Continued 

development in this area could lead to process improvement and other applica-tions. 

Introduction 

This project is investigating the use of the 

photosynthetic bacterium Rubrivivax (Rx.) 

gelatinosus CBS to quantitatively shift and condition 

crude synthesis gas into a hydrogen-rich stream 

according to the reaction: CO + H2O ↔ H2 + CO2. 

In contrast to conventional high-temperature 

catalytic shift processes, this biologically mediated 

reaction can operate at ambient temperatures, making 

it potentially promising for large-scale H2 

production. This project has two different goals: a 

nearer-term goal to investigate the utility of this 

biological process as an alternative to conventional 

shift technology, and a longer-term goal to 

understand the enzymatic processes involved in the 

CO-to-H2 reaction. 

The nearer-term goal to determine the utility of 

this process as a “drop-in” replacement to the 

conventional high-temperature shift process is 

important because the process may represent a lessexpensive option to the conventional process for 

certain process streams. The longer-term goal of 

understanding the enzymatic processes involved may 

allow the transfer of the hydrogen production system 

to another organism, which would represent a 

completely new approach to biological hydrogen 

production. 

Approach 

Work on this project is divided into fundamental 

experiments designed to understand the metabolic 

CO-shift pathway in Rx. gelatinosus CBS, and 

applied experiments focusing on the scale-up of the 

overall process. 

Our approach to the fundamental experiments is 

to use both microbiological and molecular biology 

techniques to help elucidate the overall hydrogen 

production pathway. Based on evidence from the 

closely related photosynthetic bacterium 

Rhodospirillum rubrum, we hypothesize that CO 

oxidation is catalyzed via a CO dehydrogenase 

(CODH) enzyme generating reducing equivalents, 

which are then transferred via a ferredoxin-like ironsulfur protein to the terminal hydrogenase to yield 

H2. Thus, the enzyme complexes responsible for CO 

oxidation and hydrogen production are distinct and 

can be studied separately. 

Our approach to the scale-up experiments is 

guided by an independent and very detailed technoeconomic analysis of the overall process. This 

analysis, begun in FY 2001, was refined during FY 

2002 and FY 2003. This analysis showed the need to 

operate the bioreactors at moderate pressures (150-

200 psi). Bioreactor operation at these pressures 

allows significantly higher volumetric hydrogen 

production rates while incurring no additional reactor 

costs (conventional reactor materials, e.g., carbon 

steel, can easily withstand these modest pressures). 

Our overall approach is to build incrementally larger 

and higher-pressure bioreactors. At each stage 

during scale-up, reactor models are developed and 

compared to actual reactor data to help us fully 

understand the reactor dynamics. 

Results 

The goal of our microbiology experiments was to 

demonstrate that the photosynthetic bacterium Rx. 

gelatinosus CBS could grow solely on CO in the 

dark. Previous work has shown CO-supported 

growth in the dark in Rx. gelatinosus Strain 1 (Uffen, 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

1976), in Rs. rubrum (Kerby, et al., 1995), and in 

Carboxydothermus hydrogenoformans (Svetlichny et 

al., 1991). However, all of these experiments used a 

carbon-containing complex nutrient such as yeast 

extract or trypticase in the growth medium. Because 

of this, it is hard to conclude whether CO alone can 

generate the energy necessary to support cell growth 

or whether the complex nutrients played a role as 

well. We have performed a number of experiments 

to unequivocally demonstrate that bacterium Rx. 

gelatinosus CBS can grow solely on CO in the dark. 

Figure 1 shows the results of an experiment in 

which Rx. gelatinosus CBS was grown in minimal 

medium with CO as the sole carbon substrate. This 

dark-grown culture has a doubling time of 

approximately two days in CO, as reflected both by 

the increase in optical density at 660nm (data in 

Figure 1), and by an increase in the number of 

colony-forming units on agar plates (data not 

shown). 

We collected complementary evidence of the 

ability of Rx. gelatinosus CBS to grow solely on CO 

in darkness by measuring ATP generation during 

dark growth. Since ATP is a universal energy carrier 

in biological systems, generation of ATP is generally 

accepted as proof of growth on a given substrate. We 

Figure 1.	 Growth of Rubrivivax gelatinosus CBS with 

CO as the sole carbon substrate in the dark. 

The culture was bubbled daily with 20% CO 

(solid line) while the control received N2 gas 

(dashed line). 

 FY 2003 Progress Report 

cultured two identical CBS cultures in the presence 

of CO and light. The two cultures were then placed 

in darkness, without CO, to exhaust the endogenous 

ATP levels. After an overnight incubation, the 

headspace of one culture was filled with 20% CO gas 

while the other culture headspace was filled with 

argon gas as a control. At various intervals, aliquots 

of cell samples were withdrawn and quantified for 

endogenous ATP levels (Tran and Unden, 1998). 

Data from Figure 2 clearly indicate that the culture 

that received CO immediately began to produce ATP 

over a time period of 15 min, while no net ATP 

production was measured in the argon gas control. 

Data from both Figures 1 and 2 therefore indicate 

that CO supports both cell growth and ATP synthesis 

in darkness. ATP can be used to generate new cell 

mass, support nutrient uptake and cell repair, and 

synthesize new enzymes such as the WGS catalysts, 

once the existing ones are turned over. These 

findings therefore have significant implications in 

that CO shift bioreactor can operate in darkness to 

sustain long-term hydrogen production, which will 

greatly simplify the design and operation of the 

bioreactor. 

Our work this year in molecular biology was 

remarkably successful. We have identified 16 

putative genes involved in the pathway of H2 

production (Figure 3). Of these 16 genes, four 

(hypA, cooF, cooS, and cooC) reside on the same 

operon and are thought to be involved in the first 

Figure 2.	 Kinetics of ATP production by Rubrivivax 

gelatinosus CBS in darkness with CO (solid 

line) or argon gas (dashed line). (cdw = cell 

dry weight) 

3 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

enzymatic step of the pathway, the oxidation of CO 

to CO2 and the release of protons and electrons from 

water. The remaining 12 genes are believed to play a 

role in the hydrogenase reaction, the reduction of 

protons to H2. Unlike most other hydrogen-related 

genes cloned to date, these genes are clustered within 

the chromosome, encompassing approximately 15 

kilobases. The coo-genes (for CO-oxidation) all 

show a high degree of similarity to those found in 

Rhodospirillum rubrum, which also produces 

hydrogen via the biological WGS (BioWGS) 

reaction (Fox et al., 1996). Unlike the gene 

organization in Rs. rubrum, Rx. gelatinosus CBS 

contains Hyp (hydrogenase pleiotrophy) genes 

clustered around the coo genes. Hyp genes encode 

hydrogenase accessory proteins involved in the 

insertion and co-ordination of Ni2+, Fe, CO, and CN 

ligands found within the catalytic portion of the 

hydrogenase. The hyp genes are similar to those 

found in a wide variety of hydrogenase-containing 

bacteria, including Chlorobium tepidum, 

Rhodobacter sphaeroides, Aquifex aeolicus, and 

Nostoc punctiforme. Lastly, a putative Ni2+ 

transporter is associated with the BioWGS genes. 

The translation of this gene sequence predicts that the 

putative transporter contains an N-terminal signal 

peptide and six transmembrane domains. Ni2+ is an 

essential component of the Rx. gelatinosus CBS 

hydrogenase, and is also incorporated into multiple 

enzymes involved in the BioWGS reaction. The 

putative Ni2+ transporter is comparable to those 

found in Ralstonia metallidurans, 

Rhodopseudomonas palustris, and Bradyrhizobium 

japonicum. A cooS mutant (termed GV1214) was 

obtained and analyzed during FY 2002 and 

determined to be lacking carbon monoxide 

dehydrogenase (CODH) activity (Vanzin et al., 

2002). This mutant was complemented by adding 

back to the mutant the region of the chromosome 

containing HypA through cooC. This cell line then 

produced approximate wild-type levels of hydrogen 

(data not shown). 

As mentioned above, the independent technoeconomic evaluation of the overall biological watergas shift process indicated that the bioreactor must be 

operated at elevated pressures to achieve favorable 

process economics. Our previous work with 

pressurized bioreactors has indicated that elevated 

pressures reversibly inhibit the CO-shift activity of 

the microorganism. Our current results strongly 

indicate that the presence of dissolved CO is the 

major cause of this inhibition. 

To verify this, we performed a number of CO 

conversion rate experiments in agitated shake flasks 

to determine the effect of dissolved CO concentration 

on the rate of CO uptake and subsequent H2 

production by the bacterium Rx. gelatinosus CBS. 

While gas-liquid mass transfer often complicates the 

interpretation of reactor conversion data, we verified 

that these experimental results were not influenced 

by mass transfer limitations. The results of these 

experiments are shown in Figure 4. There is 

Figure 3.	 BioWGS gene organization. Filled arrows 

indicate completed genes, while open arrows 

indicate partially sequenced genes. The 

genomic information encompasses 

approximately 15 kilobases. Scale is 

approximate. 

Figure 4.	 Effect of dissolved CO concentration on the 

rate of CO conversion by Rubrivivax 

gelatinosus CBS. At concentrations above 

approximately 0.15 mM, the conversion rate 

decreases due to substrate inhibition by CO. 

4 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

considerable scatter in the data, but the overall trend 

is clear: the rate of CO conversion to H2 passes 

through a maximum at approximately 0.15 mM 

dissolved CO, which corresponds to a gas phase 

concentration of CO of approximately 20%. These 

results are consistent with the phenomenon of 

“substrate inhibition”, in which excessive 

concentrations of a reactant can interfere with the 

enzyme catalyzing conversion to product. The curve 

in Figure 4 shows a fit to a substrate inhibition 

kinetic model. 

How does the behavior shown in Figure 4 cause 

reactor inhibition at elevated pressures? At elevated 

pressure, the solubility of CO in solution increases, 

and above a critical pressure (which depends on 

several factors), the dissolved CO concentration 

begins to exceed 0.15 mM, which causes a reversible 

inhibition of reaction rate. Thus, the inhibition can 

be avoided simply by keeping the dissolved CO 

concentration below 0.15 mM in the bioreactor. Our 

preliminary experimental and modeling results (not 

shown) indicate that elevated cell mass loadings in 

the bioreactor appear to be effective in keeping the 

dissolved CO concentration below 0.15 mM, since 

higher cell mass loadings increase the CO uptake rate 

per unit bioreactor volume. We are currently 

performing additional experiments to verify these 

results. 

NREL performed a techno-economic analysis to 

investigate the relative economics of biological vs. 

conventional water-gas shift (WGS). Reactor data 

from our work were used to estimate the size (and 

therefore cost) of the biological WGS reactor. These 

results were then compared to the conventional 

process in the context of an overall system model. 

The thermodynamics of the biological WGS process 

are more favorable than the conventional WGS 

process, but the kinetics are less favorable. Thus, a 

biological WGS reactor will always be larger (and 

therefore more expensive) than the corresponding 

conventional reactor. This difference in reactor cost 

is balanced by the cost for low-pressure steam 

production and delivery for the conventional process 

(the biological process uses liquid water). Thus, the 

overall cost savings associated with the biological 

process result from these “balance of plant” savings, 

and the overall system must be considered when 

estimating the relative costs of the two different shift 

technologies. For many biomass-derived synthesis 

gas streams, the presence of unreacted hydrocarbons 

(principally methane, CH4) requires the use of a 

secondary reformer downstream of the gasifier to 

convert the unreacted hydrocarbons to additional 

synthesis gas. Since this reformer requires steam, if 

the reformer is used, the incremental cost of steam 

generation for the conventional WGS reactor is 

minimal, and the lower cost of the conventional 

WGS reactor makes this technology the preferred 

option. Thus, it is the amount of methane present in 

the biomass-derived synthesis gas stream (and not 

the amount of CO in the stream) that controls which 

WGS technology is preferred. At lower methane 

concentrations, no reformer is needed, and the 

biological WGS process is preferred. At higher 

methane concentrations, the reformer is necessary, 

and the conventional WGS process is preferred. The 

exact methane concentration where this “crossover” 

occurs depends on a number of factors, but for the 

assumptions we made in the techno-economic 

analysis, we believe that the biological WGS process 

is a promising alternative to conventional process for 

CH4 concentrations less than about 3%-5%. The 

results of this analysis are shown in Figure 5. 

Conclusions 

•	 CO can serve both as the carbon and energy 

substrate to sustain long-term hydrogen 

production in darkness. 

Figure 5.	 Effect of methane concentration on the cost 

of hydrogen produced for both conventional 

and biological WGS processes. Below 

approximately 3-5%, the biological WGS 

process appears to be the less expensive 

option. 

5 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 At least 16 genes are required for the CO-to-H2 

reaction in Rx. gelatinosus CBS. These genes 

encode proteins not only involved in catalysis, 

but also in the transport and assembly of 

hydrogen-producing enzymes. 

•	 A number of Rx. gelatinosus WGS genes are 

closely related to those known in Rs. rubrum, 

which also produces hydrogen from CO. 

•	 Unlike other hydrogenase-containing 

microorganisms, Rx. gelatinosus CBS contains a 

large cluster of genes related to hydrogen 

production. This grouping of genes should 

facilitate their over-production and/or 

heterologous expression. 

•	 By restoring wild-type levels of hydrogen 

production in a CODH mutant, we have 

demonstrated the ability to make H2-related 

proteins of our choosing in CBS. This is a 

critical step toward the overproduction of 

microbial catalysts aimed at the production of 

hydrogen. 

•	 Elevated pressure bioreactor operation is 

complicated by the inactivation of the WGS 

pathway by elevated concentrations of dissolved 

CO. This problem can be avoided by proper 

bioreactor design. 

•	 The biological WGS reaction appears to be a 

promising alternative to conventional technology 

for synthesis gas streams containing low 

concentrations (<5%) of unreacted 

hydrocarbons. 

References 

1. Fox, J.D., Y.P. He, D. Shelver, G.P. Roberts, and 

P.W. Ludden. 1996. Characterization of the 

region encoding the CO-induced hydrogenase of 

Rhodospirillum rubrum. J. Bacteriol., 178:6200-

6208. 

2. Kerby, R.L., P.W. Ludden, and G.P. Roberts. 

1995. Carbon monoxide-dependent growth of 

Rhodospirillum rubrum. J. Bacteriol., 177: 2241-

2244. 

3. Svetlichny, V.A., T.G. Sokolova, M. Gerhardt, M. 

Ringpfeil, N.A. Kostrikina, and G.A. Zavarzin. 

1991. Carboxydothermus hydrogenoformans gen. 

nov., sp. nov., a CO-utilizing thermophilic 

anaerobic bacterium from hydrothermal 

environments of Kunashir Island. Syst. Appl. 

Microbiol., 14: 254-260. 

4. Tran, Q.H. and G. Unden. 1998. Changes in the 

proton and the cellular energetics of Escherichia 

coli during growth by aerobic and anaerobic 

respiration or by fermentation. Eur. J. Biochem., 

251: 538-543. 

5. Uffen, R.L. 1976. Anaerobic growth of a 

Rhodopseudomonas species in the dark with 

carbon monoxide as sole carbon and energy 

substrate. Proc. Natl. Acad. Sci. USA. 73: 3298-

4789. 

6. Vanzin, G.V., S. Smolinski, K. Kronoveter, P.C. 

Maness, E.J. Wolfrum, A.S. Watt, and J. Huang. 

2002. FY2002 Progress Report. Hydrogen, Fuel 

Cells, and Infrastructure Technologies. http:// 

www.eere.energy.gov/hydrogenandfuelcells/pdfs/ 

33098_sec2-1.pdf 

FY 2003 Publications/Presentations 

1. Maness, P.C. and P.F. Weaver. 2002. Hydrogen 

production from a carbon-monoxide oxidation 

pathway in Rubrivivax gelatinosus. Intl. J. 

Hydrogen Energy. 27: 1407-1411. 

2. Merida, W., P.C. Maness, R.C. Brown, and D.B. 

Levin. Enhanced hydrogen production from 

indirectly heated, gasified biomass, and removal 

of carbon gas emission using a novel biological 

gas reformer. Accepted for publication in Intl. J. 

Hydrogen Energy. 

3. Maness, P.C., G.V. Vanzin, J. Huang, and S. 

Smolinski. “The Hydrogen Production Pathway 

Linked to Carbon Monoxide Oxidation in 

Rubrivivax Gelatinosus” (Oral Presentation). 

12th Western Photosynthesis Conference, Pacific 

Grove, CO (January 2003). 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies

4. Huang, J., S. Smolinski, G.V. Vanzin, V. Tek, and 

P.C. Maness. “The Water-Gas Shift Reaction 

Generates Energy in Darkness” (Poster 

Presentation). 25th Symposium on Biotechnology 

for Fuels and Chemicals, Breckenridge, CO (May 

2003). 

5. Amos, W., Wolfrum, E., Watt, A., “Biological H2 

Production from Synthesis Gas: Preliminary 

Techno-Economics & Reactor Design Issues” 

(Poster Presentation). 25th Symposium on 

Biotechnology for Fuels and Chemicals, 

Breckenridge, CO (May 2003). 

 FY 2003 Progress Report 

7 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Biomass-Derived Hydrogen from a Thermally Ballasted Gasifier 

Robert C. Brown (Primary Contact) 

Center for Sustainable Environmental Technologies 

Iowa State University 

283 Metals Development Bldg. 

Ames, IA 50011-3020 

Phone: (515) 294-7934; Fax: (515) 294-3091; E-mail: rcbrown@iastate.edu 

DOE Program Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-1637; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Determine whether switchgrass is a suitable fuel for the ballasted gasifier. 

•	 Obtain time-resolved concentrations of important fuel components evolved. 

•	 Identify process conditions that maximize the production of hydrogen. 

•	 Evaluate methods for removing contaminants from the producer gas. 

•	 Evaluate methods for mediating the water-gas shift reaction in the product gas. 

•	 Estimate the economics of hydrogen production from switchgrass. 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

Approach 

•	 Prepare switchgrass fuel and feeder. 

•	 Prepare 5-ton per day bubbling fluidized bed gasifier and a latent heat ballasting system. 

•	 Prepare slipstream for upgrading producer gas. 

•	 Prepare gas sampling and analysis system. 

•	 Perform gasification trials. 

•	 Perform cost estimate of the gasification system. 

Accomplishments 

•	 Established analytical methods for accurate and repeatable measurements of H2S and NH3. 

•	 Characterized producer gas from gasification of switchgrass. 

•	 Achieved reductions of 95% in total tar and 99% reductions in condensable (heavy) tar by steam 

reforming. 

•	 Reduced CO in producer gas to less than 0.5 vol-% by water-gas shift reaction. 

•	 Demonstrated operation of ballasted gasifier in production of raw producer gas with hydrogen 

concentrations averaging 20 vol-% (before gas upgrading). 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Simulated performance of ballast system through thermal modeling. 

• Identified technology for separating hydrogen from carbon dioxide. 

Future Directions 

• Improve the overall cold-gas efficiency of the gasifier. 

• Establish methodology for reliable HCl measurements. 

• Demonstrate a combined particulate matter/trace contaminant control system. 

• Evaluate the feasibility of a combined catalytic reaction/carbon dioxide sorbent system. 

• Perform economic assessment of ballasted gasifier system. 

Introduction 

The goal of this project is to optimize 

performance of an indirectly heated gasification 

system that converts switchgrass into hydrogen-rich 

gas suitable for powering fuel cells. We have 

developed a thermally ballasted gasifier that uses a 

single reactor for both combustion and pyrolysis. 

Instead of spatially separating these processes, they 

are temporally isolated. The producer gas is diluted 

neither with nitrogen nor the products of combustion. 

The heat released during combustion at 850°C is 

stored as latent heat in the form of molten salt sealed 

in tubes immersed in the fluidized bed. During the 

pyrolysis phase, which occurs at temperatures 

between 600 and 850°C, the reactor is fluidized with 

steam or recycled producer gas rather than air. Heat 

stored in the phase change material is released during 

this phase of the cycle to support the endothermic 

reactions of the pyrolysis stage. 

Because air is not used during the gas-producing 

phase of the cycle, nitrogen does not dilute the 

product gas, resulting in relatively high 

concentrations of hydrogen and carbon monoxide in 

the producer gas compared to conventional gasifiers. 

The carbon monoxide, along with steam used to 

fluidize the reactor, can be shifted to additional 

hydrogen by the water-gas shift reaction. 

Approach 

The approach to this project is to employ a pilotscale (5-ton per day) gasifier to evaluate the 

thermally ballasted gasifier as a means for producing 

hydrogen from switchgrass. Gasification at the pilot 

scale is important for obtaining realistic process data, 

especially for calculating energy flows through the 

system and assessing the practicality of feeding 

switchgrass into the gasifier. 

A slipstream from the gasifier is used to evaluate 

gas cleaning and upgrading options. This slipstream 

includes: a guard bed designed to remove hydrogen 

sulfide and hydrogen chloride and some tar; a steam 

reformer designed to crack the remaining tar and 

decompose ammonia; and high-temperature and lowtemperature catalytic water-gas shift reactors to 

remove carbon monoxide from the product gas and 

increase its hydrogen content. A series of 

gasification trials are being performed to evaluate the 

effectiveness of these four reactors in removing tar 

and contaminants, and shifting producer gas towards 

increased hydrogen and decreased carbon monoxide. 

Results 

Figure 1 illustrates the slipstream system 

developed for use with the ballasted gasifier. The 

slipstream system extracts hot producer gas from the 

exhaust duct at volumetric flow rates (4.5 – 5.5 L/ 

min) appropriate to isokinetic sampling 

requirements. This gas sample passes through a 

heated particulate filter maintained at 450°C to 

prevent condensation of tars; thus, the collected 

particulate sample can be used to calculate 

particulate matter concentrations in the producer gas 

(typically about 10 g/scm). The particulate-free 

sample then passes through a guard bed of calcined 

dolomite that removes hydrogen sulfide and 

hydrogen chloride prior to passage through metal 

catalysts that would otherwise be poisoned by these 

trace contaminants. Steam is added at a level 

appropriate to steam reforming of tar over a nickel 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

catalyst contained in the second of the four reactors. 

A high temperature shift reactor and a low 

temperature shift reactor follow the tar cracker with 

the purpose of shifting CO and steam to hydrogen 

and CO2. 

Table 1 summarizes both the operating 

conditions and results of gas conditioning trials on 

producer gas generated from air-blown gasification 

of switchgrass. The “tar cracker” operating in 

conjunction with the guard bed was able to remove 

>99% of condensable (heavy) tars from the raw 

producer gas. Further details of the operation of the 

tar cracker are found in Reference 1. The 

combination of water-gas shift reactors reduced CO 

concentration from 20.1 vol-% to 0.18 vol-%. The 

outlet concentration of hydrogen was 27.1 vol-%. 

Further details on the performance of the shift 

reactors are found in References 2 and 3. 

Figure 1 also illustrates the gas sampling system 

developed for use with the ballasted gasifier, which is 

separate from the slipstream containing the catalytic 

 FY 2003 Progress Report 

reactors. Heated thimble filters remove particulate 

matter while a tar condenser, operated slightly above 

100°C, removes tar without condensing water (an 

important consideration in accurately sampling 

water-soluble trace contaminants). The sample 

stream is split into two streams. One stream goes to a 

Figure 1. Overall Schematic of Gas Sampling System 

and Slipstream From Gasifier Effluent 

Table 1: Summary of Gas Conditioning Trials on Switchgrass-Derived Producer Gas 

Reactor Guard Bed Tar Reactor High 

Temperature 

Shift 

Low Temperature 

Shift 

Set point temperature 

of reactor (oC) 

650 800 400 200 

Temperature range of 

reactor (oC) 

600-670 750-850 350-420 180-240 

SV (h-1) 900 3000 1500 1200 

Catalyst Calcined 

dolomite 

ICI 46-1 Fr-Cr based 

LB 

Cu-Zn-Al based 

B202 

Catalyst volume (ml) 200 60 120 150 

Gas Composition* 

H2 

CO 

CO2 

CH4 

C2H4 

Inlet gas 

8.5 

14.5 

18.1 

4.3 

1.5 

Outlet gas 

19.44 

8.9 

20.1 

3.5 

0.27 

Outlet gas 

23.7 

1.37 

26.8 

3.4 

0.31 

Outlet gas 

27.1 

0.18 

27.2 

3.1 

0.13 

Tar content (g/Nm3

) 19.5 ** ** ** 

*Gas composition is dry basis (vol-%) measured by gas chromatography. 

** No heavy tar by observation. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

heatless drier to produce dry gas for measuring 

hydrogen sulfide with Draeger tubes. The other 

stream is partitioned to impinger trains for 

condensing ammonia and hydrogen chloride in 

aqueous solutions. Hydrogen sulfide measurements 

were 190 – 220 ppm, about 50% lower than expected 

from the sulfur content of the biomass feedstock. 

This is attributed to absorption by calcined limestone 

added to the fluidized bed gasifier to control sand 

agglomeration. Ammonia measurements were 5000 

ppm in the raw producer gas. 

Since the ballast operates in a cyclic mode, 

time-resolved gas concentrations are important to 

assessing the performance of the system. For this 

purpose, non-dispersive infrared analyzers for CO 

and CO2 and an electrochemical cell for O2 were 

installed in the gas sampling system (not illustrated 

in Figure 1). Figure 2 illustrates the continuous 

data taken during the operation of the ballasted 

gasifier during the pyrolytic phase of the 

gasification cycle using these instruments (distinct 

points are data taken with a gas chromatograph to 

confirm the continuous measurements). This figure 

shows how H2 and CO rapidly increase from 

virtually zero concentration at the beginning of the 

pyrolytic phase. Hydrogen peaks almost instantly 

and gradually declines as the reactor cools while 

CO continues to climb over most of the pyrolysis 

phase. Both drop off rapidly after air is readmitted 

to the reactor (although the persistence of CO in this 

particular trial indicates that the amount of air 

 FY 2003 Progress Report 

added is insufficient for complete combustion of 

both fresh biomass and residual char in the reactor). 

Figure 3 illustrates experimental and simulated 

cooling curves for the ballasted gasifier after an 

initial combustion heat-up period followed by the 

admission of steam (but no biomass) to the reactor. 

The experimental cooling curve shows a distinct 

inflection as the result of the heat released from the 

latent enthalpy stored in the ballast tubes. A simple 

lumped capacitance (LC) model simulates the 

experimental data reasonably well except during the 

period of latent enthalpy change, which appears as an 

isothermal region in the cooling curve. Modeling 

work proved this to be an artifact of the LC model. 

Careful accounting of the growth of a solidification 

zone within the ballast tubes resulted in the receding 

interface (RI) model, which produces a more realistic 

cooling curve, as shown in Figure 3. See Reference 

4 for additional details. 

Conclusions 

•	 Steam reforming of raw producer gas reduced 

condensable (heavy) tars to undetectable levels. 

•	 Water-gas shift reactors were successful in 

reducing carbon monoxide to less than 0.2 vol­

%. 

•	 Reliable trace contaminant sampling and measurement was established for ammonia and 

hydrogen sulfide. 

•	 The thermal ballasting system generated raw 

producer gas with up to 23 vol-% hydrogen. 

•	 An accurate thermal model of the ballasted gasifier was developed. 

Figure 2. Time Resolved Gas Composition During the 

Pyrolysis Phase of the Gasification Cycle 

Figure 3. Comparison of Experimental Cooling Curves 

to Predictions of Thermal Models 

4 
 

Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Zhang, R., Brown, R., Suby, A., and Cummer, K., 

“Catalytic destruction of tar in biomass-derived 

producer gas,” Energy Conversion and 

Management (submitted). 

2. Zhang, R., Cummer, K., Suby, A., and Brown, R. 

C., Biomass-derived hydrogen from an air-blown 

gasifier,” Fuel Processing Technology 

(submitted). 

3. Zhang, R., Brown, R. C., and Suby, A., 

“Thermochemical conversion of switchgrass to 

hydrogen,” Energy and Fuels (submitted). 

4. Cummer, R. and Brown, R. C., “Indirectly heated 

biomass gasification using a latent heat ballast. 

Part 3: Refinement of the heat transfer model,” 

Biomass and Bioenergy (submitted). 

5. Mérida, W., Maness, P., Brown, R. C., and Levin, 

D. B., “Enhanced hydrogen production and 

removal of carbon dioxide from indirectly heated 

biomass gasification,” International Journal of 

Hydrogen Energy (accepted). 

6. Zhang, R., Brown, R. C., Suby, A., Cummer, K., 

“Catalytic cleaning of hot producer gas,” 

Proceedings of the Tenth Biennial Bioenergy 

Conference, Boise, IA, September 22 – 26, 2002 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Techno-Economic Analysis of Hydrogen Production by Gasification of Biomass 

David A. Bowen (Primary Contact), F. Lau, R. Zabransky, R. Remick, R. Slimane, S. Doong 

Gas Technology Institute (GTI) 

1700 S. Mt. Prospect Road 

Des Plaines, Illinois 60018 

Phone: (847) 768-0896; Fax: (847) 768-0600; E-mail: dave.bowen@gastechnology.org 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Subcontractors: 

Scott Q. Turn - Hawaii Natural Energy Institute, Honolulu, Hawaii 

Evan E. Hughes - Electric Power Research Institute (EPRI), Palo Alto, California 

Objectives 

•	 To determine the economics of hydrogen production by gasification of three biomass candidates: 

bagasse, switchgrass, and nutshells 

•	 To optimize hydrogen production for use in proton exchange membrane (PEM) fuel cells 

•	 To identify the economic and technical barriers associated with biomass gasification 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

•	 AB.Hydrogen Separation and Purification 

Approach 

•	 Determine the cost and availability of the three candidate biomass feedstocks. 

•	 Design a process scheme for the production of hydrogen. 

•	 Determine optimal hydrogen production through the testing of various simulation cases. 

•	 Analyze research and simulation results to determine technical and economic feasibility. 

•	 Determine the commercialization barriers to the production of hydrogen from biomass. 

Accomplishments 

•	 Estimated the cost and availability of all three biomass feedstocks. 

•	 Determined the current technologies available for biomass feeding and hot gas cleanup. 

•	 Simulated and optimized the production of hydrogen through the use of an empirical, GTI proprietary 

gasifier model and a HYSYS design and simulation package. 

•	 Performed an economic analysis of the production of hydrogen from the three biomass feedstocks. 

•	 Evaluated current public programs available to reduce the cost of biomass as a feedstock. 

•	 Determined the technical, economic, and psychological barriers to the commercialization of hydrogen 

from biomass. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

The following areas are currently being pursued by GTI, however they are not funded under this project. 

• Conduct experimental testing to verify the results obtained in this paper study. 

• Evaluate an economical way to clean syngas at reforming temperatures. 

• Determine suitable membrane materials that will promote reforming and separation. 

• Further evaluate and test pressurized biomass feeding systems on various feedstocks. 

Introduction 

Biomass represents a large potential feedstock 

resource for environmentally clean processes that 

produce power or chemicals. It lends itself to both 

biological and thermal conversion processes, and 

both options are currently being explored. Hydrogen 

can be produced in a variety of ways. The majority 

of the hydrogen produced in this country is produced 

through natural gas reforming and is used as 

chemical feedstock in refinery operations. 

In this study, the production of hydrogen by 

gasification of biomass is examined. Biomass is 

defined as organic matter that is available on a 

renewable basis through natural processes or as a byproduct of processes that use renewable resources. 

The majority of biomass is used in combustion 

processes in mills that produce electricity for end-use 

product generation. This project explores the use of 

hydrogen as a fuel derived from gasification of three 

candidate biomass feedstocks: bagasse, switchgrass, 

and a nutshell mix consisting of 40% almond 

nutshell, 40% almond prunings, and 20% walnut 

shell. 

Approach 

In this study, an assessment of the technical and 

economic potential of producing hydrogen from 

biomass gasification is made. The resource base is 

assessed to determine process scale potential from 

information on feedstock costs and availability. 

Solids handling systems are reviewed. A GTI 

proprietary gasifier model is used in combination 

with a HYSYS® design and simulation program to 

determine the amount of hydrogen that can be 

produced from each candidate biomass feed. Cost 

estimations are developed, and government programs 

and incentives are analyzed. Finally, the barriers to 

the production and commercialization of hydrogen 

from biomass are determined. The end-use of the 

hydrogen produced from this system is small PEM 

fuel cells for automobiles. 

Results 

Analysis of the resource base determined 

bagasse and switchgrass should be analyzed on a 

scale of 500, 1000, and 2000 tonnes/day and mixed 

nutshells at 500 tonnes/day. Simulation results were 

obtained for 500 tonnes/day biomass fed to the 

gasifier at moisture contents of 20% for bagasse, 

12% for switchgrass, and 12.5% for the nutshell mix. 

A scaling factor of 1 can be used to determine 

hydrogen production from an increased feed rate (i.e. 

doubling the feed rate will double the amount of 

hydrogen produced). Process flow diagrams were 

developed for all three cases and are very similar 

with the exception of the need for a dryer for the 

bagasse case, as shown in Figure 1 (the initial 

moisture content of the feed is 50% and must be 

reduced to 20% for feed into the gasifier) [1]. 

The flow streams and sizes from the process flow 

scheme were used to adjust the scale and unit 

Figure 1. Process Flow Diagram of Bagasse Case with 

a Dryer (PSA = pressure swing adsorption) 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

operations that had previously been the subject of 

cost and design studies by EPRI and GTI. Previous 

work done for GTI had provided a very detailed 

breakdown of capital costs, including labor hours on 

many categories of construction and installation. 

The work done by EPRI developed cost breakdowns 

for biomass power systems using biomass 

feedstocks. Scaling of costs to adjust to the sizes 

desired for the cases studied here was accomplished 

according to the following general rule: power law 

scaling of 0.7 for the solids handling, gasification, 

gas cleaning, shifting, and purification systems, and 

0.8 for the power, steam, balance of plant, general 

facilities, and overall combined cycle system scaling. 

Drying and steam turbine components were scaled at 

a 0.6 power law. Hydrogen production rates and the 

resulting economics are shown in Table 1 [1]. 

The economic results achieved in this study are 

comparable to those from steam methane reforming. 

For steam methane reforming plants that produce 

approximately 1.5 million Nm3

/day, the cost of 

hydrogen production ranges from $5.85/GJ ($3.00/ 

GJ natural gas) [2] to $7.46/GJ ($4.50/GJ natural 

gas) [3]. This comparison is shown in Figure 2. 

Conclusions 

Hydrogen is a valuable fuel that can provide 

sustainable energy for fuel cell vehicles. The 

 FY 2003 Progress Report 

majority of hydrogen is produced by steam methane 

reforming of natural gas, where average prices of 

$5.50 to $7.50 per gigajoule can be realized for larger 

facilities. At low natural gas prices, this is the least 

expensive way to produce hydrogen, but it relies on a 

non-renewable, fossil fuel. 

Biomass gasification represents an alternative 

means to produce hydrogen. This study evaluated 

hydrogen production by gasification of three biomass 

feedstocks: bagasse, switchgrass, and a nutshell mix. 

The process scheme involved feeding, gasifying, 

cleaning, reforming, shifting, and purifying to 

produce a hydrogen stream with better than 99.9% 

purity. The economics of hydrogen production by 

gasification of biomass predict that hydrogen can be 

Figure 2. Estimated Cost Comparison of Hydrogen 

Production 

Table 1. Economic Results for Gasification of Three Biomass Feedstocks 

Gasifier Feed 

Rate Hydrogen Produced Feedstock 

Cost Capital Cost H2 Cost (15% 

IRR) 

Feedstock Dry Tonnes / 

Day Tonnes / Day Nm3 / Day US $ / GJ US $ Million US $ / GJ 

Bagasse 400 13.2 347,000 1.50 37.0 10.23 

800 62.5 695,000 1.50 61.1 8.74 

1600 125 1,390,000 1.50 100.9 7.67 

Switchgrass 440 37.0 412,000 1.50 36.5 8.76 

880 74.0 824,000 1.50 60.6 7.54 

1760 148 1,648,000 1.50 100.9 6.67 

Nutshell Mix 438 38.7 488,000 1.50 36.3 8.26 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

produced economically. Hydrogen prices from $6.50 

- $10/GJ can be realized. As technology improves, 

natural gas prices increase, and government incentive 

programs evolve, biomass gasification will present 

an economical way to produce hydrogen for use in 

PEM fuel cells and other energy consuming systems. 

References 

1. D. Bowen, F. Lau, R. Dihu, S. Doong, R. Remick, 

R. Slimane, R. Zabransky, E. Hughes, and S. 

Turn, "Techno-Economic Analysis of Hydrogen 

Production by Gasification of Biomass." Final 

Report to U.S. Dept. of Energy, Contract DEFC36-01GO11089, June 2003. 

2. P. Morris, "Clean Fuels Means Hydrogen, Where 

Will It Come From and What Will It Cost?" Air 

Products PLC, http://www.airproducts.com/autooil/techpaper-morris/htm. 

3. C. Gregorie Padro, V. Putsche, "Survey of the 

Economics of Hydrogen Technologies." NREL, 

Golden, CO. 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. D. Bowen, F. Lau, R. Dihu, S. Doong, R. Remick, 

R. Slimane, R. Zabransky, E. Hughes, and S. 

Turn, "Techno-Economic Analysis of Hydrogen 

Production by Gasification of Biomass." Final 

Report to U.S. Dept. of Energy, Contract DEFC36-01GO11089, June 2003. 

2. D. Bowen, F. Lau. Poster presentation at the May 

2003 US DOE Hydrogen and Fuel Cell Program 

Merit Review. 

3. D. Bowen, F. Lau, R. Dihu, S. Doong, R. Remick, 

R. Slimane, R. Zabransky, E. Hughes, and S. 

Turn, "Hydrogen from Biomass Gasification." 

Canadian Hydrogen Association and Fuel Cells 

Canada Conference, Vancouver, BC, Canada, 

June 2003. 

4. D. Bowen, F. Lau, R. Zabransky, "TechnoEconomics Analysis of Hydrogen Production by 

Gasification of Biomass." US DOE Hydrogen, 

Fuel Cells and Infrastructure Technologies FY 

2002 Progress Report. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen from Biomass - Catalytic Reforming of PyrolysisVapors 

Robert Evans (Primary Contact), Lynnae Boyd, Carolyn Elam, Stefan Czernik, Rick French, Calvin 

Feik, Steven Phillips, Esteban Chornet, Yves Parent (subcontractor-Chemical Engineering 

Consulting Services) 

National Renewable Energy Laboratory 

1617 Cole Blvd. 

Golden, CO 80401 

Phone: (303) 275-3708; Fax: (303) 275-2905; E-mail: Bob_Evans@nrel.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Demonstrate the production of hydrogen from biomass pyrolysis integrated with catalytic steam 

reforming and prepare for scale-up of the system to greater than 500 kg H2/day by 2009. 

•	 Improve the efficiency of the system, including the reformer, and the use of appropriate catalysts to 

reduce the cost to below $2.90/kg H2 by 2009. 

•	 Demonstrate the use of a variety of feedstocks so that significant quantities of hydrogen can be made 

from biomass. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Control and Safety 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

•	 Z. Catalysts 

•	 AD.Market and Delivery 

Approach 

•	 Support DOE funded partners to demonstrate the integrated pyrolysis/reforming process using 

agricultural residues (peanut shells) as feedstock; document mass balance and catalyst performance in 

a long-duration test. 

•	 Validate the yields and throughputs obtained in the bench-scale system so that information can be used 

for technoeconomic analysis of the process and for the design of the future scale-up of the process, 

which will begin in FY 2004 at a scale of 250 kg H2 produced/day. 

•	 Facilitate the addition of unit operations for use in a demonstration that will use H2 to produce 

electricity and fuel vehicles such as buses. 

•	 Work with interested parties to extend the applicability of the work to other geographical locations. 

•	 Contribute state-of-the-art chemical analysis and process control so that the small-scale systems can be 

run with high confidence of safety and reliability. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Developed gas filtration unit operation that solved the problem of plugging the distribution plate with 

entrained char. 

•	 Provided technical support of the reformer installation in Blakely, Georgia, where the system was run 

for 100 hours. 

•	 Filed a provisional patent that incorporates biomass conversion to hydrogen with a co-product of 

carbon-based soil amendment system. 

•	 Supported partnership development in other areas of the country so that the results can be deployed 

when ready. 

Future Directions 

•	 Develop the Phase 3 system design that will include better heat management in the pyrolyzer and 

reformer and will add a condenser, compressor, and pressure swing adsorption (PSA) system to the gas 

conditioning system. 

•	 Initiate tests necessary to develop a circulating fluidized bed reforming process. 

•	 Develop process control systems that will facilitate the cost-effective development of safety 

engineering for small-scale biomass-to-hydrogen systems. 

Introduction 

The goal of this work is the production of 

renewable hydrogen from agricultural residues at a 

comparable cost to existing methane-reforming 

technologies by 2015. Near-term production of 

renewable hydrogen from biomass requires a coproduct strategy to compete with conventional 

production of hydrogen from the steam reforming of 

natural gas. The processing of pyrolysis co-products 

from the production of activated carbon is one 

possible path to demonstrate such a strategy. 

The original concept was that the pyrolysis oil 

could be separated into two fractions based on water 

solubility. The water-soluble fraction would be used 

for hydrogen production, and the water insoluble 

fraction could be used in adhesive formulations. The 

bio-oil can be stored and shipped to a centralized 

facility for conversion to hydrogen via catalytic steam 

reforming and shift conversion. Although the 

adhesive byproduct option remains viable, 

commercial deployment opportunities are still not 

near-term. Hence, other opportunities had to be 

developed based on the co-product strategy. The 

conversion of biomass to activated carbon is an 

alterative route to hydrogen with a valuable coproduct, as outlined in Figure 1. A third option is 

converting the charcoal into carbon-based fertilizers. 

In those two options, the volatiles produced in the 

pyrolysis step can be converted to hydrogen. This is a 

near-term possibility for deployment. Slow pyrolysis 

is used in the first step of the activated carbon process 

to optimize the yield of charcoal and organic vapors. 

Approach 

A schematic of the system is shown in Figure 2. 

Pelletized peanut shells were fed to a cross-draft, 

Figure 1. Biomass to Hydrogen Based on Pyrolysis 

with a Co-Products Strategy 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

moving-bed pyrolysis reactor heated by propane Results 

combustion gases. Superheated steam was used to 

educe a fraction of the vapors through a bag-house 

filter to remove char fines and then to a preheater 

before the reformer. Pelletized peanut shells were 

fed at a rate of 50 kg/hr to the pyrolysis reactor, 

which was controlled so the exit gas temperature was 

500°C. Using a helium tracer, it was determined that 

20% of the total gaseous products from the pyrolyzer 

were educed in the steam flow to the reformer. 

Before reforming, the steam/vapor stream entered a 

preheater that raised the gas stream temperature to 

650°-700°C. 

The catalytic fluid bed reformer was fed with up 

to 5 kg/h of pyrolysis vapor. The maximum allowable 

operating temperature and pressure are 900°C and 140 

kPa, respectively. The reformer is equipped with 

internal and external cyclones for disengaging catalyst 

particles, instrumentation, data acquisition, and safety 

features (alarms). Commercial nickel-based catalyst 

ground to particle sizes of 300-500 mm was used in 

the reactor. The catalyst is fluidized using superheated 

steam, which is also a reactant in the reforming 

process. The cyclones capture both fine catalyst 

particles and solid carbon generated by gas-phase 

pyrolysis of the vapors that may occur in competition 

with the catalytic steam reforming. The Inconel 

reactor with a perforated distribution plate is placed 

inside a three-zone electric furnace to maintain the 

reactor at the desired temperature during the 

endothermic steam reforming operation. The 

reformed products flow through the spray scrubbers 

and a cold wall condenser before passing through a 

coalescing filter to remove aerosols. 

The purpose of the 100-hour run was to reform 

the whole pyrolysis vapors in the 30-cm catalytic 

steam reforming fluid bed reactor. The more 

chemically stable, lignin-derived phenolics are more 

likely to coke on the nickel catalyst. Prior runs in the 

5-cm reformer have used only the aqueous 

carbohydrate-derived fraction of pyrolysis oil. 

Figure 3 shows the product gas composition (H2, 

CO2, CO and CH4) and the differential pressure (DP) 

across the reformer bed over the first 70 hours of the 

86 hours that the reformer was on line. Periods 

where the reformer was taken off line, a total of 16 

hours, are not included in the figure. The final 16 

hours are not shown in Figure 3, since the plugging 

of the filter before the eductor made the system 

unstable. The build-up of char across the filter also 

caused the gradual decrease in DP across the 

reformer bed, as shown in Figure 3. The 

composition of the gas indicates that the yield of 

hydrogen from this agricultural residue feedstock is 

approximately 90% of maximum. Additional 

optimization of process conditions should result in 

somewhat higher yields (note that, in a commercial 

operation, the remaining CO could be converted to 

CO2 and additional hydrogen using conventional 

water-gas shift processing). In these tests, the gas 

product stream was flared. No breakthrough of 

pyrolysis products was noted, and the methane level, 

which is a sensitive indicator of catalyst activity, did 

not increase. The significant finding here is that the 

lignin-derived pyrolysis products were reformed 

completely. The changes in product gases were due 

Figure 2. Diagram of Process as Performed for the 

100-hour Duration Run 

Figure 3.	 Product Gas Composition (H2, CO2, CO and 

CH4) and Differential Pressure (DP) Across 

the Reformer Bed 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

to a systematic decrease in mass flow to the bed due 

to an increase in pressure drop across the hot gas 

filter. This build-up of particulate matter was 

unexpected, but the change in product gas 

composition indicates better performance. The 

increase in hydrogen yield and decrease in relative 

yield of both CO and CH4 were the results of 

effectively decreasing the weight hourly space 

velocity and increasing the steam-to-carbon ratio. 

We achieved a higher rate of conversion most likely 

by allowing more time for carbon gasification from 

the catalyst surface. 

Conclusions 

•	 The steam reforming of biomass pyrolysis 

vapors and liquids, when integrated with the 

production of high value products, is a promising 

near-term approach to the production of 

renewable hydrogen. This approach will be 

applied in Georgia at a plant that makes activated 

carbon from peanut shells and has pyrolysis byproducts available for conversion. The key 

technical goal for the run is to obtain preliminary 

performance data on the catalyst, especially 

physical attrition and deactivation. 

 FY 2003 Progress Report 

•	 In the next phase, the reactor will be run for 1000 

hours with additional gas stream processing 

included. The hydrogen that is produced will be 

separated from CO and CO2 using pressure 

swing adsorption. The purified hydrogen will be 

mixed with natural gas and used in engine 

demonstrations. Other agricultural residues and 

deployment logistics are being evaluated for cost 

and co-product potential. 

FY 2003 Publications/Presentations 

"Renewable hydrogen production by catalytic 

steam reforming of peanut shells pyrolysis 

products." Robert J. Evans, Esteban Chornet, 

Stefan Czernik, Calvin Feik, Richard French, 

Steven Phillips, Yaw D. Yeboah, Danny Day, 

Shivayam Ellis, Dennis McGee, and Matthew J. 

Realff. Preprints, ACS Fuel Chemistry 

Symposium, Boston MA, 2002. 

Special Recognitions & Awards/Patents 

Issued 

Provisional Patent, Danny Day and Robert J. 

Evans, "A process for the combined production of 

hydrogen, sequestered carbon and a slow release 

fertilizer from biomass." 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Production of Hydrogen from Post-Consumer Residues 

Stefan Czernik (Primary Contact), Richard French, Robert Evans, Esteban Chornet 

National Renewable Energy Laboratory (NREL) 

1617 Cole Boulevard 

Golden, CO 80401 

Phone: (303) 384-7703; Fax: (303) 384-6363; E-mail: stefan_czernik@nrel.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Explore feasibility of producing hydrogen from low-cost, potentially high-hydrogen-yield renewable 

feedstocks that could complement biomass feedstocks, increase flexibility, and improve economics of 

the biomass-to-hydrogen process. 

•	 Determine efficiency of pyrolysis/reforming technology in application to readily available postconsumer wastes: plastics, trap grease, mixed biomass and synthetic polymers. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

Approach 

•	 Pyrolysis or partial oxidation of biomass, plastics, and other solid organic residues in the postconsumer waste stream.
 

•	 Catalytic steam reforming of the resulting pyrolysis gases and vapors. 

•	 Catalytic steam reforming of biomass-derived liquid streams (trap grease). 

Accomplishments 

•	 Demonstrated production of hydrogen from polypropylene (PP) by fluidized bed pyrolysis/reforming 

process with the yield: 34 g H2/100 g PP, which is 80% of the stoichiometric potential. 

•	 Demonstrated efficiency of fluidizable, attrition-resistant catalyst developed at NREL for trap grease 

reforming; average yield: 22 g H2/100 g grease (60% of the stoichiometric potential). 

Future Directions 

•	 Identify the nature of catalyst deactivation and improve performance of the production of hydrogen 

from waste grease. 

•	 Test and optimize pyrolysis/reforming process for complex feedstocks (textiles, mixed plastics) using 

commercial and NREL developed catalysts. 

•	 Demonstrate production of hydrogen by co-processing renewable (solid and liquid biomass and 

wastes) and fossil (natural gas) feedstocks. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

The environmental concerns and instability of 

the prices of natural gas make the use of renewable 

biomass and wastes an attractive alternative for the 

production of hydrogen. In recent years, we 

developed a production method that combines two 

stages: fast pyrolysis of biomass to generate bio-oil, 

and catalytic steam reforming of the bio-oil to 

hydrogen and carbon dioxide. Because of the low 

cost of storage and transport of bio-oil, pyrolysis and 

reforming can be carried out at different locations to 

improve the overall process economics. Such a 

concept helps overcome the barrier of high feedstock 

cost for producing hydrogen from biomass. 

This research further addresses the challenge of 

feedstock cost by expanding the feedstock base to 

other renewable low-cost materials that could be 

processed separately or in combination with biomass. 

This year we adapted the technology developed for 

biomass to two types of post-consumer waste 

materials: plastics and "trap grease". Plastics, which 

account for 8%-9% of today's U.S. waste stream, or 

about 15 Mt annually, are mostly landfilled. 

Potentially, the waste plastics could be used to 

generate 6 Mt of hydrogen per year. Waste grease is 

largely available throughout the country and so far is 

mostly discarded (i.e., not recycled or reused). The 

amount of grease collected in traps installed on the 

sewage lines of restaurants and food processing 

plants, and from wastewater treatment plants is about 

6 kg/person/year, which has the potential for 

producing 0.5 Mt of hydrogen annually. 

Approach 

The concept proposed for plastics is a two-stage 

process: fast pyrolysis or gasification to convert 

polymers to a gas/vapor stream of monomers and 

other low-molecular weight compounds followed by 

catalytic steam reforming of this gas to yield 

hydrogen and carbon oxides. "Trap grease" does not 

require a depolymerization step and can be directly 

steam reformed to produce hydrogen. 

Results 

The production of hydrogen from plastics 

(polypropylene) was carried out in a two-reactor 

system shown in Figure 1. Polypropylene was fed to 

the fluidized bed pyrolyzer, where it depolymerized 

to gases and vapors that reacted with steam in the 

second reactor – a fluidized bed catalytic reformer – 

to produce hydrogen, carbon oxides, and minor 

amounts of hydrocarbons. During a 10-hour 

operation, the hydrogen concentration in the product 

gas was above 70%, and its yield was 80% of the 

stoichiometric potential (complete conversion to 

CO2 and H2) as shown in Figures 2 and 3. 

The production of hydrogen from “trap 

grease” was carried out in the single-step 

fluidized bed catalytic steam reforming process 

(liquid grease fed to the reformer). During the 

first year of the project, we used a commercial 

catalyst that did not have sufficient mechanical 

strength, which resulted in significant catalyst 

losses due to attrition and entrainment from the 

Figure 1. Fluidized Bed Integrated Pyrolysis/Reforming 

System 

Figure 2. Product Gas Composition from Pyrolysis/ 

Reforming of Polypropylene 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Yield of Hydrogen from Pyrolysis/Reforming 

of Polypropylene 

Figure 4. Product Gas Composition from Reforming of 

Trap Grease 

reactor. As shown in Figures 4 and 5, the NREL 

developed catalyst used in this year’s tests 

showed a satisfactory performance for 120 hours 

on stream, producing hydrogen with a yield 

greater than 60% of the stoichiometric potential, 

and then deactivated, probably because of the 

contaminants in “trap grease”. The used catalyst 

is analyzed to identify the reason and the nature 

of deactivation. 

Conclusions 

•	 Using a two-reactor pyrolysis/reforming system, 

we demonstrated that hydrogen could be 

efficiently produced from plastics; 34 g 

hydrogen was obtained from 100 g of 

polypropylene, which is 80% of the 

stoichiometric potential. 

•	 Reforming of "trap grease" resulted in 25 g 

hydrogen per 100 g grease for 115 hours of 

catalyst time on stream. After this time, the 

process performance significantly decreased due 

to the catalyst deactivation. 

FY 2003 Publications/Presentations 

1. Chornet, E. and Czernik, S., Renewable Fuels: 

Harnessing Hydrogen, Nature 2002, 418, 928-

929. 

Figure 5. Yield of Hydrogen from Reforming of Trap
 

Grease (WGS = water gas shift)
 

2. Czernik, S., French, R., Feik, C., Chornet, E., 

Hydrogen by Catalytic Steam Reforming of 

Liquid Byproducts from Biomass 

Thermoconversion Processes, Industrial 

&Engineering Chemistry Research 2002, 41, 

4209-4215. 

3. 3.Czernik, S., French, R., Feik, C., Chornet, E., 

Hydrogen from Biomass-derived Liquids, in 

Proceedings of 14th World Hydrogen Energy 

Conference, Montreal, Canada, June 10-14, 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. Record of Invention filed with U.S. DOE. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

4
 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fluidizable Catalysts for Hydrogen Production from Biomass Pyrolysis/Steam 

Reforming 

Kimberly A. Magrini-Bair (Primary Contact), Stefan Czernik, Rick French, Esteban Chornet 

National Renewable Energy Laboratory 

1617 Cole Blvd. 

Golden, CO 80401 

Phone: (303) 384-7706; Fax: (303) 384-6363; E-mail: kim_magrini@nrel.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Subcontractor: Yves Parent (Chemical Engineering Consulting Services) 

Objectives 

•	 Develop attrition resistant supports and multi-functional, multi-component fluidizable catalysts from 

these supports for efficiently reforming pyrolysis vapors and liquids derived from biomass. 

•	 Develop fluidizable catalysts for reforming feedstocks derived from post-consumer waste (trap grease, 

waste plastics). 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 G. Efficiency of Gasification, Pyrolysis, and Reforming Technology 

•	 Z. Catalysts 

Approach 

•	 Develop and optimize fluidizable reforming catalysts using CoorsTek. Inc. specialty aluminas as 

supports. 

•	 Evaluate catalytic reforming performance with gas and liquid phase feedstocks derived from biomass 

and post-consumer wastes. 

•	 Design and fabricate a micro-scale reactor for rapid screening of catalysts. 

Accomplishments 

•	 Optimized catalyst composition for reforming the aqueous fraction of liquids derived from biomass 

pyrolysis. 

•	 Developed a catalyst for waste grease reforming. 

•	 Designed and fabricated a rapid catalyst test system. 

Future Directions 

•	 Develop catalysts for other renewable feedstocks. 

•	 Improve support materials for bubbling and circulating bed systems. 

•	 Understand and overcome deactivation mechanisms (coking, sulfur and phosphorous poisoning). 

•	 Develop non-nickel reforming catalysts. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

Commercial naptha reforming catalysts are used 

to process heavy crude oils in packed bed 

configurations, and they are the most likely industrial 

catalysts available for reforming biomass-derived 

pyrolysis liquids. These catalysts cannot withstand 

the harsh reaction conditions used in a fluidized bed 

for producing hydrogen from pyrolysis liquids. 

Fluidization is preferred in such a case to optimize 

the contact of catalyst with the feedstock and 

minimize coke formation. In a typical commercial 

fixed bed reactor, the pyrolysis liquids tend to form 

coke instead of being reformed. The commercial 

backed bed catalysts, which generally consist of 

nickel coated onto alumina supports, attrit 

significantly when fluidized and yield consistent 

losses of 10-20 wt% per day. Because process 

economics cannot tolerate such catalyst loss, we 

needed to identify and/or develop an attritionresistant support that can withstand fluidized 

reforming conditions. 

Numerous support screening experiments 

showed that commercially available specialty 

alumina materials produced by CoorsTek Ceramics 

could have the necessary strength to withstand 

fluidizing conditions. Catalysts made from these 

supports have been used to reform pyrolysis liquids, 

and the generated performance data have been used 

to refine subsequent catalyst compositions. This year 

we report results from continued development of 

catalysts for reforming aqueous pyrolysis liquids and 

preliminary results from testing our catalysts with 

other renewable feedstocks including biomass 

gasification vapors and waste trap grease. These 

feedstocks require fine-tuning of the catalyst 

composition to handle sulfur impurities in trap grease 

and tars contained in gasification vapors. The 

challenge now is to design novel catalysts with 

improved reforming activity, gasification activity 

(gasify coke deposits on the catalyst surface), and 

poison tolerance (sulfur and phosphorous contained 

in trap grease) for these new feedstocks. 

Approach 

We have developed robust nickel-based 

reforming catalysts from strong alumina particles 

produced by CoorsTek Ceramics. These materials, 

 FY 2003 Progress Report 

which can withstand the harsh conditions required 

for reforming pyrolysis liquids, produce hydrogen 

with efficiencies as good or better than those of the 

best commercial catalysts. Our best original catalyst 

composition, compared to the composition of a 

commercial reforming catalyst, provided good 

activity and performance for reforming aqueous 

pyrolysis liquids. Our work this year focused on 

refining that base composition to further improve 

catalyst performance for reforming the liquids. 

Additionally, we began testing the basic catalyst with 

other renewable feedstocks and assessing how 

feedstock changes impact catalyst performance. 

The overall goal is to design cost efficient feedstockflexible reforming catalysts. 

All catalysts were evaluated with the aqueous 

fraction of pyrolysis oils from pine or mixed 

hardwoods for a 24-hour period in a two-inch 

fluidized bed laboratory scale reactor equipped with 

in-line gas analyzers and process controllers. Inlet 

and outlet gas compositions at steady state conditions 

were used to calculate hydrogen, carbon dioxide, 

carbon monoxide, and methane yields. We used the 

CO2/CO ratio (from the reformed gas mixture) as a 

general measure of selectivity for water-gas shift 

(WGS) and coke gasification, and we used the H2/ 

CH4 ratio to measure reforming selectivity. Overall 

activity is measured by the H2 yield, which is the 

ratio of actual yield to theoretical yield x 100. 

Theoretical yield is the amount of hydrogen 

produced if reforming and WGS reactions convert all 

carbon in the feedstock to CO2. Performance data 

were then correlated with catalyst compositions to 

guide the next choice of catalyst “recipe” to test. 

Results 

Table 1 shows catalyst and performance data for 

four catalyst compositions compared to the 

commercial reforming catalyst C 11 NK. Our goal 

this year was to improve hydrogen yields (reforming 

activity) and to improve feeding of the pyrolysis 

liquids into the fluidized catalyst bed. The H2/CH4 

ratio shows that we can meet or exceed commercial 

catalyst selectivity for hydrogen production though 

WGS performance, measured by CO2/CO, is still 

less than that of the commercial material. Note as 

well that our catalysts use significantly smaller 

quantities of Ni, Mg, and K than does the 

2 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

commercial material. The implication of this result 

is that we can now consider using other reforming 

metals like platinum and palladium since required 

amounts are less. 

Figure 1 compares performance data for several 

catalysts and lists the composition data. Catalysts 

10-12 all contain about the same amount of 

potassium oxide (K2O), and feeding upsets are 

clearly seen as spikes in the hydrogen content. We 

think the spikes are caused by solid chunks of 

feedstock, located at the injection nozzle, breaking 

up in the fluidized catalyst bed. The commercial 

catalyst and catalysts 14-15 do not exhibit feedstock 

spiking, and we think this is attributable to the 

increased amount of K2O contained in these 

materials. Potassium promotes gasification, the 

Figure 1.	 Catalyst Performance for H2 Production from 

Reforming Aqueous Pyrolysis Liquids at 

850°C in a 2-inch Fluidized Bed Reactor; 

Feeding Deposits Are Related to Catalyst 

K2O Content 

 FY 2003 Progress Report 

formation of volatile carbon oxides from solid 

carbon, and seems to inhibit the formation of 

carbonized feedstock chunks at the injection nozzle. 

Improving feeding behavior of a complex, difficult to 

feed material is a significant accomplishment that 

will allow routine use of aqueous pyrolysis liquids in 

fluidized reactors. 

Figure 2 compares performance of one of our 

best catalysts with that of the commercial material 

for pyrolysis liquid reforming. Our catalyst produces 

hydrogen in higher yield than the commercial 

catalyst though our WGS activity is lower. Our 

catalyst also produces more methane though the 

commercial catalyst likely reaches the same methane 

concentration for extended reaction time. The WGS 

reaction, which produces H2 and CO from catalytic 

reaction of H2O and CO2, is also catalyzed by nickel. 

Figure 2.	 Catalyst Performance of our Catalyst #15 and 

the Commercial Catalyst C 11 NK for 

Pyrolysis Liquid Reforming at 850°C in a 

2-inch Fluidized Bed Reactor 

Table 1. Catalyst Selectivity Data for Reforming Aqueous Pyrolysis Oil Extracts Calculated During the Interval 

20-23 Hours of On-Stream Reaction 

CATALYST Wt % 

NiO 

Wt % 

MgO 

Wt % 

K2O 

SUPPORT 

% Al2O3 

CO2/CO H2/CH4 H2 

YIELD 

C 11 NK 20 5.0 8.0 MIX 4.1 39.6 91 

CAT 11 2.0 1.0 0.1 90 1.4 54.0 84 

CAT 12 4.0 2.0 0.1 90 1.8 57.1 87 

CAT 14 2.0 0.2 0.5 90 1.0 30.0 79 

CAT 15 4.0 0.4 1.0 90 2.1 39.9 83 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

We continue to work on improving WGS activity 

through composition changes. 

We evaluated the performance of catalyst 15 with 

two feedstocks: pyrolysis liquids and liquid trap 

grease (waste restaurant grease). The trap grease was 

washed with several volumes of hot water to remove 

soluble impurities like sodium chloride prior to use. 

The trap grease is less chemically complex than the 

pyrolysis liquids and should be easier to reform. 

Figure 3 verifies that assumption by showing a 

slightly better hydrogen yield from trap grease. 

Initial WGS activity was better for trap grease, but it 

began to decline after three hours of reaction. WGS 

activity for pyrolysis liquids never reached that of 

trap grease though the decline came later at six hours 

of reaction and reached a steady state. Methane 

production was the same for both feedstocks. 

Preliminary surface analysis of the fresh and used 

catalysts (all composition 15) showed that trap grease 

catalyst contained about 150 ppm of surface 

phosphorous, which had to come from the feedstock 

as neither the fresh catalyst nor the catalyst used for 

pyrolysis liquids contained any phosphorous. It is 

possible that phosphorous impacted WGS activity 

Figure 3.	 Catalyst #15 Performance Data for H2 

Production by Reforming Aqueous Pyrolysis 

Liquids and Waste Grease at 850°C in a 2­

inch Fluidized Bed Reactor 

 FY 2003 Progress Report 

though it did not appear to affect hydrogen 

production. This result demonstrates the impact that 

feedstock will have on overall reaction performance. 

Conclusions 

•	 Developed novel, attrition-resistant fluidizable 

reforming catalysts with CoorsTek Specialty 

Ceramics. 

•	 Evaluated performance of 16 catalysts for 24 hrs 

with pyrolysis oil-derived feedstocks in a small 

pilot scale reactor. This provides steady state 

comparison of catalyst performance with 

different feedstocks and varied catalyst 

compositions. 

•	 Improved reforming activity (compared to 

commercial catalyst) for pyrolysis oils with 

reduced nickel content catalysts though WGS 

activity remains slightly less than that of the 

commercial catalyst. 

•	 Improved pyrolysis oil feeding to the fluidized 

catalyst bed by increasing potassium oxide 

(K2O) content. 

•	 Developing sulfur- and phosphorous-tolerant 

catalyst compositions for reforming waste 

grease. 

FY 2003 Publications/Presentations 

1. K. Magrini, SC. Czernik, R. French, Y. Parent, E. 

Chornet, "Fluidizable Catalyst Development for 

Steam Reforming Biomass-Derived Feedstocks", 

in preparation. 

Special Recognitions & Awards/Patents 

Issued 

1. Record of Invention on fluidizable catalysts filed 

with DOE. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen from Biomass for Urban Transportation 

Y. D. Yeboah (Primary Contact), K. B. Bota, and Z. Wang 

Clark Atlanta University 

223 James P. Brawley Drive 

Atlanta, GA 30314 

Phone: (404) 880-6619; Fax: (404) 880-6615; E-mail: yyeboah@cau.edu 

DOE Technology Development Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmund.Gronich@ee.doe.gov 

NREL Technical Advisor: Dr. Robert Evans 

Phone: (303) 384-6284, Fax: (303) 384-6363, E-mail: bob_evans@nrel.gov 

Subcontractors: 

Scientific Carbons Inc, Blakely, GA 

Georgia Institute of Technology, Atlanta, GA 

Enviro-Tech Enterprises Inc, Matthews, NC 

Objectives 

•	 Undertake the engineering research and pilot-scale process development studies to economically 

produce hydrogen from biomass such as peanut shells. 

•	 Educate and train underrepresented minorities to enhance diversity in the nation's workforce in the 

energy area. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis and Reforming Technology 

Approach 

•	 Develop feedstock supply, process economics and deployment strategies. 

•	 Design, construct, integrate and test pyrolysis-reformer pilot reaction unit. 

•	 Undertake long term (1,000 hours) testing of the performance of the catalyst. 

•	 Design, construct and test the hydrogen separation and storage unit. 

•	 Develop an environmental and technical evaluation method based on analytical monitoring of process 

streams. 

•	 Develop partnerships, collaborations and education and training programs. 

Accomplishments 

•	 Continued developing a model of network process steps to account for feedstock, location, process, 

and the uncertainties in these factors. 

•	 Collected bio-oil and determined solubility parameters and physical property estimation methods of 

the components of the bio-oil product of peanut shell pyrolysis. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Completed system modifications, integration and 100-hour pyrolysis-reformer run for long term 

catalyst testing. 

•	 Completed analysis of the data for the 100-hour long term catalyst testing. 

•	 Identified potential agricultural uses of the carbon product from the pyrolysis unit. 

•	 Developed plans for 1,000-hour long term testing of the catalyst and process for Phase 3. 

•	 Initiated partnership and collaboration with the University of Georgia, Athens, to move the pyrolysisreformer pilot unit to their Bioconversion Center facilities in Athens, GA. 

•	 Initiated evaluation of approaches to hydrogen separation and storage, including pressure swing 

adsorption (PSA) and Quantum's technology for hydrogen storage. 

•	 Held Phase 3 project review meetings at Clark Atlanta University and the University of Georgia, 

Athens. 

Future Directions 

•	 Complete development of models and solutions. 

•	 Perform solubility and physical property measurements and estimations. 

•	 Complete extraction studies and the evaluation of phenolates as co-products for adhesives. 

•	 Modify pyrolyzer, reformer, analysis and other process units for long term testing. 

•	 Design, install and test preheater and PSA units. 

•	 Install new sensors and process control system software in pilot unit. 

•	 Move and integrate units at the University of Georgia Bioconversion Center. 

•	 Perform shakedown run of the integrated system. 

•	 Complete the proposed 1,000 hours of long term operation. 

•	 Complete the engine tests for stationary applications. 

•	 Complete all partnership arrangements. 

Introduction 

Biomass can be converted to hydrogen by two 

distinct strategies: 1) gasification followed by shift 

conversion and 2) pyrolysis of biomass to form a biooil that can be subsequently converted to hydrogen 

via catalytic steam reforming and shift conversion. 

This project uses the latter approach, which has the 

potential to be cost competitive with current 

commercial processes for hydrogen production [1]. 

The process has been demonstrated at the bench scale 

at the National Renewable Energy Laboratory 

(NREL) using model compounds and the 

carbohydrate-derived fraction of bio-oil [2,3]. The 

concept has several advantages over the traditional 

gasification technology. Bio-oil is easily 

transportable, so the second step (steam reforming) 

can be carried out at a different location, close to the 

existing infrastructure for hydrogen use or 

distribution. The second advantage is the potential 

for production and recovery of higher-value coproducts from bio-oil that could significantly impact 

the economics of the entire process. 

The project focuses on the use of agricultural 

residues such as peanut shells to produce hydrogen 

for urban transportation using the pyrolysisreforming technology. Specifically, a pilot-scale 

reactor on site at Scientific Carbons Inc.-a small 

company in Blakely, Georgia, that produces activated 

carbon by pyrolysis of densified peanut shells-is 

being used to test the concept. The primary focus of 

Phases 1 and 2 of the project was to undertake the 

process development studies in the use of the large 

quantities of peanut shells produced in Georgia as 

feedstock for the proposed pyrolysis-steam 

reforming process. Phase 1 designed, constructed 

and tested the reformer unit. In Phase 2, Scientific 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Carbons's pilot-scale pyrolyzer, which has a feed rate 

of 50 kg/hour, was integrated with the reformer and 

used to perform a demonstration of the process to 

convert the off-gas of the peanut-shell carbonization 

process to hydrogen. The integrated pilot process 

was successfully tested for 100 hours. Phase 3 will 

make further modifications and perform a 1,000-hour 

long term performance testing of the catalyst and 

pilot system. The process could be modified and 

expanded to run a variety of other feedstocks and to 

make a range of alternative products. 

Approach 

The approach used to conduct the study is based 

on six main tasks: 

1. Feedstock supply, process economics, and 

deployment strategies (modeling, extraction and 

property estimation): Literature data and 

thermodynamic models were employed to 

evaluate a large number of organic solvents for the 

extraction of phenol from aqueous bio-oils. 

Several good solvents were identified, and 

extractions were carried out on bio-oil samples 

provided by NREL. Process models for feedstock 

supply and deployment strategies were developed. 

2. Reactor modifications and shakedown: 

Modifications in the pyrolyzer and reformer were 

made, and the entire system, including the 

pyrolyzer, reformer, and analytical instruments, 

was integrated and tested. The pyrolyzer unit 

achieves its heat requirements through the use of a 

rich burning natural gas burner. A computer is 

used to track the temperature and pressure drops 

across the reactors. 

3. Long term catalyst testing: The pilot unit was 

operated in Phase 2 for 100 hours for the long 

term catalyst testing. 

4. Hydrogen separation, storage and utilization: The 

effort in hydrogen separation is focused on the use 

of pressure swing adsorption (PSA) for the 

separation of the hydrogen from carbon dioxide. 

After the baghouse and condenser, the reformer 

gas will be dried and compressed before being 

sent to the PSA system. The current plans are to 

use an accumulator to store the hydrogen before 

sending it into an engine for performance testing. 

5. Environmental and technical evaluation: A 

hydrogen analyzer and a gas chromatograph 

were set up to continuously monitor on line the 

gas composition and the performance of the 

reformer bed. 

6. Partnership building and outreach: The project 

team initiated discussions with the University of 

Georgia (UGA) to move the pilot unit from 

Blakely, Georgia, to the Bioconversion Center 

facilities at UGA. The idea was enthusiastically 

received by UGA. Several meetings were held 

among the project partners and UGA at Clark 

Atlanta University and UGA. The current plans 

are to move the unit to the Bioconversion Center 

facilities in the summer of 2003. 

Results 

Figure 1 shows photographs of the pilot unit, its 

components and the flares from the pyrolyzer and 

reformer units. The temperature and pressure 

profiles across the reformer and orifice plate are 

depicted in Figure 2. The figure indicates that the 

100 hours operation was fairly stable without any 

plugging in the plate or flow lines. No hot spots 

developed within the fluidized bed reactor. 

The composition profile of the effluent gas from 

the reformer is given in Figures 3 and 4. Figure 3 

gives the profile over the entire run period, and 

Figure 1. Pictures of the Pilot Plant Unit, Components 

and Flares 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 2. Temperature and Pressure Profiles of 

Reformer and Orifice Plate 

 FY 2003 Progress Report 

summarized in Table 1. Also shown in Table 1 are 

the yields of char, water, bio-oils and gas obtained in 

the pyrolysis unit. The results show about 60% 

hydrogen, 25% carbon dioxide, 10% carbon 

monoxide and 5% methane in the reformer gas. The 

pyrolysis resulted in about 30% char, 30% water, 

30% bio-oils and 5% gases. 

Table 1: Yields and Gas Composition for the 100-hour 

Run 

Figure 3. Composition Profile of the Reformer Gas 

over the Long-Term Run Period 

Figure 4. Gas Composition over a 20-hr Period During 

the Long-Term Catalyst Test 

Figure 4 gives the profile of a 20-hour section. The 

average gas composition (volume % on dry and 

nitrogen-free basis) over the run period is 

Pyrolyzer 

(Yields %) 

Reformer Gas 

Product Composition, 

(% Dry N2-free basis) 

Char 32 Hydrogen 57 

Water 32 Carbon Dioxide 26 

Bio-Oils 31 Carbon Monoxide 12 

Gases 5 Methane 5 

Conclusions 

•	 Demonstrated successfully pyrolysis-reformer 

concept for 100 hours operation. 

•	 Discovered agricultural uses and carbon 

sequestration strategy via novel carbon slow 

release sequestered fertilizer. 

•	 Identified economical co-product options for 

bio-oils, e.g., adhesives. 

•	 An engine will be run successfully with the 

product gas with significant reduction of NOx. 

•	 Further R&D: over 1,000 hours operation and 

higher hydrogen production rate could lead to 

economically competitive hydrogen and a viable 

integrated bioconversion process. 

References 

1. Mann, M.K. 1995. “Technical and economic 

analyses of hydrogen production via indirectly 

heated gasification and pyrolysis,” in Proceedings 

of the 1995 Hydrogen Program Review, Vol. 1, 

NREL/CP-430-20036-Vol. 1, pp. 205-236. 

2. Wang, D., S. Czernik, D. Montané, M. Mann, and 

E. Chornet, 1997, I&EC Research, 36, 1507-1518. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

3. Wang, D., S. Czernik, and E. Chornet, 1998, 

“Production of Hydrogen from Biomass by 

Catalytic Steam Reforming of Fast Pyrolysis Oil”, 

Energy&Fuels, 12, 19-24. 

FY 2003 Publications 

1. Annual Project Review Presentation made at the 

Hydrogen, Fuel Cells and Infrastructure Review 

Meeting at Berkeley, CA, May 18-22, 2003 

2. Semiannual report on project submitted to the 

Department of Energy in April 2003 

3. Evans, R; E Chornet, S. Czernik, C. Feik, R. 

French, S. Philips, J. Abedi, Y. Yeboah, D. Day, J. 

Howard, D. McGee and M. Realff (2002), 

Renewable hydrogen production by catalytic 

steam reforming of peanut shells pyrolysis 

products, American Chemical Society (ACS) 

Paper presented at the Annual ACS Meeting, 

Boston, MA 

 FY 2003 Progress Report 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Reformer Model Development for Hydrogen Production 

Josette Bellan 

Jet Propulsion Laboratory 

4800 Oak Grove Drive 

MS 125-109 

Pasadena, CA 91109-8099 

Phone: (818) 354-6959; Fax: (818) 393-5011; E-mail: josette.bellan@jpl.nasa.gov 

DOE Program Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-1637; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Research and develop low cost, highly efficient hydrogen production from renewable sources 

•	 Reduce the cost of distributed production of hydrogen from liquid fuels such as diesel and biomass oils 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance 

•	 C. Feedstock and Water Issues 

•	 D. Carbon Dioxide Emissions 

•	 E. Control and Safety 

•	 F. Feedstock Cost and Availability 

•	 G. Efficiency of Gasification, Pyrolysis and Reforming Technology 

Approach 

•	 Develop a two-part database that is the benchmark for developing and testing the elements of the 

reformer model, called submodels 

•	 Derive submodels from one part of the database to be used for the reformer simulation 

•	 Use the complement of the database to test the derived submodels 

•	 Validate the entire model using experimental data 

•	 Utilize the validated model to optimize and scale up reformers 

Accomplishments 

•	 Created a two-part database portraying the evaporation and mixing of a large number of singlechemical-species-liquid drops in a turbulent flow 

•	 Used one part of the database to develop computationally efficient models (called submodels) of the 

small scale interaction of the drops and flow 

•	 Tested the submodels on the complement of the database to assess the interaction of the submodels 

with the large scales; found a model that is stable and accurate and reduces computational costs by a 

factor of 300 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Tested a model of multicomponent-liquid (i.e. mixture of many chemical species, as in diesel and 

biomass oils) drop existing in the literature and found that it has serious limitations 

•	 Developed a computationally efficient improved model of the evaporation of a multicomponent-liquid 

drop when the fuel is a mixture of hundreds of chemical species 

Future Directions 

•	 Validate the single-chemical-species-liquid model with experimental data for an evaporating spray 

•	 Create a database of the evaporation and turbulent mixing of multicomponent-liquid drops to enable 

the extraction of submodels for complex-mixture liquids 

•	 Extract submodels for complex-mixture liquids evaporation and turbulent mixing 

•	 Test the interaction of the submodels for complex-mixture liquids evaporation and turbulent mixing 

with the large flow scales 

•	 Validate the multicomponent-liquid model with experimental data for an evaporating spray 

•	 Create a two-part database of the reforming reactions in turbulent flows in the presence of evaporating 

multicomponent-liquid drops to enable the extraction of submodels for the chemistry/turbulent-flow 

interaction 

•	 Use one part of the database to extract submodels of the interaction between chemistry and turbulence 

•	 Test these submodels on the complement of the database to assess the interaction between the 

submodels and the database 

• Validate the reformer model (i.e. turbulent, reactive flow laden with evaporating drops) by comparing 

with experimental data 

Introduction 

Reforming is a chemical process wherein a 

hydrocarbon feedstock reacts with water to form H2 

and other gaseous chemical species. These reactions 

are induced in a container, called the reactor. In this 

reactor, the feedstock is introduced in the form of a 

spray of drops. Atomization of a liquid (i.e., the 

formation of drops) enlarges the surface area of the 

liquid, thereby promoting evaporation. The 

evaporated species reacts with steam in the presence 

of catalysts which enhance the reaction. The reactor 

operates at a temperature of 700oC to 850oC and 

pressures of 3 to 25 atmospheres, which favor the 

output of the reaction [1]. Concerns encountered 

with reforming for H2 production are the efficiency 

of the process (e.g. optimization of the parameters for 

maximum yield), which must be high enough to 

render H2 economically viable; the presence of 

coking reactions, which build carbon on the catalysts, 

thereby deactivating them; and reactor scale-up to 

industrial sizes. 

The present study addresses all concerns of the 

process with the goal of understanding the details of 

the physical/chemical processes involved, so as to 

enable changes of the present operation that are 

based on physics/chemistry rather than 

circumstantial empirical correlations. This 

understanding will also be vital in proposing reactor 

scale-up. 

Approach 

The approach is based on numerical simulations 

that are experimentally validated. The idea is that 

just as the aircraft industry uses simulations to design 

aircraft (and no longer performs costly wind-tunnel 

testing), the hydrogen industry can eventually design 

reformer reactors using simulations as well. 

However, in many ways the situation in a reformer is 

considerably more challenging to model than for the 

aircraft; in the reformer one has a turbulent twophase (liquid drops and gas) reacting flow with phase 

change (drop evaporation). Moreover, the feedstock 

is invariably a complex mixture of hydrocarbons that 

cannot be effectively treated as a single chemical 

2 
 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

species because different components of the mixture 

are responsible for different aspects of the process. 

The methodology uses the contemporary direct 

numerical technique called DNS to achieve a 

transitional state, defined as a state displaying 

turbulent features. The DNS is performed in a 

domain much smaller than that of interest because 

currently and in the foreseeable future there is no 

large enough computer to simulate turbulent flows of 

practical interest; even with the small domain size, 

these DNS calculations are very computationally 

intensive, lasting thousands of computer hours. 

However, neither the small DNS domain size nor the 

costly computations are of concern because this 

simulation is supposed to be only a tool for model 

development. The models extracted from DNS are 

Subgrid Scale (SGS) models, and they represent the 

small-scale behavior of the flow. This small-scale 

behavior cannot be computationally resolved for 

flows of practical interest; therefore, SGS modeling 

is used. The simulations wherein the large scale of 

engineering interest are computed, and the small 

scales, all of which have a major impact on large 

scales, are modeled, is called Large Eddy Simulation 

(LES). These LESs are intended to be 

computationally much cheaper than the DNS, so as 

to be able to use them on a routine basis for 

engineering design. The goal is here to create DNS 

databases, develop SGS models, and ultimately 

perform LES. The predictive ability of LES crucially 

depends on the quality of the SGS models. 

Results 

We have created DNS databases of transitional 

states both for gaseous flows and for flows 

containing millions of drops. For drop-laden flows, 

we have used in the computation either singlecomponent (SC) or multicomponent (MC) drops. To 

model MC drop evaporation, we used a model 

already existing in the literature, which we showed 

contained limitations when exercised for drops 

evaporating in mixtures of air and hydrocarbon 

vapor. The limitations motivated us to develop a 

more robust model of MC drop evaporation, which 

was validated in its predictive capability [2]. 

SGS models were developed using one part of 

the DNS database and then tested on the complement 

of the database. The results showed that currently 

used SGS models are inherently incorrect, in that 

they are unable to reproduce the DNS database [3]. 

Particular deficiencies are mostly seen in their 

inability to predict the correct drop distribution in the 

flow and the correct mixture fraction, which is 

essential for predicting reforming reactions. From 

the analysis of the database, we have developed 

accurate SGS models that are as computationally 

inexpensive as those incorrect ones that are currently 

used. This comparison is presented in Figures 1-6, 

which also include in the captions the computational 

times necessary to achieve these states starting from 

two segregated gaseous streams moving with respect 

to each other, where the bottom stream is laden with 

drops that may evaporate (the initial gas temperature 

is larger than the initial drop temperature). The 

initial mass loading with liquid drops is 50%. The 

results show that Figure 2 is only a caricature of 

Figure 1, rather than a replicate, and the same can be 

said of Figure 5 with respect to Figure 4. In contrast, 

Figure 3 replicates reasonably well Figure 1, and 

Figure 6 compares very favorably with Figure 4, and 

this at only a fraction of the computational time of 

the original simulation. 

Figure 1. Drop number density (in m-3) obtained from 

a DNS. The figure illustrates the results from 

a computation that lasted 2981 hours of 

computer time. In the figure, the small scales 

are removed, and only one out of 8 drops is 

shown, in order to have an appropriate 

comparison with LES. 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Drop number density (in m-3) obtained from 

a LES using currently used SGS models. The 

simulation lasted 37 hours of computer time. 

Figure 4. Vapor mass fraction obtained from the same 

DNS as in Figure 1. Just as in Figure 1, the 

small scales are removed, and only one out of 

8 drops is shown, in order to have an 

appropriate comparison with LES. 

Figure 3. Drop number density (in m-3) obtained from a 

LES using the best SGS model developed in 

this program. The simulation lasted 37 hours 

of computer time (same number of hours as 

in Figure 2). 

Figure 5.Vapor mass fraction obtained from a LES. 

The figure illustrates the results from the 

same computation as in Figure 2. 

Conclusions be stated about the modeling of evaporating drops of 

complex hydrocarbon mixtures. Models developed 

It is now apparent that current models are highly in this project have the ability to remedy these 

deficient in their portrayal of turbulent mixing and deficiencies and will thus be used in further 

drop evaporation in a turbulent flow. The same can computationally efficient simulations. 

4 
 

 

Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

Figure 6. Vapor mass fraction obtained from a LES. 

The figure illustrates the results from the 

same computation as in Figure 3. 

References 

1. Ogden, J., Review of small stationary reformers 

for hydrogen production, Report IEA/H2/TR-02/ 

002 

2. Harstad, K., Le Clercq, P. C., and Bellan, J., A 

statistical model of multicomponent-fuel drop 

evaporation for many-droplet gas-liquid flow 

simulations, accepted in the American Institute of 

Aeronautics and Astronautics Journal, 2003 

3.	 Leboissetier, A., Okong’o, N. and Bellan, J., 

Consistent Large Eddy Simulation of a temporal 

mixing layer laden with evaporating drops. Part 

III: A posteriori modeling, to be submitted to the 

J. Fluid Mech., 2002 

FY 2002 Publications/Presentations 

1. “Direct Numerical Simulations of Two-phase 

Laminar Jet Flows with Different Cross-Section 

Injection Geometries”, (H. Abdel-Hameed and J. 

Bellan), Phys. Fluids, 14(10), 3655-3674, 2002 

2. “Consistent Large Eddy Simulation of a temporal 

mixing layer laden with evaporating drops. Part I: 

Direct Numerical Simulation and formulation”, 

(N. Okong’o and J. Bellan), submitted to the J. 

Fluid Mech., 2002 

3. “Consistent Large Eddy Simulation of a temporal 

mixing layer laden with evaporating drops. Part 

II: A priori modeling”, (N. Okong’o and J. 

Bellan), submitted to the J. Fluid Mech., 2002 

4. “Direct numerical simulation of a transitional 

temporal mixing layer laden with 

multicomponent-fuel evaporating drops using 

continuous thermodynamics”, (P. C. Le Clercq 

and J. Bellan), submitted to the J. Fluid Mech., 

2002 

5. “A statistical model of multicomponent-fuel drop 

evaporation for many-droplet gas-liquid flow 

simulations”, (K. G. Harstad, P. C. Le Clercq and 

J. Bellan), accepted in the AIAA J, 2003 

6. “A robust statistical model for the evaporation of 

multicomponent-fuel drops containing a multitude 

of chemical species”, (K. G. Harstad, P. LeClercq 

and J. Bellan), paper AIAA 2003-1321, presented 

at the 41st Aerospace Sciences Meeting, Reno, 

NV, 2003 

7. “The statistical modeling of multicomponent-fuel 

drop evaporation for fuels containing a multitude 

of species”, (K. G. Harstad, P. LeClercq and J. 

Bellan), presented at the Joint Meeting of the US 

Sections of the Combustion Institute, March 17-

19, 2003 

8. “A priori study of models for large eddy 

simulations of drop-laden flows”, (N. Okong’o 

and J. Bellan), presented at the Joint Meeting of 

the US Sections of the Combustion Institute, 

March 17-19, 2003; also ILASS 2003, Monterey, 

CA, May 18-21, 2003 

9. “A posteriori study of models for large eddy 

simulations of drop-laden flows”, (A. 

Leboissetier, N. Okong’o and J. Bellan), ILASS 

2003, Monterey, CA, May 18-21, 2003 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Special Recognitions & Awards/Patents 

Issued 

1. NASA Certificate of Recognition for each one of 

the papers above 

2. Invited publication (appeared July 2002) by the 

Chemical Propulsion Information Agency 

Bulletin, sponsored by the DoD Information 

Analysis Center 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Maximizing Photosynthetic Efficiencies and Hydrogen Production in 

Microalgal Cultures 

Tasios Melis (Primary Contact) 

University of California, Berkeley 

Department of Plant & Microbial Biology 

111 Koshland Hall 

Berkeley, CA 94720-3102 

Phone: (510) 642-8166; Fax: (510) 642-4995; E-mail: melis@nature.berkeley.edu 

DOE Program Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-1637; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Minimize, or truncate, the chlorophyll (Chl) antenna size in green algae to maximize photobiological 

solar conversion efficiency and hydrogen production. 

•	 Demonstrate that a truncated Chl antenna size would minimize absorption and wasteful dissipation of 

sunlight by individual cells, resulting in better light utilization efficiency and greater photosynthetic 

productivity by the green alga culture. 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Light Utilization Efficiency 

Approach 

•	 Employ DNA insertional mutagenesis, screening, biochemical and molecular genetic analyses for the 

isolation of "truncated Chl antenna size" strains in the green alga Chlamydomonas reinhardtii. 

•	 Clone and characterize the gene(s) that affect the "Chl antenna size" in Chlamydomonas reinhardtii. 

•	 Apply such genes to generate a "truncated Chl antenna size" in this green alga. 

Accomplishments 

•	 First-time cloning of Tla1, a 'Chl antenna size regulatory gene' (30-year breakthrough). 

•	 DNA, mRNA and protein sequences were deposited in the GenBank (GenBank Accession No. 

AF534570 and AF534571). 

•	 Manuscript on this gene and its application to this project was published in the peer-reviewed 

international journal 'Planta'.
 

•	 The DOE's Joint Genome Institute validated the sequence information on the Tla1 gene and credited 

our work regarding the function of this gene. 

•	 Results from this work apply directly to green alga hydrogen production, biomass accumulation, and 

carbon sequestration efforts. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Identify additional Tla-type genes. 

• Functionally characterize these genes (how do they work?). 

• Perform genetic crosses to combine different tla-type properties and phenotypes. 

• Establish transformation protocols with Tla-type genes to downregulate the Chl antenna size in 

Chlamydomonas reinhardtii. 

Introduction 

The goal of the research is to generate green 

algal strains with enhanced photosynthetic 

productivity and hydrogen production under mass 

culture conditions. To achieve this goal, it is 

necessary to optimize the light absorption and 

utilization properties of the cells (Kok 1953; Myers 

1957; Radmer and Kok 1977). A cost-effective way 

to achieve this goal is via a reduction in the number 

of chlorophyll (Chl) molecules that function in 

photosynthesis. Thus, efforts are under way to 

isolate microalga mutants with a truncated 

chlorophyll antenna size. 

The rationale for this R&D is that a truncated 

light-harvesting Chl antenna size in green algae will 

Figure 1.	 Schematic of the fate of absorbed sunlight in 

fully pigmented (dark green) algae. 

Individual cells at the surface of the culture 

over-absorb incoming sunlight (i.e., they 

absorb more than can be utilized by 

photosynthesis), and ‘heat dissipate’ most of 

it. Note that a high probability of absorption 

by the first layer of cells would cause 

shading, i.e., would prevent cells deeper in 

the culture from being exposed to sunlight. 

prevent individual cells at the surface of the culture 

from over-absorbing sunlight and wastefully 

dissipating most of it (Figure 1). A truncated Chl 

antenna size will permit sunlight to penetrate deeper 

into the culture, thus enabling many more cells to 

contribute to useful photosynthesis and hydrogen 

production (Figure 2). It has been shown that a 

truncated Chl antenna size will enable up to ~3 times 

greater solar energy conversion efficiency and 

photosynthetic productivity than could be achieved 

with fully pigmented cells (Melis et al. 1999). The 

research seeks to develop Chlamydomonas 

reinhardtii strains having a permanently truncated 

Chl antenna size, and to isolate and characterize the 

genes and proteins that confer this property to the 

green algae. This information will find direct 

application in hydrogen production, biomass 

accumulation and carbon sequestration. 

Figure 2.	 Schematic of sunlight penetration through 

cells with a truncated chlorophyll antenna 

size. Individual cells have a diminished 

probability of absorbing sunlight, thereby 

permitting deeper penetration of irradiance 

and hydrogen production by cells deeper in 

the culture. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Approach 

The immediate objective of the research is to 

identify genes that control the Chl antenna size of 

photosynthesis, and further, to manipulate such genes 

so as to confer a truncated Chl antenna size in the 

model green alga Chlamydomonas reinhardtii. 

Identification of such genes in Chlamydomonas will 

permit a subsequent transfer of this property, i.e., 

"truncated Chl antenna size", to other microalgae of 

interest to the DOE Hydrogen, Fuel Cells and 

Infrastructure Technologies Program. 

This objective is currently being approached 

through DNA insertional mutagenesis/screening and 

biochemical/molecular/genetic analyses of 

Chlamydomonas reinhardtii cells. 

Results 

In FY 2003, work described the molecular, 

genetic and functional properties of tla1, a 

Chlamydomonas reinhardtii DNA insertional 

transformant having a truncated light-harvesting 

chlorophyll antenna size. The plasmid insertion into 

the nuclear DNA of this transformant interrupted 

Tla1, a newly identified gene, which is apparently 

responsible for the regulation of the Chl antenna size 

in green algae (Polle et al. 2003). To the best of our 

knowledge, this is a first-time cloning and genomicproteomic characterization of a Chl antenna size 

regulatory gene in photosynthesis. A summary of the 

results obtained is given in bullet form, below: 

•	 6,500 DNA insertional transformants were generated and screened (Polle et al. 2003). Only one 

mutant with a 'truncated Chl antenna size' could 

be identified. 

•	 Genetic crosses and mapping of the DNA around 

the insertion site confirmed that the exogenous 

plasmid interfered with a novel gene, termed by 

us as Tla1. 

•	 DNA, mRNA and protein sequences of Tla1 

were elucidated and deposited in the GenBank 

(GenBank Accession No. AF534570 and 

AF534571). 

•	 Absorbance-difference kinetic spectrophotometry (Dspec) revealed that interference with the 

Tla1 gene expression resulted in a truncated photosystem II (PSII) Chl antenna size, down to 

 FY 2003 Progress Report 

50%, and a photosystem I (PSI) Chl antenna size, 

down to 67% (Table 1). 

Table 1. C. reinhardtii cellular chlorophyll content and 

photosystem chlorophyll antenna size in wild 

type and tla1 mutant as determined by Dspec 

analysis (n = 5, ±SD). 

wild type tlal

% 

change 

Longterm 

goal 

Chl/cellmol x10-15 

2.4 ±0.5 0.9 ±0.06 38% 

Chl-PSII 222±26 114±36 51% 37 

Chl-PSI 240±4 159±12 66% 95 

•	 Sodium-dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) analysis revealed lack of 

specific light-harvesting complex proteins from 

the antenna of the tla1 (Polle et al. 2003). 

•	 A light-saturation curve of photosynthesis measurements revealed a greater light intensity for 

the saturation of photosynthesis in the tla1 

mutant than in the wild type, revealing a minimized ability to absorb light and less wasteful 

dissipation of excitation energy as heat. 

• The 	 tla1 mutant showed enhanced light utilization 

efficiency and greater photosynthetic productivity 

under mass culture conditions (Figure 3). 

Conclusions 

•	 The partially truncated chlorophyll antenna size 

of the tla1 mutant alleviates the over-absorption 

of incident sunlight by individual cells and the 

wasteful dissipation of over-absorbed irradiance. 

•	 A truncated light-harvesting chlorophyll antenna 

size in the tla1 mutant diminishes the severe cell 

shading that occurs in normally pigmented wild 

type and permits a more uniform illumination of 

the cells in a mass culture. 

•	 A truncated light-harvesting chlorophyll antenna 

size in the tla1 mutant leads to better solar conversion efficiencies and greater photosynthetic 

productivity of the algae under bright sunlight 

conditions. 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Photosynthetic productivity measurements 

were conducted with wild type and the tla1 

mutant of Chlamydomonas reinhardtii as a 

function of chlorophyll concentration in a 

mass culture (Polle et al. 2003). 

Measurements were conducted in the 

greenhouse at a solar incident intensity 

(photosynthetically active radiation) of about 

-1 1,500 μmol photons m-2 s . 

References 

1. Kok B (1953) Experiments on photosynthesis by 

Chlorella in flashing light. In: Burlew JS (ed), 

Algal culture: from laboratory to pilot plant. 

Carnegie Institution of Washington, Washington 

DC, pp 63-75 

2. Melis A, Neidhardt J and Benemann JR (1999) 

Dunaliella salina (Chlorophyta) with small 

chlorophyll antenna sizes exhibit higher 

photosynthetic productivities and photon use 

efficiencies than normally pigmented cells. J. 

appl. Phycol. 10: 515-52 

3. Myers J (1957) Algal culture. In: Kirk RE, Othmer 

DE (eds), Encyclopedia of chemical technology. 

Interscience, New York, NY, pp 649-668 

4. Polle JEW, Kanakagiri S and Melis A (2003) tla1, 

a DNA insertional transformant of the green alga 

Chlamydomonas reinhardtii with a truncated 

light-harvesting chlorophyll antenna size. Planta 

217: 49-59 

5. Radmer R and Kok B (1977) Photosynthesis: 

Limited yields, unlimited dreams. Bioscience 29: 

599-605 

FY 2002 Publications/Presentations 

1. Kanakagiri S and Melis A (2002) 

Chlamydomonas reinhardtii TLA1 nuclear gene 

for the regulation of the photosystem chlorophyll 

antenna size in photosynthesis, complete cds., 

(bases 1 to 2181). GenBank Accession Number 

AF534570 

2. Kanakagiri S and Melis A (2002) 

Chlamydomonas reinhardtii chlorophyll antenna 

size regulatory protein (TLA1) mRNA, complete 

cds. GenBank Accession Number AF534571 

3. Melis A (2002) Green alga hydrogen production: 

progress, challenges and prospects. Intl. J. 

Hydrogen Energy 27: 1217-1228 

4. Polle JEW, Kanakagiri, S, Jin ES, Masuda, T and 

Melis A (2002) Truncated chlorophyll antenna 

size of the photosystems – a practical method to 

improve microalgal productivity and hydrogen 

production in mass culture. Intl. J. Hydrogen 

Energy 27: 1257-1264 

5. Masuda T, Tanaka A and Melis A (2003) 

Chlorophyll antenna size adjustments by 

irradiance in Dunaliella salina involve 

coordinate regulation of chlorophyll a oxygenase 

(CAO) and Lhcb gene expression. Plant Mol. 

Biol. 51: 757-771 

6. Polle JEW, Kanakagiri S and Melis A (2003) tla1, 

a DNA insertional transformant of the green alga 

Chlamydomonas reinhardtii with a truncated 

light-harvesting chlorophyll antenna size. Planta 

217: 49-59, DOI: 10.1007/s00425-002-0968-1 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Algal H2-Production Systems: Creation of Designer Alga for Efficient and Robust 

Production of H2 

James W. Lee 

Oak Ridge National Laboratory 

P.O. Box 2008 

Oak Ridge, TN 37831-6194 

Phone: (865) 574-1208; Fax: (865) 574-1275; E-mail: leejw@ornl.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

Develop advanced renewable photolytic hydrogen generation technologies through creation of a designer 

alga by genetic insertion of a proton channel into the photosynthetic thylakoid membrane. By 2015, 

demonstrate an engineering-scale biological system that produces hydrogen at a plant-gate cost of $10/kg 

projected to commercial scale. 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 J. Rate of Hydrogen Production 

Approach 

Creation of designer alga for efficient and robust production of H2 through genetic insertion of a proton 

channel into the thylakoid membrane. 

Accomplishments 

This is a new project. Because of the Congress and DOE budget situation under the "Continuing 

Resolution," this project did not receive any funding until April 2003. In April 2003, the DOE authorized 

$50K for J. Lee (1) to attend the Merit Review and (2) to make preparation for a full start of the project on 

October 1, 2003. So, the following are the results of our preliminary studies and the project preparation 

work. 

•	 Identified the technical variables (problems) needed to optimize algal H2 production. 

•	 Designed a method—genetic insertion of a proton channel into the thylakoid membrane—to solve the 

identified technical problems. 

•	 Demonstrated the proof of principle through preliminary studies. 

Future Directions 

Since this is a new project that is yet to be fully started, its proposed milestones represent the future 

directions. If funding support is fully provided, the project objective could be achieved within 4-5 years 

with the following milestones. 

•	 Year 1—Design and construction of DNA sequence coding for polypeptide proton channel 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Year 2—Genetic transfer of hydrogenase promoter-linked polypeptide proton-channel DNA into algal 

strain DS521 

•	 Year 3—Characterization and optimization of the polypeptide proton-channel gene expression 

•	 Year 4—Demonstration of efficient and robust production of H2 in designer alga (ready for next phase: 

scale-up and commercialization) 

Introduction 

This R&D project will create algal H2­

production systems by a new and novel approach that 

has recently been developed at ORNL. In this 

approach, a “designer alga” for efficient and robust 

H2 production will be created by genetic insertion of 

hydrogenase promoter-programmed polypeptideproton channels into photosynthetic thylakoid 

membranes. 

Approach 

We have recently developed a systematic 

approach to create a "super" photosynthetic 

organism—a "designer alga" that is specifically 

designed for production of molecular hydrogen 

through photosynthetic water splitting (ORNL 

Invention Disclosure ID 0981).1 This designer alga 

will be able to overcome the four major physiological 

problems that currently challenge researchers and 

investors in the field of photosynthetic H2 

production: (1) restriction of photosynthetic H2 

production by accumulation of a proton gradient, (2) 

competitive inhibition of photosynthetic H2 

production by CO2, (3) requirement of bicarbonate 

binding at photosystem II (PSII) for efficient 

photosynthetic activity, and (4) newly discovered O2 

sensitivity in algal H2 production. 

The key element of our proposed approach is 

creation of a designer alga for efficient and robust 

production of H2 through genetic insertion of a 

programmable polypeptide proton channel into the 

thylakoid membrane. The genetic insertion of 

programmable thylakoid-membrane proton channels 

is proposed to be achieved by transformation of a 

host alga with a genetic vector that contains a 

polypeptide proton-channel gene linked with a 

hydrogenase promoter. The envisioned super alga 

that can be created by the proposed work should be 

able to perform autotrophic photosynthesis using 

ambient-air CO2 as the carbon source and grow 

normally under aerobic conditions such as in an open 

pond. When the algal culture is grown and ready for 

H2 production, the proton-channel gene will then be 

expressed simultaneously with the induction of the 

hydrogenase enzyme under anaerobic conditions 

because of the use of the hydrogenase promoter. The 

expression of the proton-channel gene should 

produce polypeptide proton channels in the thylakoid 

membrane, thus dissipating the proton gradient 

across the thylakoid membrane without adenosine 

triphosphate (ATP) formation. 

As illustrated in Figure 1, our recent 

experimental studies with the proton uncoupler 

carbonyl cyanide m-chlorophenylhydrazone (FCCP) 

have already demonstrated that insertion of a protonconductive channel in the thylakoid membrane could 

significantly enhance H2 production by eliminating 

the problems of both the proton-gradient 

accumulation and the newly discovered alternative 

O2 sensitivity that is dependent on the proton 

gradient.2 Furthermore, the cessation of 

photophosphorylation (ATP formation) caused by 

action of the proton channels can, in turn, switch off 

the Calvin cycle activity (CO2 fixation), which 

requires ATP and competes with the ferredoxin (Fd)/ 

hydrogenase H2-production pathway for the 

photosynthetically generated electrons. As a result, 

the competitive inhibition of H2 production by CO2 

will now be eliminated, and photosynthetic H2 

production in the designer alga will be able to occur 

in the presence of CO2. Since photosynthetic H2 

production in a successful designer alga no longer 

requires a CO2 (HCO3 

-

)-free environment, the 

requirement for HCO3 

-

 binding at photosystem II 

(PSII) for efficient photosynthetic activity will also 

no longer be a problem. The requirement can now be 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1. Stimulation of photosynthetic H2 production in 

C. reinhardtii 137c following addition of the 

proton uncoupler FCCP in a background 

atmosphere of 1000-ppm O2. Addition of 5 μM 

FCCP produced a dramatic increase in H2 

production, followed by a slow decay. The 

slow decay is due to a side effect of FCCP, 

known as ADRY,3

 in which FCCP gradually 

inhibits PSII activity. This ORNL experimental 

result indicates that use of a polypeptide proton 

channel that does not have the ADRY effect 

could enhance H2 production by eliminating the 

problems of both the proton-gradient 

accumulation and the newly discovered 

alternative O2 sensitivity. 

satisfied by leaving some CO2 in the medium. In 

conclusion, the use of polypeptide proton channels in 

the thylakoid membrane can provide four advantages 

for H2 photoevolution: (1) the accumulation of a 

proton gradient that impedes the photosynthetic 

electron transport from water to Fd/hydrogenase will 

be prevented; (2) the competitive inhibition of 

photosynthetic H2 production by CO2 (Calvin cycle 

activity) will be eliminated; (3) the requirement for 

bicarbonate binding at PSII for efficient 

photosynthetic activity will be satisfied; and (4) the 

newly discovered O2-sensitive pathway that 

competes with the H2-production pathway for 

photosynthetically generated electrons could also be 

avoided by the dissipation of the proton gradient with 

the switchable proton channel. 

Results 

The proof-of-principle experimental results from 

our preliminary studies were also presented in a 

poster presentation at the May 2003 DOE Merit 

Review Meeting. We are now making preparations 

for a full start of this project on October 1, 2003. 

Because of the current funding limit, the technical 

lab work of this project will not be able to start until 

the arrival of the FY 2004 funding support. 

Conclusions 

Creation of designer alga by genetic insertion of 

a proton channel into the thylakoid membrane is one 

of the key R&D tasks that are required for the 

photobiological H2-production system to work. We 

have already developed a systematic approach to 

achieve the proposed work. The proof of principle 

for this designer alga H2-production R&D project 

has been demonstrated through preliminary studies. 

References 

1. Lee, J. W., and E. Greenbaum 2001. “Method for 

creating efficient and robust photosynthetic H2­

production systems,” ORNL Invention Disclosure 

ID 0981. 

2. Lee, J. W., and E. Greenbaum 2002. “A new 

oxygen sensitivity in photosynthetic H2 

production,” Applied Biochemistry and 

Biotechnology, vol. 105-108, pp. 303-313. 

3. Samuilov, V. D., E. L. Barsky, and A. V. Kitashov 

1995. “ADRY agent-induced cyclic and noncyclic electron transfer around photosystem II,” 

Photosynthesis: from Light to Biosphere, P. 

Mathis (ed.), Vol. II, 267–270. The Netherlands, 

Kluwer Academic Publishers. 

FY 2003 Publications/Presentations 

1. Lee, J. W. and E. Greenbaum 2003 “A new 

oxygen sensitivity and its potential application in 

photosynthetic H2 production,” Applied 

Biochemistry and Biotechnology, vol. 105-108, 

pp. 303-313. 

2. Lee, J. W., L. Mets, and E. Greenbaum 2002 

“Improvement of photosynthetic CO2 fixation at 

high light intensity through reduction of 

chlorophyll antenna size,” Applied Biochemistry 

and Biotechnology, vol. 98-100, pp. 37-47. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

3. Lee, J. W. 2003 “Overcoming nation’s roadblocks 

to photosynthetic H2 production,” presented at the 

National Hydrogen Association’s 14th Annual 

Meeting, March 4-6, 2003, Washington, DC. 

Special Recognitions & Awards/Patents 

Issued 

1. Lee, J. W. and E. Greenbaum 2001 “Method for 

creating efficient and robust photosynthetic H2­

production systems,” ORNL Invention Disclosure 

ID 0981; U.S. Patent Application filed. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Algal Systems for Hydrogen Photoproduction 

Maria L. Ghirardi (Primary Contact) and Michael Seibert 

National Renewable Energy Laboratory (NREL) 

1617 Cole Blvd. 

Golden, CO 80401 

Maria Ghirardi: Phone: (303) 384-6312; Fax: (303) 384-6150; E-mail: maria_ghirardi@nrel.gov 

Michael Seibert: Phone: (303) 384-6279; Fax: (303) 384-6150; E-mail: mike_seibert@nrel.gov 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260, Fax: (202) 586-9811, Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Generate algal hydrogenase mutants with higher O2 tolerance to function with aerobic H2-production 

systems being developed in collaboration with Oak Ridge National Laboratory (ORNL) and 

University of California (UC) Berkeley. 

•	 Optimize the rates of H2 production using an anaerobic production system discovered by UC Berkeley 

and NREL. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 K. Continuity of Photoproduction 

Approach 

Subtask 1 (Hydrogenase Function and Molecular Engineering): 

•	 Apply different mutagenesis techniques to generate O2-tolerant algal hydrogenases. 

•	 Select transformants that express recombinant hydrogenases and study their H2-production capability 

in the presence of varying amounts of added O2. 

•	 Genetically combine the O2-tolerance phenotype with truncated antenna (UC Berkeley) and proton 

channel (ORNL) mutants. 

Subtask 2 (Biochemical and Process Characterization): 

•	 Develop a sulfur-deprived system for continuous H2 photoproduction. 

•	 Optimize engineering and biochemical parameters. 

•	 Demonstrate continuous H2 production for a total of 800 hours by 2008. 

Accomplishments 

•	 By homology modeling, identified residues in algal hydrogenase HydA1 that form the 5.5-7.0 D

diameter gas channel and mapped them to three regions: close to the catalytic site, mid-way to the 

surface, and close to the surface (subtask 1). 

•	 Mutagenized one of the residues located next to the catalytic site (valine 240) and demonstrated H2 

production with increased tolerance to O2 (subtask 1). 

•	 Developed a system for continuous H2 production based on a two-reactor, sulfate-chemostat design 

(subtask 2). 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Demonstrated continuous H2 production for a total of 480 hours using the new photobioreactor system 

(subtask 2). 

Future Directions 

•	 Perform molecular dynamics simulation to validate our results with the O2-tolerant mutant and guide 

further site-directed mutagenesis work. 

•	 Generate and test multiple algal hydrogenase mutants by a variety of mutagenesis techniques (e.g., 

site-directed, random in vitro, and gene shuffling). 

•	 Accelerate the identification of O2-tolerant clones by developing new high-throughput assays. 

•	 Use spectroscopic and biochemical techniques to investigate and correct or circumvent the rate 

limitations inherent to the sulfur-deprived system. 

•	 Examine alternative photobioreactor designs. 

•	 Increase the duration of H2 production (1,500 h at >2 ml/h in 2010) using a mutant that incorporates 

the best properties of the NREL, UC Berkeley and ORNL individual mutants. 

Introduction 

The green alga, Chlamydomonas reinhardtii, has 

the biochemical machinery necessary to efficiently 

photoproduce H2 from water. However, under 

normal conditions where O2 is a by-product of 

photosynthesis, sustained algal H2 photoproduction 

cannot be maintained for more than a few minutes 

(Ghirardi et al., 1997). Oxygen is a powerful 

inhibitor of algal [Fe]-hydrogenase (the catalyst that 

releases H2 gas) function, and H2 photoproduction 

stops abruptly if O2 is present. Oxygen inactivation 

is thought to occur by the direct binding of O2 to one 

of the iron species (with an unoccupied coordination 

site) located at the catalytic center (Adams, 1990). 

Our current project addresses two different strategies 

for surmounting the O2-sensitivity problem. These 

include (a) molecular engineering of the hydrogenase 

to remove the O2 sensitivity (subtask 1) and (b) 

development of physiological means to separate O2 

and H2 production (subtask 2). 

Our early work for the DOE Hydrogen Program 

involved the cloning and sequencing of two algal 

hydrogenase genes (Forestier et al., 2001, 2003), and 

this provided us with the tools and background 

knowledge to make rapid progress in the molecular 

engineering area. The work on subtask 1 has focused 

on a knowledge-based approach and is addressing 

regions in one of the algal hydrogenases (HydA1) 

that could be involved in access of O2 to the catalytic 

site. This annual report describes the method that we 

used to (a) identify this region and (b) design, 

generate and test the first site-directed mutant 

targeted to improved O2 tolerance. 

In the absence of an O2-tolerant hydrogenase, we 

demonstrated (with UC Berkeley) that it is possible 

to physiologically manipulate C. reinhardtii to 

generate anaerobic conditions, induce the 

hydrogenase gene and photoproduce H2 sustainably 

for about 3-4 days (Melis et al., 2000; Ghirardi et al., 

2000). This method was based on the partial 

inactivation of photosynthetic O2 evolution resulting 

from depriving the cultures of sulfate. Although 

technically successful, the sulfur-deprivation process 

is currently too expensive. In order to address the 

cost issue, we describe here the development of a 

continuous system that decreases the cost of H2 

production. 

Approach 

Subtask 1 (Hydrogenase Function and Molecular 

Engineering): There are a number of mutagenesis 

approaches to molecular-engineer enzymes for 

altered catalytic activity. Some of these approaches 

involve random changes in the enzyme’s gene 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

sequence (either by in vitro error-prone polymerase 

chain reaction or gene shuffling), followed by highthroughput screening for the desired mutants. 

However, it is also possible to alter an enzyme’s 

activity by applying a knowledge-based approach. In 

attempting to confer O2 tolerance to algal 

hydrogenases, we chose the latter. Our approach is 

based on the hypothesis that inactivation of a 

hydrogenase depends on the access of O2 to the 

enzyme’s catalytic site. We assumed that this access 

occurred through a gas channel, a hydrophobic 

pathway identified in other hydrogenases by X-ray 

structure analyses (Montet et al., 1997; Nicolet et al., 

1998) and identified by our group in algal [Fe]-

hydrogenases (King et al., patent pending). 

According to a hypothesis presented for NiFe 

hydrogenases (Bernhard et al., 2001; Volbeda et al., 

2002), a narrower channel might discriminate 

between the reaction product, H2, and the inhibitor, 

O2. We designed mutants in which residues with 

bulkier side chains are substituted for some of the 

small residues that line the gas channel. We report 

here the generation of the first site-directed 

hydrogenase mutant specifically designed to 

demonstrate increased tolerance to O2 exposure. 

Future work will involve the generation of mutants 

with multiple amino acid substitutions in the gas 

channel, and it may also address the complementary 

use of random mutagenesis to target protein 

sequences that we cannot rationally relate to O2 

tolerance. 

Subtask 2 (Biochemical and Process 

Characterization): The use of sulfur deprivation to 

metabolically shift the algal cultures from an O2- to a 

H2-production process was reported by UC Berkeley 

and NREL in 2000 (Melis et al., 2000). As originally 

conceived, the method involved cycles of O2 

production (in sulfur-replete medium) followed by 

cycles of H2 production (in sulfur-deprived medium) 

[Ghirardi et al., 2000]. This temporal-separation 

batch process was studied by NREL and found to be 

too costly (Amos, 2000). Among the variables 

responsible for the high cost were the use of 

centrifugation to cycle the cultures from one phase to 

the next and the limited time during which the 

cultures photoproduce H2. We investigated two 

approaches to remove the centrifugation step: (a) the 

use of judicious dilution of the sulfur-replete cultures 

to deprive them of sulfate (Laurinavichene et al., 

 FY 2003 Progress Report 

2002) and (b) the design of a new twophotobioreactor system, based on cell growth under a 

sulfate chemostat in one reactor, followed by H2-

production under sulfur-deprived conditions in a 

second reactor. The cultures in the second bioreactor 

should produce H2 continuously in the light but at 

limited rates. 

Results 

Subtask 1 (Hydrogenase Function and Molecular 

Engineering): The putative amino acid sequences of 

the two cloned algal hydrogenases, HydA1 and 

HydA2, were derived from their gene sequences. 

The amino acid sequences were then used to generate 

homology models of the respective protein 

structures, using the Swiss-Model program and 

further refinements by GROMOS (Forestier et al., 

2003; King et al., submitted). Modeling was based 

on the known X-ray structure of another [Fe]-

hydrogenase, CpI, found in the anaerobic bacterium 

Clostridium pasteurianum (Peters et al., 1998). 

Figure 1 shows the resulting structures of CpI, 

HydA1, and HydA2. The core regions of HydA1 and 

HydA2 exhibit a very high degree of structural 

similarity between each other and CpI, and the 

locations of the H-cluster catalytic sites overlap 

closely with those from CpI. The catalytic site 

consists of a 2Fe2S center linked by a cysteine 

residue to a 4Fe4S center, which is bound to the 

protein structure by three other cysteine residues 

(Peters et al., 1998; Nicolet et al., 1998). Moreover, 

the 2Fe2S center was shown to be ligated by unusual 

molecules such as CO, CN, and di(thiomethyl)amine 

(Nicolet et al., 2002). The main differences between 

the bacterial and the algal hydrogenases are (a) the 

presence of extra sequences in the N-terminal portion 

of CpI that bind additional FeS centers (Happe et al., 

2002; Forestier et al., 2003), which serve as an 

electron relay from a soluble donor bound to the 

surface of the protein to the catalytic site, and (b) the 

presence of loops L1 and L2 in HydA1 and HydA2 

that correspond to intervening gene sequences 

present only in the algal hydrogenases. Speculation 

suggested that the loops could be involved in the 

docking of ferredoxin (Winkler et al., 2002). We 

propose that their function could be related to 

regulating catalysis by transferring regulatory signals 

from the surrounding medium to the catalytic site. 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 Model of the X-ray Structure of the Clostridium 

pasteurianum CpI and Homology Models of 

the Two Algal Hydrogenases, HydA1 and 

HydA2 

The catalytic H-clusters in the three proteins are 

located in close proximity to a solvent-accessible 

area, termed the gas channel. Small, hydrophobic 

residues were identified as components of the 

channel wall. Homology modeling done at NREL 

suggested that mutating amino acid residues along 

the gas channel could narrow the channel in the 

region next to the catalytic site and in turn lower the 

access of O2 (King et al., submitted). One of those 

residues, valine 240, was replaced by molecular 

engineering techniques with a bulkier counterpart, 

tryptophan. Table 1 shows that the H2-production 

activity of the mutant (measured by two different 

assay methods, see legend) is more resistant to O2 

inactivation than the wild-type strain. This result 

confirms our initial hypothesis and justifies future 

Table 1. Effect of O2 exposure on the rates of H2 

photoproduction by the WT and V240W strains 

of Chlamydomonas reinhardtii. Assay I 

measures the initial rate of light-induced H2 

production measured with a Clark electrode; 

assay II measures the rate of H2 production 

induced by the addition of dithionite-reduced 

methyl viologen and is measured over a period 

of 10-15 min. The samples were exposed to the 

indicated concentrations of O2 for 2 min 

preceding each assay. 

O2 

% Uninhibited H2-production rate 

concentration, 

% 

Assay I (light) Assay II (MVred) 

WT V240W WT V240W 

0 100 100 100 100

0.1 42 - - -

1 12 100 19 88

1.5 48 - -

2 0 12 2.4 45

3 0 5 -

4 - - 1.5 24

molecular engineering techniques to further improve 

O2 tolerance by modifying gas-channel residues. 

Subtask 2 (Biochemical and Process 

Characterization): Sulfur deprivation of algal 

cultures selectively inactivates photosynthetic O2 

evolution and creates an anaerobic environment. 

Anaerobic conditions are sufficient to induce the 

hydrogenase gene, initiate synthesis of the 

hydrogenase protein, and promote subsequent H2 

photoproduction. The latter cannot be sustained for 

more than 3-4 days, however, due to pleiotropic 

effects of sulfate deprivation on the algae at later 

times. We conducted a detailed study of the 

relationship among the different metabolic pathways 

under sulfur-deprived conditions and concluded that 

the initial rate of H2 photoproduction is limited by 

the rate of reductant utilization. This results in an 

over-reduced plastoquinone pool (Antal et al., 2001 

and in preparation). The limitation is not due to low 

hydrogenase activity (Ghirardi et al, submitted), but 

is possibly related to regulatory mechanisms 

associated with the non-dissipation of a proton 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

gradient, as suggested for anaerobic, sulfur-replete 

cultures (Lee and Greenbaum, 2002). 

Since the initial rate of H2 photoproduction cannot 

be increased easily by biochemical or engineering 

manipulations (Kosourov et al., 2003), we attempted 

to develop a system in which the cultures produce H2 

at a similar fixed rate but for much longer periods of 

time. Figure 2 shows the concept. In the first 

photobioreactor, the algal cells are grown in a 

chemostat mode (by continuous dilution with medium 

containing sufficient amounts of sulfate). The cultures 

in the second photobioreactor are initially sulfurdeprived and allowed to start photoproducing H2. At 

that point, the second photobioreactor is connected to 

the first, and the H2-producing cultures are 

continuously replaced by photosyntheticallycompetent cells from the first photobioreactor. The 

two main objectives of the above design are to 

continuously (a) replace sulfur-deprived cells with 

fresh cultures to avoid the long-term inhibitory effects 

of sulfur deprivation on H2 photoproduction and (b) 

remove accumulated fermentation products from the 

H2-photoproduction reactor. 

The performance of the two-photobioreactor 

system was tested over a period of three weeks to 

meet our milestone for FY 2003. Figure 3 

demonstrates that the system works as expected and 

is able to photoproduce H2 at a rate that is constant 

during the first two weeks but decreases during the 

third week. Preliminary economic analyses indicate 

that the expected cost of the system is almost four 

times lower than that of the corresponding batch 

Figure 2.	 Schematic Diagram of the TwoPhotobioreactor, Continuous Algal H2 

Photoproduction System 

 FY 2003 Progress Report 

Figure 3.	 Accumulation of H2 by illuminated, sulfurdeprived algal cultures in the continuous mode. 

The arrow indicates the time point at which the 

second photobioreactor was connected to the 

first. Notice that the cell density, indicated by 

the Chl concentration, decreased towards the 

end of the experiment. 

system (from $760 to $200/kg [Amos, unpublished]). 

Further improvements both to the system and to the 

organism by NREL, UC Berkeley and ORNL will be 

crucial to continuing to lower the cost of H2 

photoproduction. 

Conclusions 

•	 The generation of the first successful algal 

hydrogenase mutant (V240W) validates our 

knowledge-based mutagenesis approach to 

improve the O2 tolerance of the enzyme and 

justifies our hypothesis that direct O2 access to 

the catalytic site both inactivates enzyme activity 

and limits H2 photoproduction. 

• Algal H 	 2 photoproduction can be extended for 

much longer periods of time using the sulfurdeprivation method to physically (rather than 

temporally) separate O2 and H2 production 

activities; this approach currently lowers the cost 

of the process by about a factor of four when 

compared to the batch system. 

References 

1.	 Adams, M.W.W. (1990) Biochim. Biophys. Acta 

1020, 115-145. 

2.	 Amos, W.A. (2000) Cost Analysis of 

Photobiological Hydrogen Production from 

Chlamydomonas reinhardtii Green Algae. 

5 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Milestone report, National Renewable Energy 

Laboratory, Golden, CO. 

3.	 Antal, T.K., Krendeleva, T.E., Laurinavichene, 

T.V., Makarova, V.V., Tsygankov, A.A., Seibert, 

M. and Rubin, A. (2001) Proc. Russian Acad. 

Scie. 381, 371-375. 

4.	 Bernhard, M., Buhrker, T., Bleijlevens, B., De 

Lacey, A.L., Fernandes, V.M., Albracht, S.P.J. 

and Friedrich, B. (2001) J. Biol. Chem. 76, 

15592-15597. 

5.	 Forestier, M., Zhang, L., King, P., Plummer, S., 

Ahmann, D., Seibert, M. and Ghirardi, M.L. 

(2001) Proceedings of the 12th International 

Congress on Photosynthesis, Brisbane, Australia. 

http://www.publish.csiro.au/ps2001. 

6.	 Forestier, M., King, P., Zhang, L., Posewitz, M., 

Schwarzer, S., Happe, T., Ghirardi, M.L. and 

Seibert, M. (2003) Eur. J. Biochem. 270, 2750-

2758. 

7.	 Ghirardi, M.L., Togasaki, R.K. and Seibert, M. 

(1997) Appl. Biochem. Biotechnol. 63-65, 141-

151. 

8.	 Ghirardi, M.L., Zhang, L., Lee, J.W., Flynn, T., 

Seibert, M., Greenbaum, E. and Melis, A. (2000) 

Trends Biotech. 18, 506-511. 

9.	 Ghirardi, M.L., Kosourov, S. and Seibert, M. 

Proceedings of the Boden Conference in 

Artificial Photosynthesis, Sydney, Australia 

(submitted). 

10. Happe, T., Hemschemeier, A., Winkler, M. and 

Kaminski, A. (2002) Trends in Plant Scie. 7, 246-

250. 

11. King, P., Forestier, M., Zhang, L., Ghirardi, M.L. 

and Seibert, M. Proceedings of the Boden 

Conference in Artificial Photosynthesis, Sydney, 

Australia (submitted). 

12. Kosourov, S., Seibert, M. and Ghirardi, M.L. 

(2003) Plant Cell Physiol. 44, 146-155. 

13. Laurinavichene, T.V., Tolstygina, I.V., Galiulina, 

R.R., Ghirardi, M.L., Seibert, M. and Tsygankov, 

 FY 2003 Progress Report 

A.A. (2002) Int. J. Hydrogen Energy 27, 1245-

1249. 

14. Lee, J. and Greenbraum, E. (2002) Proceedings 

of the 2001 DOE Hydrogen Program Review 

<http://www.eere.energy.gov/ 

hydrogenandfuelcells/pdfs/305 35d.pdf>. 

15. Melis, A., Zhang, L., Forestier, M., Ghirardi, 

M.L. and Seibert, M. (2000) Plant Physiol. 122, 

127-135. 

16. Montet, Y., Amara, P., Volbeda, A., Vernede, X., 

Hatchikian, E.C., Field, M.J., Frey, M. and 

Fontecilla-Camps, J.C. (1997) Nature Struct. 

Biolog. 4, 523-526. 

17. Nicolet, Y., Piras, C., Legrand, P., Hatchikian, 

C.E. and Fontecilla-Camps, J.C. (1998) Structure 

7, 13-23. 

18. Nicolet, Y., Cavazza, C. and Fontecilla-Camps, 

J.C. (2002) J. Inorg. Biochem. 

19. Peters, J.W., Lanzilotta, W.N., Lemon, B.J. and 

Seefeldt, L.C. (1998) Science 282, 1853-1858. 

20. Volbeda, A., Montet, Y., Vernede, X., Hatchikian, 

E.C. and Fontecilla-Camps, J.C. (2002) Int. J. 

Hydrogen Energy 27, 1449-1461. 

21. Winkler, M., Hemschemeier, A., Gotor, C., Melis, 

A. and Happe, T. (2002) Int. J. Hydrogen Energy 

27, 1431-1439. 

FY 2003 Publications 

1. Laurinavichene, T., Tolstygina, I.V., Galiulina, 

R.R., Ghirardi, M.L., Seibert, M. and Tsygankov, 

A. (2002) Dilution methods to deprive 

Chlamydomonas reinhardtii cultures of sulfur for 

subsequent hydrogen photoproduction. Int. J. 

Hydrogen Energy 27, 1245-1249. 

2. Flynn, T., Ghirardi, M.L. and Seibert, M. (2002) 

Accumulation of O2-tolerant phenotypes in H2-

producing strains of Chlamydomonas reinhardtii 

by sequential applications of chemical 

mutagenesis and selection. Int. J. Hydrogen 

Energy 27, 1421-1430. 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies

3. Tsygankov, A., Kosourov, S., Seibert, M. and 

Ghirardi, M.L. (2002) Hydrogen photoproduction 

under continuous illumination by sulfur-deprived, 

synchronous Chlamydomonas reinhardtii 

cultures. Int. J. Hydrogen Energy 27, 1239-1244. 

4. Kosourov, S., Seibert, M. and Ghirardi, M.L. 

(2003) Effects of extracellular pH on the 

metabolic pathways in sulfur-deprived, H2-

producing Chlamydomonas reinhardtii cultures. 

Plant Cell Physiol. 44, 146-155. 

5. Forestier, M., King, P., Zhang, L., Posewitz, M., 

Schwarzer, S., Happe, T., Ghirardi, M.L. and 

Seibert, M. (2003) Expression of two [Fe]-

hydrogenases in Chlamydomonas reinhardtii 

under anaerobic conditions. Eur. J. Biochem. 270, 

2750-2758. 

6. Laurinavichene, T.V., Fedorov, A.S., Ghirardi, 

M.L., Seibert, M. and Tsygankov, A. Hydrogen 

photoproduction by immobilized, sulfur-deprived 

Chlamydomonas reinhardtii cells. Submitted. 

7. Hahn, J.J., Ghirardi, M.L. and Jacoby, W.A. The 

effect of process variables on photosynthetic algal 

hydrogen production. Submitted. 

8. King, P., Forestier, M., Zhang, L., Ghirardi, M.L. 

and Seibert, M. Molecular engineering of a 

Chlamydomonas reinhardtii hydrogenase for 

increased O2 tolerance. Proceedings of the Boden 

Conference in Artificial Photosynthesis, Sydney, 

Australia. Submitted. 

9. Ghirardi, M.L., Kosourov, S. and Seibert, M. 

Artificial photosynthetic systems for algal 

hydrogen production. Proceedings of the Boden 

Conference in Artificial Photosynthesis, Sydney, 

Australia. Submitted. 

FY 2003 Presentations/Posters 

1. Invited presentation at Oak Ridge National 

Laboratory, October 2002. “Photosystem II, the 

Engine for Algal Hydrogen Production”, M. 

Seibert. 

2. Invited Mechanical Engineering Departmental 

Seminar, University of Colorado, Boulder, 

November 2002. “Algal H2 Production— 

 FY 2003 Progress Report 

Physiology, Molecular Genetics and Process 

Development”, P. King, S. Kosourov, M.L. 

Ghirardi and M. Seibert (MS presented). 

3. Invited presentation at the Boden Conference on 

Artificial Photosynthesis, Sydney, Australia, 

January 2003. “Modifying Photosynthesis for 

Continuous Algal Hydrogen Photoproduction”, 

M.L. Ghirardi, S. Kosourov and M. Seibert (MLG 

presented). 

4. Invited presentation at the Boden Conference on 

Artificial Photosynthesis, Sydney, Australia, 

January 2003. “Cloning and Molecular 

Engineering of Chlamydomonas [Fe]-

hydrogenases for Oxygen Tolerance”, M. Seibert, 

P. King, L. Zhang, M. Forestier, S. Schwartz, T. 

Happe and M.L. Ghirardi (MS presented). 

5. Invited seminar in the Research School of 

Biological Sciences, Australian National 

University, January 17, 2003. “Algal H2 

Production—Physiology, Process Development, 

and Molecular Genetics”, P. King, S. Kosourov, 

M.L. Ghirardi and M. Seibert (MS presented). 

6. Presentation at the University of Colorado’s Super 

Microbiology Group, April 2003. “Cloning of a 

Second Putative [Fe]-Hydrogenase from the 

Green Alga Chlamydomonas reinhardtii”, M. 

Forestier, P. King, L. Zhang, M. Posewitz, S. 

Plummer, S. Smolinski, M. Ghirardi and M. 

Seibert (MLG presented). 

7. Invited presentation at the U.S. Air Force AFOSR 

workshop on Biohydrogen and Artificial 

Photosynthesis, Denver, CO, April 2003. “Algal 

Hydrogen Photoproduction”, M.L. Ghirardi. 

8. Poster at the Symposium on the Biotechnology for 

Fuels and Chemicals, Breckenridge, CO, May 

2003. “Algal Hydrogen Production – Physiology 

and Process Development”, M. Seibert, L. Zhang, 

V. Makarova and M.L. Ghirardi (MS presented). 

9. Invited presentation at the Bio2003 conference in 

Washington D.C., June 2003. “Algal Hydrogen 

Photoproduction”, M.L. Ghirardi, A. Fedorov, P. 

King, S. Kosourov, M. Posewitz, S. Smolinski, L. 

Zhang and M. Seibert (MLG presented). 

7 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Patents 

1. Kosourov, S., Ghirardi, M. and Seibert, M. 

“Multi-stage microbial system for continuous 

hydrogen production”. Patent application filed 

October 2002. 

2. King, P., Ghirardi, M.L. and Seibert, M. 

“Oxygen-tolerant hydrogenases and methods for 

designing and making same”. Provisional patent 

application filed April 18, 2003. 

FY 2003 Videos 

1. City in a Pyramid, Discovery Channel, April 2003 

2. Video for KLTV Channel 8, Lakewood, CO, 

March 2003 

8 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Photoelectrochemical Systems for H2 Production 

John A. Turner (Primary Contact), Joe Beach*, Todd Deutsch#, John Einspahr+, Jennifer Leisch* , 

Ken Menningen+, Lara Kjeldsen*, Ken Varner?, Heli Wang, Scott Warren‡ 

National Renewable Energy Laboratory (NREL) 

1617 Cole Blvd 

Golden, Colorado 80401 

Phone: (303) 275-4270; Fax: (303) 275-3033; E-mail: jturner@nrel.gov 

*

Colorado School of Mines 

#

University of Colorado

+University of Wisconsin 

‡Cornell University

?

University of North Carolina 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Identify and characterize new semiconductor materials that are capable of splitting water using 

sunlight as the only energy input. 

•	 Improve the durability (stability) of semiconductor materials in aqueous solutions. 

•	 Develop multijunction high-efficiency water-splitting systems to meet the 2015 target of 14% solar-tohydrogen efficiency. 

•	 Apply basic science understanding for control of the energetics of the semiconductor in solution (band 

edge engineering). 

•	 Develop techniques for the preparation of transparent catalytic coatings and their application to 

semiconductor surfaces. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Material Durability 

•	 O. Photoelectrochemical Efficiency 

Approach 

•	 Discover, research and develop semiconductor materials for improved photoelectrochemical (PEC) 

systems. 

•	 Optimize and control energetics, developing a fundamental understanding of semiconductor surface 

interactions with aqueous solutions. 

•	 Identify materials for protective coatings and materials for catalysis. 

Accomplishments 

•	 First PEC study of InxGa1-xN (0<x<0.14) material. 

•	 First PEC study of GaAsPN material. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• First synthesis of CuInGaSSe material with band gaps in the range 1.6-2.0 eV. 

• First study of the surface modification of GaInP2 with water soluble metallo-porphyrins. 

Future Directions 

• Evaluate nitride materials as longer lifetime water splitting systems. 

• Develop multijunction systems for high efficiency. 

• Explore thin film materials as low-cost water splitting systems. 

• Develop protective coatings that reduce corrosion and provide catalysis. 

• Explore approaches for control of surface energetics. 

Introduction 

The direct PEC splitting of water is a one-step 

process for producing H2 using solar irradiation; 

water is split directly upon illumination. This type of 

direct conversion system combines a photovoltaic 

material and an electrolyzer into a single monolithic 

device. For this one-step process to be viable, two 

basic criteria must be met: the light harvesting 

system must have the correct energetics to effect the 

decomposition of water, and the system also must be 

stable in an aqueous environment. Direct conversion 

photoelectrochemical systems not only eliminate 

most of the costs of an electrolyzer, but they also 

have the possibility of increasing the overall 

efficiency of the process (as compared to 

photovoltaie (PV)/electrolysis), leading to a further 

reduction in the cost of delivered hydrogen. 

Approach 

PEC hydrogen production is in an early stage of 

development, and it depends on a breakthrough in 

materials development. The primary effort in this 

project is to synthesize a semiconducting material or 

a semiconductor structure with the necessary 

properties. For the direct PEC decomposition of 

water to occur, three key energetic conditions and the 

criteria of stability for the semiconductor must be 

met. For the energetic conditions, the 

semiconductor's band gap must be sufficiently large 

to split water and yet not too large as to prevent 

efficient absorption of the solar spectrum (ideally 

1.8-2.2 eV), the band edges of the semiconductor 

must overlap the hydrogen and oxygen redox 

potentials, and the charge transfer across the 

semiconductor/liquid interface must be fast enough 

to prevent band edge migration. In addition, the 

semiconductor's surface must be stable against 

corrosion both in the dark and under illumination. 

Our study of PEC direct-conversion systems involves 

two areas of research: semiconducting materials and 

surface treatments. Semiconducting materials can be 

divided into two types based on their solid state 

structure: single photon absorbers and multiphoton 

devices. Surface treatments include coatings to 

address energetic issues, corrosion problems, and 

catalysts for the water splitting reactions. 

Materials research in this area is progressing on 

two fronts: 1) working on the high efficiency 

materials in order to apply basic scientific 

understanding to lower efficiency, low-cost 

materials, and 2) working on the durability of lowcost materials in order to apply basic scientific 

understanding to higher efficiency, lower durability 

materials. Currently, the highest efficiency systems 

have the shortest lifetimes, and the lower efficiency 

systems have the longest lifetimes. The optimal 

system will likely be a compromise between 

efficiency and lifetime. 

Results 

As part of our search for semiconductor 

materials with inherently greater stability, we have 

been studying the group III-nitrides for use as PEC 

materials. Earlier work in our group has shown that 

GaN can split water and is stable under certain 

operating conditions. While it is known that GaN is 

chemically very stable, its band gap is too large (~3.4 

eV) to be an efficient PEC device. We have also 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

shown that adding indium to the material can lower 

the band gap and that it appears that the composition 

of InxGa1-xN can be adjusted to produce a band gap 

suitable for solar water-splitting applications. Our 

best InxGa1-xN material currently synthesized has a 

band gap of 2.71 eV (Figure 1). To be a useful 

material for water splitting, this band gap must be 

lowered further by increasing the amount of indium. 

Work is continuing in this area. 

Another material that shows excellent stability in 

aqueous solution and has a bandgap in the 

appropriate range for good solar absorption (2.25 eV) 

is gallium phosphide (GaP). Unfortunately, this is an 

indirect band gap, leading to low solar absorption 

efficiency and low conversion efficiency. Recent 

work has shown that adding a small amount of 

nitrogen to the GaP lowers the band gap and creates a 

direct transition. The combination of a smaller band 

gap and a direct transition would produce a much 

more efficient system. The GaPxN(1-x) material is 

being synthesized at NREL as part of their work for 

the DOE Solar Energy Program, which makes it 

particularly interesting for an initial study. Figure 2 

shows our data on measurement of the band gap. As 

expected, there is a direct transition and a nearly 

ideal band gap of 1.9 eV. Further characterizations 

are necessary to determine if this material can 

function as a water-splitting device. 

Thin-film copper indium gallium diselenide 

(CIGS) devices are well known for their high 

conversion efficiency when prepared as 

polycrystalline thin films. Electrodeposition is a 

 FY 2003 Progress Report 

potentially scalable technique for large area thin film 

fabrication at reduced costs. In fact, CIGS films have 

been successfully prepared from electrodeposited 

precursors to yield solar energy conversion devices 

with an efficiency of 15.4%. Sulfur incorporation 

has also been used in CIGS solar energy materials to 

increase device performance and to provide a graded 

band gap structure. Our effort in this area was to 

incorporate sulfur throughout the entire film, to 

obtain a material exhibiting a higher band gap that is 

suitable for water splitting. The combination of 

lower system manufacturing cost (from 

electrodeposition) and a high efficiency material 

represents an important area of research for hydrogen 

production systems. In addition, indium in the film 

may provide some protection against corrosion. In 

aqueous solution, indium can form a conducting 

oxide layer that stabilizes the interface and may 

protect the underlying material. In this initial effort, 

Cu(In,Ga)(Se,S)2 thin semiconducting films were 

made from electrodeposited Cu(In,Ga)Se2 

precursors, followed by physical vapor deposition of 

In2S3, Ga, and Se. The band gaps of these materials 

were found to be between 1.6 and 2.0 eV (Figure 3), 

which spans the optimal band gap necessary for 

application for the top junction in PV multijunction 

devices and unassisted water photolysis. Note also 

that this research demonstrates the ability to 

synthesize materials with a full range of band gaps 

from a single material set. 

In the area of bandedge engineering, gallium 

indium phosphide (GaInP2) surfaces were modified 

with metallo-porphyrin compounds in order to shift 

Figure 1. Band Gap Analysis of the Photocurrent 

Figure 2. Band Gap Analysis of GaPN Material Spectrum for Sample In0.14Ga0.86N 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Photoresponse Measurements of Thin Films 

With Varying Composition (Atomic percent 

sulfur in each film is shown) 

the semiconductor's band edges. Compounds used 

included Nickel(II)-Tetra(N-Methyl-2-pyridyl) 

porphyrin chloride [NiTMPyP(2)], Fe(III)TMPyP(2), 

and VO(IV)TMPyP(4). Sample treatments using 

these water-soluble compounds were applied by 

immersion of the semiconductor in a solution of the 

porphyrin for varying lengths of time. The position 

and movement of GaInP2 band edges were 

monitored by capacitance measurements, and shifts 

of up to 1 volt were observed after some surface 

treatments. While a shift of 1 volt should be 

sufficient to allow GaInP2 to split water, no water 

splitting was observed. Work is continuing to 

determine what is preventing the system from 

operating as we expected. 

Conclusions 

•	 Nitride materials based on GaInN are possible 

high-efficiency, water-splitting materials, showing good stability and the correct energetics. 

•	 Initial studies on nitride materials based on 

GaPN showed that achieving the necessary band 

gap was possible. 

•	 Surface studies of water-soluble, porphyrin-modified GaInP2 showed that it is possible to affect 

the energetic position of the semiconductor band 

edges. 

•	 Work on the thin-film CuInGaSSe system 

showed that it is possible to synthesize material 

with band gaps in the range 1.6-2.0 eV. 

FY 2003 Presentations 

•	 Presentation for the Chemistry Department of the 

Colorado School of Mines entitled "Photoelectrochemical Direct Water Splitting Systems." 

•	 Presentation for North Carolina State University 

entitled "Photoelectrochemical Systems for 

Hydrogen Production via Direct Water Splitting." 

•	 Presentation at the American Institute of Chemical Engineers' Spring meeting, speaking in a session on climate change. 

•	 Presentation at the American Physical Society's 

Spring meeting, speaking in a session on climate 

change. 

•	 Presentation at the U.S. DOE Hydrogen Program's first Quarterly Program Performance and 

Results Briefing, for upper DOE management. 

•	 Lecture on renewable energy and hydrogen at the 

University of Colorado for a class on energy and 

the environment. 

•	 Banquet speaker at the Northwest regional 

American Chemical Society meeting in Spokane, 

Washington. 

•	 Presentation at the California Alternative Energy 

Retreat in Bishop, California, speaking on the 

general topic of hydrogen. 

•	 Presentation at the California Hydrogen Business 

Council, speaking on the NREL Hydrogen Program research. 

•	 Presentation at the Georgia Tech "Blue Skies" 

symposium speaking on the hydrogen economy. 

•	 Two talks at the XII International Materials 

Research Congress, Mexico, "Band edge Engineering of p-GaInP2 Electrodes with Porphyrins, 

Pthalocyanins and other Organic Molecules," 

and "Corrosion Studies of Stainless Steels for 

Bipolar Plate Material in Polymer Electrolyte 

Membrane Fuel Cells." 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Presentation at the National Hydrogen Association meeting entitled "Hydrogen and Energy Security: Key Issues and Potential" with Jim Ohi. 

•	 Presentation on the hydrogen economy at the 

ASM International Oak Ridge Chapter, Oak 

Ridge, Tennessee. 

•	 Two presentations at Ashland University, Ashland, Ohio, one entitled "Renewable Energy Systems, Energy Storage and Hydrogen," and a 

second one for local high school students entitled 

"Energy and Hydrogen, Today and Tomorrow." 

•	 Presentation on fuel cells and hydrogen to the 

Clean Energy States Alliance Spring 2003 

Meeting. 

•	 Presentation at GE Central Research on photoelectrochemical water splitting. 

•	 Presentation at the International Electrochemical 

Society meeting (invited) entitled "Integrated 

Multijunction Photovoltaic/Electrolyte System 

for Water Photoelectrolysis." 

FY 2003 Publications 

1. V. M. Aroutiounian, V. M. Arakelyan, G. E. 

Shahnazaryan, G. M. Stepanyan, J. A. Turner, 

and O. Khaselev, "Investigation of Ceramic 

Fe2O3 <Ta> Photoelectrodes for Solar Energy 

Photoelectrochemical Converters," International 

Journal of Hydrogen Energy, 27, p 33 (2002). 

2. Scott Warren and J. Turner, "Increasing the 

Efficiency in Photoelectrochemical Hydrogen 

Production," USDOE Journal of Undergraduate 

Research, p 75 (2002). 

3. J. D. Beach, H. Al-Thani, S. McCray, R. T. Collins, 

and J. Turner, "Bandgaps and Lattice Parameters of 

0.9 um Thick InxGa1-xN Films for 0<x<0.140," J. 

Appl. Phys, Vol 91, No. 9, (2002). 

4. X. Mathew, A. Bansal, J. Turner, R. Dhere, N. 

Mathews and P. Sebastian, 

"Photoelectrochemical Characterization of 

Surface Modified CdTe for Hydrogen 

Production," J. New Mat. For Electrochemical 

Systems, Vol 5 149-154 (2002). 

Special Recognitions & Awards/Patents 

Issued 

1. Outstanding Mentor Award from the Office of 

Science, U.S. Department of Energy. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Photoelectrochemical Hydrogen Production 

Eric L. Miller (Primary Contact), Daniela Paluselli, Bjorn Marsen, Richard Rocheleau 

Hawaii Natural Energy Institute, University of Hawaii at Manoa (UH) 

1680 East-West Road, POST 109 

Honolulu, Hawaii 96822 

Phone: (808) 956-5337; Fax: (808) 956-2335; E-mail: ericm@hawaii.edu 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Develop low-cost, thin-film metal-oxide materials with suitable properties for use in “Hybrid
 

Photoelectrodes” (HPE) for solar water splitting.
 

•	 Develop optimized HPE designs based on best available thin-film metal-oxide and photovoltaic-grade 

semiconductor materials. 

•	 Demonstrate stable water splitting using HPEs based on best available materials systems. 

•	 Demonstrate 7.5% solar-to-hydrogen (STH) efficiency with 1000 hour life by 2005; demonstrate 9% 

STH with 2000 hour life by 2010. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Material Durability 

•	 N. Materials and System Engineering 

•	 O. Photoelectrochemical Efficiency 

Specific technical issues for durability and efficiency in the UH hybrid designs include the development of 

‘low-temperature’ (<300°C) processes which yield photoactive and stable metal-oxide films compatible 

with hybrid photoelectrode fabrication, and continued development of optimized materials and device 

designs are needed to meet program goals. 

Approach 

Materials Research: Current focus on developing low-temperature reactive sputtering process to produce 

photoactive and stable metal-oxide films including Fe2O3 and WO3 

•	 Partnership Support (Duquesne University & others): to develop further understanding of structure 

and composition of photoactive metal oxides for the engineering of new, process-compatible materials. 

Photoelectrode Testing: Current focus on incorporating best available materials into “Hybrid 

Photoelectrode” structures to evaluate performance and stability 

•	 Partnership Support (University of Toledo): to design and fabricate multi-junction amorphous-silicon 

alloy devices with specified voltage and current characteristics. 

Photoelectrode Optimization: Continued development of optimized materials and device designs for use 

in high-performance / low-cost “Hybrid Photoelectrodes .” 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

Fe2O3 films successfully deposited using low-temperature sputter process: 

•	 Ability to engineer key film properties successfully demonstrated. 

•	 Excellent film adhesion and stability in alkaline media achieved. 

•	 Photocurrents up to 0.1 mA/cm2 achieved under 1-sun (typical outdoor sunlight without concentration) 

in films deposited to date. 

WO3 films successfully deposited using low-temperature sputter process: 

•	 Ability to engineer key film properties successfully demonstrated. 

•	 Excellent film adhesion and stability in acid media achieved. 

•	 Photocurrents up to 1.2 mA/cm2

 achieved under 1-sun in films deposited to date. 

Stable operation of “Hybrid Photoelectrode” demonstrated: 

•	 Structure: amorphous silicon alloy tandem (University of Toledo) with sputtered indium tin oxide 

(ITO) and low-temperature sputtered WO3 (UH) - 2.5 cm2 area. 

•	 Stable hydrogen production in 1 N H2SO4 measured for over 10 hours. 

•	 Photocurrents up to 0.5 mA/cm2

 in 1-sun outdoor tests (0.7% STH). 

•	 Performance consistent with measured properties of the WO3 material and the tandem silicon cell. 

•	 Analysis indicates significant efficiency enhancement possible with improved metal-oxide properties. 

Future Directions 

•	 Continued development of the "Hybrid Photoelectrode" using in-house and partnership resources. 

•	 Expand efforts to optimize hybrid-compatible materials for efficiency and long-life. 

•	 Design, fabricate and test "Hybrid Photoelectrodes" incorporating optimized materials. 

Introduction 

Under the sponsorship of the U.S. Department of 

Energy (DOE), the Thin Films Laboratory at the 

Hawaii Natural Energy Institute of the University of 

Hawaii (UH) has been developing high-efficiency, 

potentially low-cost, photoelectrochemical (PEC) 

systems to produce hydrogen directly from water 

using sunlight as the energy source. The main thrust 

of the PEC systems research at UH has been the 

development of integrated multi-junction 

photoelectrodes based on low-cost semiconductor, 

catalytic, and protective thin films [1].

Figure 1 shows a generic planar photoelectrode 

structure, where sunlight absorbed in photoactive 

regions produces electricity to drive the hydrogen 

evolution reaction (HER) and the oxygen evolution 

reaction at opposite surfaces. In order to meet the 

DOE’s goals, the photoelectrode system must be 

Figure 1.	 Generic Planar Photoelectrode Structure 

With Hydrogen and Oxygen Evolved at 

Opposite Surfaces 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

low-cost, and it must be capable of operating stably 

in corrosive aqueous electrolyte environments with 

solar-to-hydrogen (STH) conversion efficiencies 

greater than 7.5% by 2005, 9% by 2010 and greater 

than 10% by 2015 [2]. In an attempt to meet the cost 

and performance goals, UH has been concentrating 

on the development of a “Hybrid Photoelectrode” 

(HPE) which incorporates low-cost metal-oxide and 

photovoltaic-grade semiconductor thin films, as 

described in the following section. 

Approach 

The basic “Hybrid Photoelectrode” structure 

developed at UH is shown in Figure 2. This multijunction device combines thin-film solid-state with 

PEC junctions to meet the voltage, current and 

stability requirements for hydrogen production. The 

design approach has relied on continued use of 

integrated models for photoelectrode design [3], 

establishment of industry and university partners 

with thin-film materials expertise, and fabrication 

and evaluation of photoelectrode test devices. 

Significant advantages of the HPE design over other 

structures investigated at UH [4] include elimination 

of lateral current collection; simplification of device 

geometry for ease of fabrication; and improved 

stability based on the thick, seamless outer metaloxide layer. 

The primary focus of our current work has been 

the development of HPEs based on low-cost solidstate junction materials such as amorphous silicon (aFigure 2.	 The Multi-Junction "Hybrid Photoelectrode" 

Structure, Showing Constituent Thin-Film 

Layers (Photons are absorbed both at the 

metal-oxide/electrolyte interface and at the 

buried solid-state junction.) 

Si) and copper-indium-gallium-diselenide (CIGS) 

coated with photoactive nano-structured metal oxides 

such as iron oxide (Fe2O3) and tungsten trioxide 

(WO3). There has been extensive investigation into 

these metal-oxide films for their PEC water splitting 

properties; Figure 3, for example, shows hydrogenproduction characteristics for Fe2O3 films deposited 

by spray-pyrolysis at Duquesne University [5] and 

for pyrolytic WO3 films developed at the University 

of Geneva [6]. It can be seen that hydrogen currents 

can be quite high in the metal-oxide PEC junctions, 

but only at sufficient levels of voltage bias. In the 

HPE configuration, the necessary voltage bias is 

automatically generated in the buried solid-state 

junction utilizing low-energy photons not absorbed at 

the PEC interface. 

Unfortunately, fabrication of hybrids using 

pyrolytic oxides is not possible at this time, since 

substrate temperatures for the established pyrolysis 

Figure 3.	 Published Photoelectrochemical Hydrogen 

Production Characteristics of Metal-Oxide 

Thin Films: A. Fe2O3 film (Duquesne 

University); B. WO3 film (University of 

Geneva) 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

processes, generally exceeding 400°C, are high 

enough to damage the underlying solid-state 

junction. It has therefore been an important part of 

our research approach to develop low-temperature 

(<300°C) processes yielding photoactive and stable 

metal-oxide films. Specific emphasis has been on 

developing low-temperature reactive-sputter 

processes for Fe2O3 and WO3 films, along with 

fabrication and testing of HPE prototypes using 

amorphous silicon solid-state junctions (fabricated at 

the University of Toledo) with the best available 

sputter-deposited oxide films. 

Results 

Significant progress was made this year in the 

development of low-temperature reactively-sputtered 

metal-oxide films for use in water-splitting “Hybrid 

Photoelectrodes”, and in the demonstration of 

operational devices using these materials. 

Importantly, all project milestones in materials 

research and photoelectrode development have been 

met to date. 

A key milestone in our materials research was 

the successful fabrication of photoactive Fe2O3 and 

WO3 films using low-temperature reactive sputtering 

processes. Reactive sputtering is a vacuum 

deposition technique [7] where a range of process 

parameters, including substrate temperature, ambient 

gas partial pressures, and sputtering power, can 

influence film characteristics. We found, for 

example, that structural, electronic and 

photoelectrochemical properties of sputtered Fe2O3 

and WO3 films could be significantly altered by 

varying oxygen partial pressure and substrate 

temperature. 

Figure 4 demonstrates the range of variations in 

grain structure (Figure 4a) and electronic 

conductivity (Figure 4b) observed in the sputtered 

iron-oxide films. It was found that the films 

deposited at the high end of our ‘low-temperature’ 

range (200°C) with low oxygen percentages (5%) 

exhibited the best conductivities (attributable to large 

grain structure and oxygen vacancy levels). 

Unfortunately, although they exhibited excellent 

stability in electrolyte, the hydrogen photocurrents in 

these films were limited to 0.1 mA/cm2 in outdoor 

tests. In contrast, photocurrents up to 1.2 mA/cm2 

 FY 2003 Progress Report 

were readily achieved in the sputtered WO3 films 

investigated to date, as seen in Figure 5a for a sample 

deposited at 200°C with 12% oxygen. Similar to the 

iron-oxide samples, the tungsten-trioxide films were 

stable in electrolyte, and also exhibited a processdependent range of property variations. Figure 5b, 

for example, shows the WO3 films’ conductivities, 

again with the highest observed in films deposited at 

200°C with low oxygen percentages. 

A critical milestone in our photoelectrode 

development effort was the successful demonstration 

of functional “Hybrid Photoelectrodes” using 

sputtered materials. The operational devices were 

fabricated using tandem amorphous silicon junctions 

(fabricated by the University of Toledo) coated with 

reactively-sputtered WO3 films (1.0-2.0 μm). Ten 

photoelectrodes with an active area of 2.5 cm2

 have 

been fabricated to date and evaluated using the test 

structure shown in Figure 6a. All ten exhibited 

hydrogen photocurrent during outdoor testing, and 

importantly, the observed performances were 

consistent with analyses based on behavior of the 

silicon and tungsten-trioxide films used. Figure 6b 

Figure 4.	 Measured Property Variations in LowTemperature Sputtered Iron-Oxide Films: A) 

Grain Structure Dependence on Deposition 

Parameters; B) Large Variations in Electrical 

Conductivity 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 5.	 Properties of Low-Temperature Sputtered 

Tungsten-Trioxide Films: A) Photocurrents 

in Acid Media; B) Electrical Conductivity as 

a Function of Deposition Parameters 

Figure 6.	 Successful "Hybrid Photoelectrode" 

Demonstration: A) Test Structure; B) 

Analysis Based on Performance of 

Component Films, and Measured 

Performance of the Integrated Device shows the predicted 1-sun operating point of 0.45 

mA/cm2

 for one of the test devices, consistent with 

the measured performance shown in the inset. The 

best devices tested to date have generated hydrogen 

at up to 0.8% STH without serious degradation over 

a 10-hour operating period. Although the efficiency 

is low in these initial prototypes, there is clear room 

for improvement by enhancing the WO3 

photocurrent levels, as seen in Figure 6b. On this 

basis, future plans must include heavy emphasis on 

the further materials development of metal-oxide 

films. 

Conclusions 

•	 The optical/electronic properties of present 

hybrid-compatible metal oxides have been 

identified as the key limiting factor to hydrogenproduction efficiency in HPEs at this time, 

clearly defining the primary focus for continued 

research efforts. 

•	 We are confident that with continued 

development and testing of HPEs based on best 

available materials from both in-house and 

partnership resources, we will be able to meet the 

2005 and 2010 program goals. 

References 

1. E. L. Miller, R. E. Rocheleau, X. M. Deng, 

“Design Considerations for a Hybrid Amorphous 

Silicon/Photoelectrochemical Multijunction Cell 

for Hydrogen Production .” International Journal 

of Hydrogen Energy, 28 (6) (2003) 615-623. 

2. Multi-Year Research, Development and 

Demonstration Plan Planned Activities for 2003­

2010 (draft 6/3/03), U.S. Department of Energy: 

www.eere.energy.gov/hydrogenandfuelcells/ 

mypp/. 

• Expanded efforts to optimize hybrid-compatible 

materials for efficiency and life are needed. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

3.	 R. E. Rocheleau, E. L. Miller, 

“Photoelectrochemical Production of Hydrogen: 

Engineering Loss Analysis.” International 

Journal of Hydrogen Energy, 22(8) (1997) 

771-782. 

4. R. E. Rocheleau., E. L. Miller, A. Misra, “HighEfficiency Photoelectrochemical Hydrogen 

Production Using Multijunction Amorphous 

Silicon Photoelectrodes.” Energy and Fuels, 12 

(1998) 3-10. 

5. S. Khan, J. Akikusa, “Photoelectrochemical 

Splitting of Water at Nanocrystalline n- Fe2O3 

Thin Films Electrodes.” Journal of Physical 

Chemistry, B 103 (1999) 7184-7189. 

6. C. Santato, M. Ulmann, J. Augustynski, 

“Photoelectrochemical Properties of 

Nanostructured Tungsten Trioxide Films.” 

Journal of Physical Chemistry, B 105 (2001) 936­

940. 

7. A. Elshabini-Riad & F.D. Barlow III, “Thin Film 

Technology Handbook.” McGraw-Hill (1998). 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. E. L. Miller, R. E. Rocheleau, X. M. Deng, 

“Design Considerations for a Hybrid Amorphous 

Silicon/Photoelectrochemical Multijunction Cell 

for Hydrogen Production.” International Journal 

of Hydrogen Energy, 28 (6) (2003) 615-623. 

2. E. L. Miller, R. E. Rocheleau, S. Khan, “A Hybrid 

Multijunction Photoelectrode for Hydrogen 

Production Fabricated with Amorphous Silicon/ 

Germanium and Iron Oxide Thin Films.” 

International Materials Research Congress XI, 

Cancun, Mexico (2002). 

Special Recognitions & Awards/Patents 

Issued 

1. E. L. Miller & R.E. Rocheleau, “Hybrid SolidState/Electrochemical Photoelectrode for 

Hydrogen Production”: provisional patent with 

the UH Office of Technology Transfer and 

Economic Development. 

6 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Photoelectrochemical Hydrogen Production Using New Combinatorial Chemistry 

Derived Materials 

Eric W. McFarland (Primary Contact), Sung Hyeon Baeck, Thomas F. Jaramillo, Alan KleimanShwarsctein 

Department of Chemical Engineering 

University of California, Santa Barbara, CA 9310-5080 

Phone: (805) 893-4343; Fax: (805) 893-4732; E-mail: mcfar@engr.ucsb.edu 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Continue synthesis and screening of libraries designed in year 1 and follow promising (lead) materials 

as they are identified. 

•	 Explore the composition-function relationship of dopants in ZnO hosts. 

•	 Investigate metal oxide libraries for electrocatalytic hydrogen production and expand our highthroughput screening to include relative electrocatalytic overpotential as a routine screen. 

•	 Develop a high-throughput optical screening system to measure the effective bandgap of metal oxides 

in libraries. 

•	 Synthesize and screen model libraries optically for bandgap as a primary screen; create secondary 

libraries of compositions with solar spectrum adsorption and subsequently screen the derivate libraries 

for appropriate redox/flatband levels and finally for H2 production. 

•	 Investigate library design for synthesis of semiconductor heterostructures utilizing two-photon 

absorption processes. 

•	 Continue to expand our investigation of nanoporous materials with emphasis on the ZnO, WO3 and 

TiO2. 

•	 Participate as a member of the USA Annex-14 Expert Group in the International Energy Agency’s 

(IEA’s) Hydrogen Implementing Agreement on photoelectrolytic hydrogen production. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Material Durability 

•	 N. Materials and System Engineering 

•	 O. Photoelectrochemical Efficiency 

Approach 

•	 Using new and existing high-throughput synthesis and screening technology, create and screen suitable 

new mixed metal oxide materials for electrochemical/photoelectrochemical hydrogen production. 

•	 Improve and expand the chemical synthesis routes developed for automated high-throughput
 

experimentation.
 

•	 Utilize the automated synthesis systems to create libraries of potential hydrogen electrocatalysts/ 

photocatalysts. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Rapidly screen libraries for potential materials with electrocatalytic and/or photoelectrocatalytic activity. 

•	 Synthesize, using conventional routes, selected materials identified in libraries for detailed structural 

and electronic analysis. 

Accomplishments 

•	 Designed and fabricated combinatorial chemistry systems for synthesis and screening of hydrogen 

production photocatalysts (Figures 1a, 1b). 

•	 Demonstrated that compositional and preparative modifications of known metal oxide hosts may 

improve their photoelectrocatalytic properties (Figure 2). 

•	 Achieved first electrochemical synthesis of ordered nanoporous metal oxides (Figure 5). 

•	 Discovered nanoparticulate Pt/WO3, which is photoactive and resistant to CO poisoning. 

•	 Developed methods for and demonstrated controlled electrosynthesis of high-activity Au nanocluster 

catalysts. 

•	 Identified H intercalation as a critical component of poisoning resistance of metal oxide 

electrocatalysts.
 

Future Directions 

•	 Expand the exploration of new materials with the parallel synthesis and screening systems with 

particular emphasis on expanding the exploration of the composition-function relationships of 

quartenary ZnO systems. 

•	 Develop an automated spray pyrolysis methodology and system as a means of high-throughput 

synthesis and demonstrate the system for dopants in iron-based hosts. 

•	 Expand the search for improved photoelectrochemical performance from nanoporous/nanoparticulate 

morphologies of known hosts. 

•	 Using calibrated standards, obtain quantitative values of the efficiencies of the materials under 

investigation in terms of electrons per photon and power efficiency. 

•	 Begin definition and design of photoelectrochemical reactor systems which can incorporate the new 

materials, and perform preliminary process design calculations on a large-scale hydrogen plant to 

establish cost estimate models. 

Introduction 

The overall project objective is to utilize 

combinatorial material science to expedite the 

discovery of an efficient, practical, and economically 

sensible material for the photoelectrochemical 

production of hydrogen from water and sunlight. 

This represents a shift in the research paradigm from 

conventional serial chemical research to a 

combinatorial approach that features systematic and 

high-speed exploration of new metal-oxide based 

solid-state materials. By investigating large arrays of 

diverse materials, we are working to improve the 

understanding of the fundamental mechanisms and 

composition-structure-property relationships within 

these systems while discovering new and useful 

energy-producing photocatalysts. 

Approach 

As we have developed automated chemical 

synthesis and screening systems during the first two 

years of the program, in the second year we have 

focused on the preparation and analysis of diverse 

metal-oxide libraries with semiconducting and other 

properties suitable for photoelectrocatalysis. 

Diversity has included (1) variations in composition 

(by variable doping, electrochemical synthesis 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

conditions, and surface redox catalysts) and (2) 

variations in structure (by deliberate and diverse 

ionic and non-ionic templating agents, synthesis 

conditions, and doping). The libraries are primarily 

screened by photoelectrochemical methods, 

including zero-bias photocurrent and cyclic 

photovoltammetry. 

Results 

Task 1. We created tungsten-molybdenum mixed 

oxide libraries (W1-xMoxO3) using a parallel 

synthesis method. The film compositions were 

Figure 1.	 Automated Electrochemical Synthesis and 

Screening: (a) Rapid synthesis - a perforated 

polypropylene block with 63 independent orings is sealed upon a substrate, allowing for 63 

distinct electrolyte compositions. A probe with 

reference and counter electrodes are 

automatically dipped into each bath, and a 

potentiostat conducts electrodeposition of each 

sample. (b) High-throughput screening - a 

scanning photoelectrochemical cell traverses a 

library, illuminating each sample with a 

chopped light source, and photocurrent is 

measured. 

 FY 2003 Progress Report 

readily controlled by varying the ratios of the two 

metals in the electrolyte. By X-ray diffraction 

patterns and Raman spectroscopy, atomically-mixed 

metal oxides were confirmed to exist rather than 

simply mixed phases of pure tungsten oxide and pure 

molybdenum oxide (Figure 2). Zero-bias 

photocurrents of the mixed oxides were strongly 

dependent on the film composition. The maximum 

photoresponse was observed with W0.5Mo0.5O3, and 

photoactivity decreased as film composition 

approached either pure oxide. The photoresponse of 

the W0.5Mo0.5O3 mixed oxide film, 18.5 μA/cm2 

, 

was 50.4% higher than that of the pure tungsten 

oxide film. Cation intercalations were carried out for 

Figure 2.	 (top) Raman spectroscopy of tungstenmolybdenum mixed oxides with respect to film 

compositions and (bottom) Zero-bias 

photocurrent of tungsten-molybdenum mixed 

metal oxide films. All samples were n-type 

semiconductors. Illumination was provided by 

a 150-W Xe lamp. 

3 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

the tungsten-molybdenum mixed oxide library using 

H+, Li+, Na+, and K+ . Interestingly, as the ratio of 

tungsten to molybdenum approaches unity, 

electrochromic properties improve. Compared to 

either pure tungsten oxide or pure molybdenum 

oxide, the mixed oxides show considerably enhanced 

intercalation properties, with the W0.5Mo0.5O3 film 

exhibiting the highest intercalation properties of all. 

Metal oxide libraries were also successfully 

synthesized by electroless deposition on copper 

substrates from metal peroxo electrolytes (WO3, 

MoO3, ZrO2, Nb2O5). The reducing electrons were 

provided by the copper substrate as it was oxidized to 

CuO. 

Task 2. Several hundred samples of different 

ZnO-based materials have been synthesized and 

screened for zero-bias photocurrent. All materials 

were binary systems consisting of ZnO and a single 

other element – typically a transition metal – and a 

range of dopant concentrations was explored for each 

element. The aim of the dopant is to improve upon 

the photocatalytic activity of ZnO, particularly under 

visible illumination, and to increase the stability of 

the material. Table 1 has been constructed to 

qualitatively indicate the impact of the dopants on the 

material properties vs. pure ZnO (“very poor”, 

“poor”, “average”, “good”, and “excellent”). Cobalt 

showed the greatest improvements in terms of visible 

light photocurrent, and the photoactivity of cerium 

samples remained high for several minutes, as 

opposed to pure ZnO, whose photocurrent decayed to 

15% of its initial value after the same amount of 

time. Iron, nickel, ruthenium, and manganese also 

showed improvements to ZnO. After having 

explored 24 different binary ZnO systems, of 

different concentrations, we are looking forward to 

focusing on the best materials to begin our 

investigation of ternary and quaternary libraries. 

Task 3. Diverse compositions of cobalt-iron-nickel 

oxide materials supported on 304 stainless steel have 

been synthesized by combinatorial spray pyrolysis. 

These samples have been studied for water oxidation 

electrocatalysis by tafel slopes and exchange current 

in basic electrolytes (KOH 20% w/w). Different 

precursor solutions were used to create 

compositional differences. The best electrocatalysts 

found to date in this study were synthesized with iron 

or nickel at 10-20% of the cobalt concentration in 

 FY 2003 Progress Report 

solution. Ternary libraries will be explored in the 

near future. 

Tasks 4 & 5. We are currently completing our 

infrastructure for the automated measurement of 

bandgap of combinatorial libraries. The system is 

shown schematically in Figure 3. In this design, an 

integrating sphere is affixed to our x-y-z 

combinatorial stages. In a fully automated fashion, 

the integrating sphere steps down upon each sample 

independently, and each sample is illuminated by a 1-

kW Xe lamp (ThermoOriel). An optical fiber carries 

the diffuse reflectance of the sample to an Ocean 

Optics S2000 detector, which measures the spectra 

and allows for bandgap calculation. This 

combinatorial method for bandgap measurement will 

be the first screening conducted on libraries. 

Task 6. Heterostructures of Cu2O/TiO2 have been 

synthesized and screened for photocatalytic activity. 

Table 1. Qualitative impact (excellent, good, average, 

poor, very poor) of 24 different elements when 

co-deposited with ZnO as compared to pure ZnO. 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

The Cu2O/TiO2 heterojunction scheme can be 

viewed in Figure 4. Cu2O is a photocatalyst that 

benefits from a small bandgap (2.0 eV), which allows 

for excellent solar absorption. It is limited, however, 

by photocorrosion which degrades the material 

rapidly. TiO2, on the other hand, is a robust 

photocatalyst that is stable for long periods of time 

(ca. thousands of hours); however, it is limited by 

poor visible photon absorption (bandgap 3.0 eV). By 

creating a heterojuction of Cu2O covered with TiO2, 

a photocatalytic system (which operates as a 

photocathode) results which absorbs more visible 

light than pure Cu2O and is as stable as pure TiO2. 

Task 7. We have been developing a general 

method for the production of high surface area 

nanostructured films by utilizing electrochemicallydriven self-assembly of surfactants. We have 

successfully electrodeposited mesoporous WO3, 

TiO2 by controlling deposition conditions (Figure 

5). Mesoporous tungsten oxide films with lamellar 

structure were successfully synthesized by 

electrodeposition using sodium dodecylsulphate 

(SDS) as a templating agent. Nanophases can be 

varied by changing the deposition potential, which 

directly affects the surface charge densities of the 

electrode and, therefore, the surface assembly 

patterns of the inorganic-surfactant aggregates. 

Compared to nonporous tungsten oxide prepared 

with isopropanol, lamellar phase mesoporous 

tungsten oxide showed higher photocatalytic activity 

Figure 3.	 Schematic design of combinatorial 

measurement of diffuse reflectance for 

ultraviolet-vis spectroscopy and bandgap 

calculation. 

 FY 2003 Progress Report 

and greater current density for hydrogen 

intercalation. Functional improvements are most 

probably due to the larger surface area of 

mesoporous tungsten oxide and facilitated charge 

transport. 

Task 8. We have actively contributed to the Annex 

14 of the IEA, including attendance and participation 

in the expert meeting in Paris, France, April 27-28. 

Results were presented to the Annex working group 

from our laboratory, and we shared ideas concerning 

the future of international collaboration in the area of 

photoelectrochemical water splitting. 

Figure 4.	 Cu2O/TiO2 Heterojunction on Ti Foil: (top) 

The Cu2O functions as a light absorber and the 

TiO2 overlayer protects against corrosion. The 

band diagram demonstrates why the device 

operates as a photocathode despite n-type TiO2 

on the surface. (bottom) The device produces 

nearly 1 mA/cm2 of photocurrent at –1 V bias 

vs. Ag/AgCl under 1 sun illumination. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 5.	 Nanoporous Metal Oxide Photocatalyts: (top) 

Transition electron microscopy images of 

tungsten oxide films deposited in the presence 

of SDS and (bottom) 2D-grazing incidence xray diffraction pattern of lamellar tungsten 

oxide on indium tin oxide coated glass. 

Conclusions 

As we complete the second year of the project in 

the fall of 2003, we will have developed 

combinatorial methods for high-throughput synthesis 

and screening of new mixed-metal oxides active for 

photoelectrochemical production of hydrogen. 

Mixed WO3-MoO3 has shown improvements over 

the pure oxide components, and binary ZnO:Me (Me 

= Co, Ni, Fe, Ru, Ce, Mn) have demonstrated 

improved photocatalytic performance compared to 

pure ZnO. A new means of nanoporous metal oxide 

synthesis has been demonstrated and Pt and Au 

nanoparticles created electrochemically which show 

promise as new surface electrocatalysts. 

FY 2003 Publications/Presentations 

1. S.-H. Baeck, T. Jaramillo, G. Stucky, and E. 

McFarland, "Controlled Synthesis of 

Nanoparticulate Tungsten Oxide", Nano Letters, 

2(8), 831-834(2002). 

2. S.-H. Baeck, C. Brandly, T. Jaramillo, and E. 

McFarland, "Combinatorial Electrochemical 

Synthesis and Characterization of Tungsten based 

Mixed Metal Oxide", Journal of Combinatorial 

Chemistry, 4(6), 563-568 (2002). 

3. S.-H. Baeck, T. Jaramillo, and E. McFarland, 

"Influence of Composition and Morphology on 

Photo and Electrocatalytic Activity of 

Electrodeposited Pt/WO3", Abstracts of Papers of 

American Chemical Society, 224: 062-FUEL Part 

1 (2002). 

4. S.-H. Baeck and E. McFarland, "Combinatorial 

Electrochemical Synthesis and Characterization of 

Tungsten-Molybdenum Mixed Oxides," Korean 

Journal of Chemical Engineering, 19 (4), 593-596 

(2002). 

5. K.-S. Choi, H. Lichtenegger, G. Stucky, and E. 

McFarland, "Electrochemical Synthesis of 

Nanostructured ZnO Films Utilizing SelfAssembly of Surfactant Molecules at Solid-Liquid 

Interfaces", Journal of the American Chemical 

Society, 124(42), 12402-12403 (2002). 

6. W. Siripala, A. Ivanovskaya, T. Jaramillo, S.-H. 

Baeck, and E. McFarland," A Cu2O/TiO2 

Hetrojuction Thin Film Cathode for 

Photoelectrocatalysis", Solar Energy Materials & 

Solar Cells, 77(3), 229-237 (2003). 

7. T. Jaramillo, S.-H. Baeck, B.R. Cuenya, and E. 

McFarland, "Catalytic Activity of Supported Au 

Nanoparticles Deposited From Block Co-polymer 

Micelles", Journal of the American Chemical 

Society, 125(24), 7148-7149 (2003). 

8. K.-S. Choi, E. McFarland, and G. Stucky, 

"Electrocatalytic Properties of Thin Mesoporous 

Platinum Films Synthesized Utilizing Potential6 
Hydrogen, Fuel Cells, and Infrastructure Technologies

Controlled Surfactant Assembly", Advanced 

Materials, Accepted and in Press (2003). 

9. S.-H. Baeck, K.-S. Choi, T. Jaramillo, G. Stucky, 

and E. McFarland, "Enhancement of 

Photocatalytic and Electrochromic Properties of 

Electrochemically Fabricated Mesoporous WO3 

Thin Films", Advanced Materials, Accepted and 

in Press (2003 August). 

10.S.-H. Baeck, T. Jaramillo, G. Stucky, and E. 

McFarland, "Synthesis of Tungsten Oxide on 

Copper Surfaces by Electroless Deposition", 

Chemistry of Materials, Accepted and in Press 

(2003 August). 

 FY 2003 Progress Report 

7 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Discovery of Photocatalysts for Hydrogen Production 

D. Brent MacQueen (Primary Contact), Albert Hirschon, Theodore Mill, and Michael Coggiola 

SRI International 

333 Ravenswood Avenue 

Menlo Park, CA 94025 

Phone: (650) 859-5286; Fax: (650) 859-5286; E-mail: brent.macqueen@sri.com 

Nobi Kambe and Timothy Jenks 

NanoGram Corporation 

46774 Lakeview Boulevard 

Fremont, CA 94532 

Phone: (510) 407-3232; E-mail: kambe@nanogram.com 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 To design and construct tools for the high throughput screening of the properties of photocatalysts 

relevant to the photoelectrochemical generation of hydrogen. 

•	 To use the high throughput screening tools to identify materials with the appropriate energetics for 

water splitting. 

•	 To use the industrially relevant laser pyrolysis materials production capability of our partner,
 

NanoGram Corp., to produce commercial scale quantities of photocatalysts.
 

•	 Demonstrate that materials issues that are a hindrance to the commercialization of
 

photoelectrochemical water splitting can be addressed through a materials discovery process.
 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Materials Durability 

•	 N. Materials and Systems Engineering 

•	 O. Photoelectrochemical Efficiency 

Approach 

•	 Develop tools for the high throughput analysis of material properties relevant to photoelectrochemical 

hydrogen generation. 

•	 Work with existing nanoparticulate powder manufacturer to test materials with existing technology to 

produce kg/hr scale quantities. 

•	 Identify candidate materials for further study via high throughput screening. 

Accomplishments 

•	 Constructed Solar Simulator. 

•	 Designed and constructed 25-cell photolysis analysis module. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Acquired diffuse reflectance instrument employing Ocean Optics Spectrometer. 

•	 Initiated evaluation of NanoGram NPMTM produced nanoparticulate titania. 

Future Directions 

•	 Modify stable metal oxide semiconductors to shift bandgap to increase utilization of the solar spectrum 

and increase solar to hydrogen efficiencies. 

•	 Complete 25-cell module for electrochemical analysis of materials to provide band edge energy and 

photoaction spectrum analysis. 

•	 Incorporate hydrogen sensor technology developed for fuel cell safety applications into analysis 

modules for direct hydrogen determination. 

•	 Increase level of collaboration between other DOE funded laboratories via establishment of mutual 

database. 

Introduction 

The process whereby semiconductor materials 

absorb light and convert that light to electricity has 

been known for some time and is the cornerstone of 

the photovoltaic (PV) industry. As an alternative to 

generating electricity, the electron/hole pair 

generated by the absorption of light by a 

semiconductor could be used to facilitate a chemical 

transformation, thereby storing the energy for later 

use. This is the basis for the photoelectrochemical 

(PEC) generation of hydrogen from sunlight, water 

and a semiconductor-based photocatalyst. In this 

process, electrons generated by the absorption of 

light are used to reduce water, generating hydrogen, 

and the holes are used to oxidize water, generating 

oxygen. The hydrogen produced could then be used 

as a fuel in either electrolytic or combustion 

processes. It is more efficient to generate hydrogen 

using PEC directly than to use a PV array to feed an 

electrolyzer. 

The key materials requirements for efficient PEC 

hydrogen production are: A) a semiconductor with a 

bandgap relevant to the solar spectrum so as to 

maximize solar utilization, B) band edge energies 

relevant to the reduction and oxidation potentials of 

water to minimize energy mismatch, C) fast 

interfacial electron transport to minimize 

recombination and D) stability in the presence of an 

aqueous electrolyte. The key technical barriers to the 

implementation of PEC hydrogen production relate 

to the fact that materials that satisfy all of these 

requirements, simultaneously, have not been found. 

This is not due to a conflict with these requirements 

and known laws of physics (there are none), but 

rather reflects the immature stage of this technology. 

In the earliest work on this technology, 

semiconductor materials developed for the PV 

industry were analyzed and found to be unsuitable 

due to their poor stability in aqueous electrolytes. 

Current work is under way with respect to the 

identification of materials specifically for the 

purpose of photoelectrochemical generation of 

hydrogen. 

Approach 

The use of high throughput techniques to speed 

the discovery process has been in place for a number 

of years; pharmaceutical companies were the first to 

invest heavily in the combinatorial synthesis and 

high throughput analysis concept. The key to the 

concept is to test as many samples as possible as 

quickly as possible for a specific property rather than 

to do a complete characterization on a specific 

material or class of materials. In this manner, 

candidates for further study can be culled from very 

large sample sets. In our approach to develop tools 

for the high throughput screening of materials for 

properties relevant to PEC hydrogen production, we 

have designed and built a 25-cell module to analyze 

the photolysis products generated upon illumination 

of samples with a simulated solar spectrum. The 

basic design incorporates a vacuum sealed sample 

module with a pressure transducer to monitor the 

pressure as a function of photolysis time, see Figure 

1. The pressure transducer data is computer 

2 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

monitored, and at set pressure intervals, a Gillson 

sample handler (top right of Figure 1) that has been 

modified is triggered to sample the head space gas 

and feed it to a gas chromatograph for analysis. The 

vacuum seal component of this design ensures that 

each cell is isolated, and the quick release and seal 

capabilities make loading quick and easy. 

In the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program (HFCIT) Multi-Year Program 

Plan, the need to have processes for the 

commercially relevant production of PEC materials 

is identified. Part of the sample lots that we are 

investigating are produced by NanoGram Corp. 

using their nanoparticle manufacturing technology, 

NPMTM. NanoGram has the process technology to 

produce these materials at rates of kilograms per hour 

and higher should a demand for these materials arise. 

Results 

To date, the key results involve the design and 

construction of the 25-cell photolysis analysis 

module, which we have now fully engaged in the 

initial screening of sample sets of nanoparticulate 

titania provided by our partner, NanoGram Corp. 

The photolysis setup delivers a photon flux on the 

order of 80 mW/cm2

 to the sample cells as 

determined by actinometry. An interesting 

observation is that the pressure transducer response 

factor is slowly changing. This was noticed during 

Figure 1. Picture of 25-Cell Photolysis Analysis 

Module 

 FY 2003 Progress Report 

the course of a routine pressure testing in which we 

had initially observed very a very narrow distribution 

of pressure responses; however, after a number of 

experiments, the distribution of response factors 

appeared to increase, see Figure 2. As such, we now 

routinely collect a calibration curve for the pressure 

transducers. As shown in Figure 3, while the 

response factors of the various pressure transducers 

does vary considerably, the response of any given 

transducer is very linear over pressure ranges 

encountered during the normal course of operation. 

A sample data set collected during the course of 

a photolysis experiment is shown in Figure 4. 

Contained with the 25 sample cells are 6 TiO2 

samples in triplicate, one Niobate in triplicate and 

four blanks containing a similar particulate that is 

known to be inactive. The data set has been 

corrected for the photon flux for each specific cell 

and for the pressure transducer response. From this 

Figure 2. Leak Test Results Indicating Range of 

Pressure Transducer Response Factor 

Figure 3. Results of Calibration of Pressure Transducer 

Response Factor 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 4. Time Versus Pressure Results 

experiment, the niobate sample resulted in the best 

efficiency and the highest pressure versus time plots, 

followed by an oxygen-deficient phase of titania 

which does extend the absorption spectrum into the 

visible. The niobate, while still exhibiting 

efficiencies of less than 1%, is a material that we will 

be investigating further in various modified forms. 

To date, we have received over 50 different samples 

from NanoGram, with the majority of them being 

titania samples prepared over a significant range of 

particulate sizes, see Table 1. 

In our initial screen of the TiO2 samples, a 

platinum catalyst was deposited onto the particle sets 

via the photoreduction of a platinum salt. Samples 

have also been prepared using chemical reduction of 

impregnated platinum salts; however, these to date 

Table 1. Partial TiO2 Sample List Indicating Particle 

Size and Surface Area 

 FY 2003 Progress Report 

have not been screened. In the titania series prepared 

with the photoreduced platinum catalyst, we see no 

statistical variation in the efficiency of hydrogen 

generation as a function of particle size, and in all 

cases efficiencies were in the range of 0.1% solar 

photons to hydrogen. Interestingly, there does appear 

to be a trend developing with respect to the hydration 

of the titania. These results are very premature, and 

considering the overall rather disappointing 

performance of these materials to date, it is doubtful 

that time will be spent analyzing them further with 

the platinum catalyst. We are currently evaluating 

these materials with other catalysts. We are also 

currently expanding the materials we are looking at 

to include some niobate structures. These materials 

have shown evidence of water splitting in the past 

and the extension of their absorbance spectra into the 

visible relative to the titania samples, see Figure 5. 

Conclusions 

Our initial results, while far from complete or 

conclusive, indicate that the nanoparticulate titania 

samples provided by NanoGram Corp. exhibit very 

poor efficiencies for the conversion of photons of 

solar relevance to hydrogen. In no case were 

conversion efficiencies greater than 0.3% observed in 

any of the titania samples. This clearly indicates that 

we need to expand the composition of materials 

being explored. With the relocation of one of 

NanoGram Corporation's laser pyrolysis instruments 

to the SRI campus, we will be able to facilitate this 

expansion of material candidates considerably. 

Figure 5. Absorbance spectra generated from diffuse 

reflectance data for a titania, TOX 17, and a 

niobate semiconductor sample. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Publications/Presentations 

1. Brent MacQueen, "Photoelectrochemical 

Hydrogen Production", Invited Lecture, 

Hydrogen Workshop of the Global Climate 

Energy Project, March 2003, Stanford 

University, Palo Alto CA. 

 FY 2003 Progress Report 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low Cost, High Efficiency Reversible Fuel Cell Systems 

Dr. Christopher Milliken (Primary Contact), Dr. Robert Ruhl 

Technology Management, Inc. 

9718 Lake Shore Blvd. 

Cleveland, OH 44108 

Phone: (440) 995-9500; Fax: (440) 720-4527; E-mail: milliken@stratos.net 

DOE Technology Development Manager: Matthew Kaufmann 

Phone: (202) 586-5824; Fax: (202) 586-9811; E-mail: Matthew.Kauffman@ee.doe.gov 

Objectives 

•	 Improve performance of reversible solid oxide stacks (capable of operating in both fuel cell and 

electrolysis modes) by reducing polarization and rate of degradation. 

•	 Demonstrate an integrated fuel cell hot subassembly with a stack of about 50 reversible type cells 

operating on natural gas. 

•	 Evaluate the economic impact of reversible solid oxide fuel cell/electrolyzer systems and consider 

applications where a competitive advantage may be achieved. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance (O&M) 

• Q. Cost 	 

•	 R. System Efficiency 

•	 S. Grid Electricity Emissions 

•	 T. Renewable Integration 

•	 U. Electricity Costs 

Approach 

•	 Evaluate alternate materials and cell geometry parameters to reduce cell polarization. 

•	 Reduce operating temperature to improve stack life. 

•	 Test a stack of up to 50 reversible cells in a new integrated system assembly. 

•	 Perform cost and environmental evaluations of alternative equipment and system configurations. 

Accomplishments 

•	 Optimized cell geometry by modeling the stack and system. 

•	 Designed, fabricated, and evaluated reversible stack performance over a range of temperatures and 

operating conditions. 

•	 Demonstrated stable operation for >1200 hours in small reversible stacks at acceptable efficiency. 

•	 Met all stack performance targets. 

•	 Completed preliminary economic analysis and identified applications where reversible electolyzer/fuel 

cell systems may have a competitive advantage. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Fabricate and test a stack of up to 50 reversible cells using standardized processes. 

• Complete evaluation of alternative stack operating conditions. 

• Complete cost and environmental assessment of alternative system configurations. 

• Complete present project in Fall of 2003. 

Introduction 

The Technology Management, Inc. (TMI) 

reversible (fuel cell - electrolyzer) system employs a 

stack of high temperature solid oxide cells to 

electrochemically produce either electricity (from 

fuel and air or fuel and oxygen) or hydrogen (from 

water and supplied electricity). A fuel cell version of 

the system operating at atmospheric pressure could 

operate on natural gas (or other carbon-containing 

fuel) and air. A high-pressure reversible electrolyzer 

version would make high-pressure hydrogen and 

oxygen from water and also operate in reverse (on 

demand) to generate electricity from these gases. 

The novel reversible stacks require simpler and more 

efficient auxiliary equipment than conventional fuel 

cell systems. Calculations have shown that the 

proposed systems could achieve higher efficiencies 

in both fuel cell and electrolysis modes than existing 

alternatives. 

During the current phase of the project, TMI has 

demonstrated reversible cells and stacks which 

bettered the quantitative performance targets set for 

polarization voltage, operating efficiency, rate of 

performance loss, and seal leakage rate. This success 

resulted from a cell and stack development program 

that studied the effects of component dimensions and 

fabrication details, assembly procedures, startup 

procedures, and operating conditions. A complete 

test system for stacks up to 50 cells has been 

designed, built, and operated (with stacks up to 19 

cells thus far). Cost and engineering studies were 

extended significantly to identify cases where 

vehicle-grade, high-pressure hydrogen could be 

produced at the refueling point from natural gas at 

costs below DOE targets. The use of the proposed 

reversible electrolyzers for energy storage also 

appears to offer sizeable advantages over the 

expected cost, size, and weight of known 

rechargeable batteries. 

Approach 

The overall goals for reversible stack 

performance are (a) high efficiencies at selected 

power levels and (b) low degradation rate (power 

loss over time at constant flows). High efficiencies, 

in turn, require low polarization voltages and low 

seal leakage rates. Low polarization voltages in solid 

oxide stacks result from low concentration 

polarization and low resistive polarization, the latter 

being quantified by area specific resistance (ASR, 

expressed in Ohm-cm2

). Seal leakage rates may be 

computed as a valve coefficient (Cv, a relative 

measure of flow through an orifice). Simulations and 

prior experiments have shown that achieving the 

desired performance of TMI’s reversible stacks is 

significantly more difficult in fuel cell mode than in 

electrolysis mode. The current phase uses the 

following goals in fuel cell mode. 

• ASR < 1.00 Ohm-cm2 

• Cv < 10-5 

• Degradation rate < 5% per 1000 hours 

Fabrication improvements, materials 

substitution, temperature optimization, and assembly 

improvements were evaluated to reduce ASR. 

Dimensional optimization and startup details are 

being used to minimize seal leakage. A lower 

degradation rate is achieved via improvements in 

fabrication details and seal leakage. Concentration 

polarization was reduced by combining increased 

porosity, improved dimensional stability, and 

adjusted component dimensions. 

The design of a larger system for operation with 

up to 50 cells is based upon prior work by TMI on 

other test systems augmented by additional systemspecific engineering calculations. 

Cost and engineering studies build on work 

performed during the prior phases of this project as 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

well as cost studies by TMI for other projects. Data 

on natural gas and electricity pricing are from the 

Energy Information Administration. Hydrogen cost 

targets are taken from public DOE hydrogen and fuel 

cells documents. 

Results 

Reversible Stack Development. At the start of the 

present phase, measurements of reversible cell 

performance were poor and insufficient to achieve 

targets. There were also considerable variations 

from cell to cell. Concentration polarization was 

initially high, thereby limiting maximum possible 

current densities to only about 100 mA/cm2 . Major 

improvements have been the result of increased 

porous layer thicknesses and improved dimensional 

stability, thereby maintaining higher effective 

porosities. 

Early ASR measurements ranged from about 2.2 

to over 3.0 Ohm-cm2

, which were in excess of the 

goal of 1.00 Ohm-cm2 . ASR was improved by 

reducing seal leakage, optimizing electrical contact 

between cell layers, and by slightly increasing 

temperature. Studies have found that ASR varies 

with both fuel utilization (fuel oxygen potential) and 

current density. Recent ASR measurements have 

ranged from 0.84 to about 1.4 Ohm-cm2 in single 

cells and stacks, increasing at high fuel utilization. 

Early seal leakage rates varied, sometimes being 

more than ten times the target Cv of 10-5 . 

Improvements in dimensional tolerances, assembly 

procedures, and startup procedures have resulted in 

measured Cv values below the target, with the best 

values being less than 10-6 . 

Early degradation rates were highly variable, 

sometimes exceeding 20% per 1000 hours. One 19-

cell stack operated for over 360 continuous hours on 

natural gas with less than 2% per 1000 hours 

degradation. However, if a stack has one or more 

significant leaks, considerably higher rates are still 

seen. The temperature dependence of degradation 

rate has not yet been quantified. 

A limited number of cells and stacks were tested 

in electrolysis mode, with the results confirming 

those from earlier work. Measured ASR in this mode 

equaled that in fuel cell mode. In projected 

commercial solid oxide electrolyzers, allowable 

ASRs are higher than those for highly efficient fuel 

cell systems due to electrolyzer heat balance 

considerations. 

Cell and Stack Fabrication. Evolutionary 

improvements and modifications were made to 

existing TMI materials specifications, fabrication 

methods, and cell dimensions to accommodate the 

reversible cell and stack design. Minor 

modifications of standard TMI fabrication 

procedures were sufficient to produce thicker fuel 

and oxygen electrodes. Larger diameter, thicker 

seals were made using methods from internally 

funded programs. Over one hundred reversible cells 

have been fabricated for this project thus far. 

Integrated System Demonstration. An important 

objective of this phase is to demonstrate a complete 

working system containing a sizeable reversible 

stack because stack performance is strongly 

dependent upon the system variables. 

Figure 1 shows the test system for stacks up to 50 

cells. This system has been designed, built, 

commissioned, and operated with stacks up to 19 

cells thus far. The cylindrical assembly includes the 

reversible stack, heat exchanger, fuel processing, air 

blower, startup heater, electrical connections, 

thermocouples, stack mounting assembly, and 

insulation. The rectangular enclosure contains test 

instrumentation, active electrical load circuit, 

detachable startup systems, and fuel control valve. 

Figure 1. Laboratory System Assembly 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

The best performance parameters measured to date 

on this system (with 9- to 19-cell stacks) are shown in 

Table 1 (seal orifice coefficient was estimated from 

open-circuit voltage: up to 1.12 V/cell). 

Table 1. Best Performance Parameters for Reversible 

Stack System 

Parameter Units Goal Measured 

Area specific 

resistance 

Ohm-cm2

 < 1.00 0.96 

Power 

degradation rate 

per 1000 

hrs 

< 5% < 2% 

Seal orifice 

coefficient 

 < 10-5 < 10-6 

Cost and Engineering Studies. The installed and 

operating costs of systems producing hydrogen for 

vehicles are critical. The ultimate widespread use of 

hydrogen vehicles will only occur if and when 

affordable hydrogen is readily available. Vehicular 

hydrogen must also be very pure and available at 

pressures up to about 80 MPa (11,600 psi) for 

refilling vehicle tanks rated at about 69 MPa (10,000 

psi). Hydrogen production processes that result in 

the lowest delivered-to-vehicle costs are expected to 

eventually dominate the market. 

TMI believes it may have a candidate technology 

for achieving very low delivered hydrogen costs. 

Configured as shown in Figure 2 and sited at vehicle 

Figure 2. System Concept 

refueling sites, TMI reversible stack and system 

technology would be employed for both fuel cell 

system modules (using natural gas or other 

carbonaceous fuel) and the reversible electrolyzer 

subsystem, capable of producing 80 MPa pure 

hydrogen for vehicles as well as performing energy 

storage (battery replacement). The calculated 

projected energy conversion efficiencies in fuel cell, 

electrolyzer, and energy storage modes, as well as the 

overall natural gas to high-pressure pure hydrogen 

mode, can be shown to be superior to known 

competing technologies. 

TMI cost studies to date show that the lowest 

vehicle-delivered costs (below $1.50 per kg 

hydrogen) are projected for residential systems 

which can co-produce vehicle hydrogen, AC power, 

and hot water. 

Conclusions 

•	 Improved reversible solid oxide stack performance has been achieved. 

•	 Sizeable reversible solid oxide fuel cell/ 

electrolyzer stacks and a complete test system 

have been demonstrated. 

•	 Projected cost (at the refueling nozzle) of vehicle 

hydrogen from natural gas has been computed to 

be as low as $1.50 per kg hydrogen. 

•	 Projected solid oxide electrolyzer efficiencies 

near 95% have been achieved. 

•	 Highly versatile system concepts using 

reversible electrolyzers and fuel cells have been 

proposed. 

FY 2003 Publications/Presentations 

1. "Low Cost, High Efficiency Reversible Fuel Cell 

Systems", R. C. Ruhl, DOE Hydrogen and Fuel 

Cells Annual Merit Review, Berkeley CA, May 

20, 2003 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

High-Efficiency Steam Electrolyzer 

Andrew L. Vance (Primary Contact), John W. Trent, Ervin F. See and Robert S. Glass 

Lawrence Livermore National Laboratory 

P.O. Box 808, L-350 

Livermore, CA 94550 

Phone: (925) 423-9166; Fax: (925) 422-6892; E-mail: vance6@llnl.gov 

DOE Technology Development Manager: Matthew Kauffman 

Phone: (202) 586-5824; Fax: (202) 586-9811; E-mail: Matthew.Kauffman@ee.doe.gov 

Objectives 

•	 Develop a highly efficient steam electrolyzer for distributed hydrogen production 

•	 Utilize natural gas as an anode depolarizer to reduce electricity consumption 

•	 Demonstrate prototype electrolyzers with successively higher hydrogen production capacities in the 

laboratory 

•	 Demonstrate a 5-kW electrolyzer for proton exchange membrane (PEMFC) vehicle refueling in the 

field 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• Q. Cost 	 

•	 R. System Efficiency 

•	 U. Electricity Costs 

Approach 

•	 Optimize cathode and anode materials for enhanced electrochemical kinetics and obviate carbon 

deposition problems 

•	 Study the effect of microstructure on electrode performance 

•	 Develop tubular electrolyzer stack for pressurized operation 

•	 Develop tube fabrication and ceramic-to-metal seal processes 

•	 Optimize system components and engineering design and perform long-term durability testing on 

components and systems 

•	 Engineer pressure vessel and electrolyzer components to maximize unit safety and lifetime 

•	 Design, build, and demonstrate prototype electrolyzers with successively higher hydrogen production 

capacities and demonstrate in the laboratory (to 5 kW) 

•	 Perform a field demonstration of a 5-kW electrolyzer for PEMFC vehicle refueling 

Accomplishments 

•	 Improved performance of anode and cathode materials by optimizing composition and coating 

techniques 

•	 Explored tube fabrication techniques to develop scalable production method 

•	 Built and demonstrated laboratory-scale electrolyzer capable of producing 700 sccm of hydrogen 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Designed new electrolyzer system targeting 1-kW hydrogen production 

•	 Confirmed tube assembly seals in test sample withstand thermal cycling between ambient and 700°C 

•	 Initiated collaboration with the Connecticut Global Fuel Cell Center for tube fabrication 

•	 Completed construction of 1-kW electrolyzer engineering test bed system and pressure tested to 150 

psi at 700°C (tube assemblies will be delivered in August for September test) 

Future Directions 

•	 Assemble and test 1-kW electrolyzer 

•	 Evaluate and optimize 1-kW electrolyzer 

•	 Perform long-term testing of components and system 

•	 Evaluate improved anode formulations to minimize carbon deposition 

•	 Design and build 5-kW electrolyzer 

•	 Field test 5-kW system 

Introduction 

A hydrogen economy will require readily 

available and affordable hydrogen fuel. Current 

methods of hydrogen production do not fulfill these 

requirements. We are working on an electrolyzer 

system that can provide distributed hydrogen 

production while taking advantage of the nation's 

existing natural gas infrastructure. Electrolysis is a 

promising hydrogen production technology both 

because of its ability to produce pure hydrogen from 

water and because it does not require large, 

centralized plants. Unlike other technologies, the 

cost of hydrogen production scales well from larger 

to smaller systems. Electrolysis units could be 

widely distributed and scaled to meet the hydrogen 

requirements of different users such as individual 

households, local fueling stations and industrial 

facilities. A significant drawback to traditional 

electrolysis is the large electricity consumption 

required to convert water to hydrogen and oxygen. 

The electricity requirements mean such systems are 

expensive to operate. In addition, if the electricity is 

provided from coal or gas-fired power plants, 

electrolytic hydrogen production does not mitigate 

greenhouse gas emissions. 

The concept described in this report is intended 

to resolve some of the problems associated with 

electrolytic hydrogen production. By utilizing 

natural gas in place of air in the anode compartment 

in a solid oxide electrolyzer, the electricity 

requirements of the system are greatly reduced. The 

system has the capability to produce pure hydrogen 

or hydrogen humidified to levels appropriate for 

direct use in a PEM fuel cell. With inherent 

electrochemical compression, the requirement for 

external compression for pressurization could be 

reduced. This technology offers numerous 

advantages for distributed hydrogen production for 

stationary and transportation hydrogen fuel cells. 

Our preliminary calculations indicate that using this 

concept, hydrogen could be produced at a cost 

competitive with gasoline (on a per gallon equivalent 

basis) while also lowering carbon dioxide emissions. 

Approach 

As mentioned above, natural gas is used to 

depolarize the anode in our solid oxide-based NaturalGas-Assisted Steam Electrolyzer (NGASE), reducing 

electricity usage and therefore leading to lower cost 

operation. We are currently pursuing a system 

operating in total oxidation mode in which the steam 

at the cathode is reduced to hydrogen and oxide anions 

while the methane is oxidized at the anode to carbon 

dioxide and water. In this mode, hydrogen is produced 

on the cathode side and is easily converted to a pure 

hydrogen stream by condensation of the 

accompanying water vapor. The system could also be 

modified to operate in partial oxidation mode in which 

additional hydrogen is produced on the anode side by 

water-shifting the carbon monoxide produced by 

methane partial oxidation. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Our approach is to improve system efficiency by 

the judicious choice of materials and by engineering 

the system components to maximize durability and 

safety. In 2003, we are building and testing an 

experimental system of 1 kW hydrogen production 

capacity. We plan to utilize this system as a test bed 

for future systems while also working to optimize 

materials performance. We are also conducting 

component durability testing. 

Results 

Past accomplishments include demonstrating the 

effectiveness of the use of natural gas in the anode 

chamber for lowering electricity consumption. It was 

shown that methane provided a reduction from 1.5 

volts with a conventional system (with air in the anode 

compartment) to 0.5 volts at 1 A/cm2

 current density. 

An initial test system utilizing a four-tube array was 

demonstrated that produced 700 sccm of hydrogen at 

750°C and 35 psi of steam. Results from this system 

were used to generate an improved design. 

In FY 2003, the continuing resolution caused 

delays in component procurement and system 

construction, and the project also experienced some 

personnel shifts. We have worked to design a new 

system that should avoid some of the problems 

encountered in the previous prototype while offering 

greater flexibility. For example, the last system was 

limited to operating pressures of 35 psi due to leaks in 

the pressure vessel. Our current engineering test bed 

consisting of all necessary system components minus 

tube assemblies (Figure 1) has been built and tested to 

Figure 1. Electrolyzer Engineering Test Bed 

 FY 2003 Progress Report 

150 psi at a temperature of 700°C and has proven to be 

leak free. This system is designed to accept arrays of 

four tubes up to 18 inches long and can be readily 

modified to accept higher numbers of tubes. Thus, 

with minimal cost and effort, our hydrogen generating 

capacity could be increased without the need to build 

an entirely new system. 

In order to address the issue of carbon deposition 

at the anode, we have begun examining potential 

improved anode materials. Candidate materials with 

compositions approximating that of the cermet anode 

are screened by temperature programmed oxidationmass spectrometry by placing powders in a quart tube 

and passing methane through the powder as the 

temperature is ramped up to 700°C. The gaseous 

reaction products are analyzed by a residual gas 

analyzer mass spectrometer. The telltale sign of 

carbon deposition is the evolution of hydrogen as the 

methane is converted to carbon and hydrogen. 

Materials that display reduced carbon deposition 

tendencies will be further evaluated by single cell 

testing to mimic actual electrolyzer operating 

conditions. 

We have initiated a collaboration with the 

Connecticut Global Fuel Cell Center for the 

fabrication of tubes by an extrusion technique. The 

Connecticut group has more than ten years experience 

in tube extrusion, and this will accelerate system 

development efforts. After the application of 

electrolyte and cathode coatings, the tubes will be 

brazed into specially designed flexible electrical 

isolators (Figure 2). In the previous system, the tubes 

were connected in parallel, resulting in resistive 

losses; the new design will allow the tubes to be 

connected in series to allow reduced current operation. 

We are working with an industrial vendor to optimize 

these components. 

Conclusions 

•	 We have designed a new electrolyzer system that 

shows promise for economically attractive 

distributed hydrogen production. 

•	 The electrolyzer engineering test bed has been 

assembled and pressure tested to 150 psi at 

700°C, and we have confirmed both the pressure 

vessel seals and the tube assembly seals can 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Drawing of Flexible Electrical Isolator 

withstand repeated temperature cycling between 

ambient and 700°C. 

•	 Our new system is designed to be flexible and 

scalable, allowing increased hydrogen generating 

capacity without the need to build a new system 

from the ground up. 

•	 We have initiated a collaboration with the 

Connecticut Global Fuel Cell Center for 

fabrication of anode-supported tubes and are 

working with an industrial vendor for component 

assembly. 

•	 Carbon deposition at the anode remains a 

potential challenge that we believe can be solved 

in the near-term by slight humidification of the 

methane along with applying a potential to the 

tubes. We are also carrying out materials studies 

to evaluate potential improved anode materials. 

•	 We expect to complete the assembly of the 

current 1-kW electrolyzer system by late August 

with system testing to commence in September. 

•	 Our system is designed to allow easy scale-up to 

5 kW of hydrogen generating capacity. 

FY 2003 Publications/Presentations 

1. DOE Hydrogen and Fuel Cells 2003 Annual 

Merit Review, Oral Presentation, A.L. Vance, 

J.W. Trent, E.F. See, L.P. Martin, R.S. Glass 

"High-Efficiency Steam Electrolyzer" May 20, 

2003. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

High-Temperature Solid Oxide Electrolyser System 

J. Stephen Herring (Primary Contact), James O'Brien, Carl Stoots, Paul Lessing and Ray Anderson 

Idaho National Engineering and Environmental Laboratory (INEEL) 

P. O. Box 1625 MS 3860 

Idaho Falls, Idaho 83415-3860 

Phone: (208) 526-9497; Fax: (208) 526-2930; E-mail: sth@inel.gov 

DOE Technology Development Manager: Matthew Kauffman 

Phone: (202) 586-5824; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Subcontractor: Joseph Hartvigsen, S. Elangovan and Robert Lashway 

Ceramatec, Inc., Salt Lake City, Utah 

Objectives 

•	 Develop and test energy-efficient, regenerative, solid oxide electrolyser cells (SOECs) for hydrogen 

production from steam using a high temperature heat source 

- Reduce ohmic losses to improve energy efficiency 

- Increase SOEC durability and sealing with regard to thermal cycles 

- Minimize electrolyte thickness 

- Improve material durability in a hydrogen/oxygen/steam environment 

•	 Demonstrate cell performance and associated equipment operation in a flexible test loop 

•	 Optimize stack configuration for incorporation into a full-scale plant 

•	 Test integrated SOEC stacks operating in the electrolysis mode 

•	 Specify and test hydrogen-permeation-resistant materials for high-temperature heat exchangers 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• Q. Cost 	 

•	 R. System Efficiency 

•	 U. Electricity Costs 

•	 W. High Temperature Materials 

•	 X. Policy and Public Acceptance 

Approach 

•	 Develop solid oxide electrolyte, electrode, and catalyst materials optimized for high-temperature 

steam electrolysis 

•	 Develop a flexible test loop at INEEL for performance testing of single electrolysis cells and cell 

stacks and for hydrogen permeation testing 

•	 Test single solid oxide electrolysis cells for performance over a range of operating temperatures, gas 

compositions, and current densities both at Ceramatec and at INEEL 

- Initial testing will be performed on baseline cells, fabricated using existing Ceramatec solid oxide 

fuel cell (SOFC) technology (Yttria-stabilized zirconia electrolyte-supported cells) 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- Subsequent testing will be performed on cells developed with different electrolyte compositions, 

electrode-supported cells, various catalysts, etc. 

•	 Develop a high performance electrolysis stack configuration based on the results of the single-cell 

tests, including high-performance bi-polar plates 

•	 Perform electrolysis testing in realistic cell stacks over a range of operating conditions and system 

pressures 

•	 Perform high-temperature hydrogen permeation testing of candidate heat exchanger materials 

Accomplishments 

•	 Test loop designed, passed safety approvals and placed in operation January 21, 2003 

•	 Single "button" cells tested for performance in electrolysis and fuel cell modes at Ceramatec and at 

INEEL 

•	 Initial parameters incorporated in conceptual full-scale plant design 

•	 Planning for multi-cell stack testing begun 

•	 Numerical analysis by Argonne National Laboratory under way 

Future Directions 

•	 Evaluate alternative electrolytes and catalysts in single-cell testing 

•	 Develop multi-cell stacks and stack testing capability 

•	 Conduct test of multi-cell stacks 

•	 Analyze operation of cells and overall plant with numerical techniques 

Introduction 

Of the many methods proposed for hydrogen 

production, water-splitting is considered ideal 

because it avoids CO2 emissions. Two types of 

water-splitting technologies have been studied: 

thermochemical and electrolysis. Chemicalreaction-based water-splitting processes are hindered 

by the extremely corrosive process environment (for 

example, in the iodine-sulfur process, H2SO4 is 

produced and then dissociated at 850°C). 

Conventional low-temperature electrolysis of steam 

results in an unsatisfactory thermal efficiency. 

This work is an experimental research project 

being conducted via a collaboration between the 

INEEL and Ceramatec, Inc. of Salt Lake City, Utah, to 

test the high-temperature, electrolytic production of 

hydrogen from steam using a reversible, solid oxide 

cell. The research team is designing and testing solid 

oxide cells for operation in the electrolysis mode, and 

evaluating materials for the high-temperature heat 

exchanger, condenser, and other components 

necessary for producing hydrogen using a hightemperature process heat source plus electrical power. 

This high-temperature process heat and the electrical 

power requirement could be supplied simultaneously 

by a high-temperature nuclear reactor. Operation at 

high temperature reduces the electrical energy 

requirement for electrolysis and also increases the 

thermal efficiency of the power-generating cycle. The 

high-temperature electrolysis process will utilize heat 

from a specialized secondary loop carrying a steam/ 

hydrogen mixture. It is expected that with this 

combination of a high-temperature reactor and hightemperature electrolysis, the process will achieve a 

thermal conversion efficiency of 40 to 50% while 

avoiding the challenging chemistry and corrosion 

issues associated with the thermochemical processes. 

Planar solid oxide cell technology is being utilized 

because it has the best potential for high efficiency due 

to minimized voltage and current losses. INEEL and 

Ceramatec scientists have been developing planar 

solid oxide cell technology for the past 20 years. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Approach 

Solid oxide cells will be developed and tested for 

operation in the electrolysis mode. Initial testing will 

document the performance of single “button” cells, 

such as the cell shown in Figure 1. Subsequent testing 

will document the performance of multiple-cell stacks 

operating in the electrolysis mode. Testing will be 

performed both at Ceramatec and at INEEL. A logical 

progression is being followed in the test project. The 

first cells to be tested were single cells based on 

existing materials and fabrication technology 

developed at Ceramatec for production of solid oxide 

fuel cells. These cells use a relatively thick (~175 μm) 

electrolyte of yttria- or scandia-stabilized zirconia, 

with nickel-zirconia cermet anodes and strontiumdoped lanthanum manganite cathodes. Additional 

custom cells with lanthanum gallate electrolyte have 

been developed and tested. During the second phase 

of this project, multiple-cell stacks will be developed 

using the most promising materials identified through 

the single-cell testing. 

In order to carry out the initial phase of the test 

project at INEEL, a new test loop has been developed 

for testing of single solid oxide electrolysis cells. A 

photograph of the setup is shown in Figure 2. It will 

be modified later for testing of multiple-cell stacks. 

The test loop is designed for cell operation in the 

700-1000oC temperature range. The following 

parameters are measured and controlled during 

testing: cell temperature, anode-side gas flow rate 

and composition (Ar, H2, H2O), inlet and outlet 

dewpoint temperature, applied cell voltage ( ±0-1 V 

 FY 2003 Progress Report 

differential from open-cell voltage), cell current, 

area-specific resistance, and hydrogen production 

rate. This facility is more heavily instrumented (52 

channels of instrumentation) than the test facility 

used at Ceramatec for single-cell testing. 

The scope of corrosion / permeation work to be 

performed in the second and third years of this 

project will focus on testing of various candidate 

high-temperature heat exchanger materials over a 

wide range of temperatures and partial pressures. 

Effects of permeation barrier treatments such as 

calorizing, oxide layers, and/or coatings will also be 

assessed. Candidate materials include Inconel and 

Hastelloy alloys, as well as ceramics. Permeation 

test materials will be characterized before and after 

testing using Scanning Electron Microscopy and 

Auger Electron Spectroscopy. Rates of permeation 

will be measured using techniques such as hydrogen 

permeation current, ultrasonics, and direct 

measurement of hydrogen leakage by capture of 

escaping hydrogen (using a containment envelope 

and carrier gas) and subsequent on-line gas analysis. 

Results 

Initial testing has been performed using single 

electrolyte-supported (thick) button cells fabricated 

by Ceramatec. Results of several representative 

“button” cell tests are presented in Figures 3 – 6. 

Figure 3 shows the open-cell potential measured 

across the reference electrodes of a button cell during 

heat-up in the INEEL test furnace. The measured 

values are compared to a prediction obtained from 

the Nernst equation, which quantifies the ideal openFigure 1.	 Details of Solid-Oxide Button Cell Fabricated 

by Ceramatec (TC = thermocouple, YSZ = 

yttria-stabilized zirconia) 

Figure 2. High-Temperature Single-Cell Steam 

Electrolysis Test Setup at INEEL 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

circuit potential from thermodynamic principles as a 

function of cell temperature, gas composition, and 

system pressure. Agreement between the measured 

values and the predictions is excellent, instilling 

confidence in the experiment design. The INEEL 

test loop is instrumented with precision dewpoint 

sensors located upstream and downstream of the 

electrolysis cell, allowing for direct measurement of 

steam consumption or production in electrolysis or 

fuel-cell modes, respectively. Figure 4 provides a 

plot of dewpoint change as a function of electric 

current for a single-cell test performed at INEEL in 

both electrolysis and fuel-cell modes. The figure 

shows both the measurements and a prediction, 

revealing good agreement. Figure 5 displays the 

results of a direct current (DC) potential sweep test 

 FY 2003 Progress Report 

performed on a scandia-stabilized zirconiaelectrolyte cell at INEEL in which a power-supply 

voltage is applied to the cell in order to force 

operation over a range of voltages. The results 

shown in the figure demonstrate reversible operation 

between the fuel-cell and electrolysis modes of 

operation. The slope of the potential sweep is 

highest for large negative current densities where the 

effects of steam starvation begin to have an effect. A 

similar figure representing a DC potential sweep test 

performed at Ceramatec on a lanthanum gallateelectrolyte cell is presented in Figure 6. The figure 

Figure 3.	 Open-Cell Electrical Potential Measured 

Across a Button Cell as a Function of Cell 

Temperature During Heat-up 

Figure 4. Dew Point Change as a Function of Cell 

Electric Current, Measurements And Theory 

Figure 5.	 DC Potential Sweep Showing Reversible 

Operation of a Scandia-Stabilized Zirconia 

Button Cell Tested at INEEL in Both FuelCell and Electrolysis Modes at 850oC 

Figure 6.	 DC Potential Sweep Showing Reversible 

Operation of a Lanthanum-Gallate Button Cell 

Tested at Ceramatec in Both Fuel-Cell and 

Electrolysis Modes at 800oC (LSGM = 

lanthanum strontium gallium magnesium oxide) 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

again demonstrates reversible operation between the 

fuel-cell and electrolysis modes of operation. It also 

clearly demonstrates the effects of steam starvation 

in the electrolysis mode at low steam concentrations. 

This cell exhibited excellent performance with an 

area-specific resistance (ASR) of 0.57 Ω-cm2 

, 

indicating low ohmic losses. 

Initial results of these single-cell tests are very 

promising in terms of demonstrating high efficiency 

high-temperature steam electrolysis using solid oxide 

cells. Subsequent testing will be focused on testing 

cells fabricated from alternate materials optimized 

for the electrolysis application. Long-duration 

performance tests will also be performed. Stack 

configurations will be developed and tested. 

Conclusions 

•	 High-temperature steam electrolysis using a 

high-temperature heat source is a viable nearterm strategy for large-scale hydrogen 

production. 

 FY 2003 Progress Report 

•	 Solid oxide cells represent a logical choice for 

high-temperature steam electrolysis due to their 

high operating temperature and high efficiency. 

•	 INEEL and Ceramatec have initiated a research 

project that is showing promising initial results 

on the thermoelectric efficiency issues related to 

the high-temperature electrolysis process. 

FY 2003 Publications/Presentations 

1. O'Brien, J. E., Herring, J. S., Lessing, P. A., and 

Stoots, C. M., "High Temperature Steam 

Electrolysis from Advanced Nuclear Reactors 

Using Solid Oxide Fuel Cells," presented at the 

First International Conference on Fuel Cell 

Science, Engineering and Technology, Rochester, 

NY, April 21-23, 2003 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Thermocatalytic CO2-free Production of Hydrogen from Hydrocarbon Fuels 

Nazim Muradov (Primary Contact), Franklyn Smith 

Florida Solar Energy Center (FSEC) 

1679 Clearlake Road, Cocoa, Florida 32922 

Phone: (321) 638-1448; Fax: (321) 638-1010; E-mail: muradov@fsec.ucf.edu 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Objectives 

•	 Develop an economically viable process for centralized and distributed production of hydrogen from 

hydrocarbons with minimal CO2 emissions 

•	 Improve the catalytic activity of carbon catalysts and process sustainability 

•	 Increase the yield of high-value carbon products and reduce the cost of hydrogen production 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 D. Carbon Dioxide Emissions 

Approach 

•	 Produce hydrogen-rich gas via thermocatalytic decomposition of hydrocarbons utilizing a part of the 

carbon product as a catalyst for the process 

•	 Improve the catalyst activity and process efficiency by continuous activation of carbon particulates in 

presence of activating agents 

•	 Design, fabricate and test 3-kWth thermocatalytic reactor for CO/CO2-free production of hydrogenrich gas and a carbon product from hydrocarbon fuels 

Accomplishments 

•	 Demonstrated that the catalyst activity and the process sustainability could be improved by activation 

of carbon particulates in the presence of small amounts of steam and/or CO2 

•	 Determined the effect of impurities potentially present in commercial hydrocarbon feedstocks (e.g., 

H2S, N2, moisture, high hydrocarbons) on the process efficiency and the catalyst activity and stability 

•	 Demonstrated the efficient removal of small amounts of CO/CO2 and olefins from the hydrogen gas 

via catalytic hydrogenation processes 

•	 Designed, fabricated and tested 3-kWth thermocatalytic reactor using commercial hydrocarbon fuels 

(pipeline natural gas, commercial propane) 

•	 Conducted reactor modeling and scaling-up studies (in cooperation with industry) 

•	 Evaluated potential markets and new application areas for carbon products 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Optimize the performance of a pyrolytic reformer for distributed production of hydrogen gas with the 

CO and H2S content below 10 ppm using commercial hydrocarbon fuels 

•	 Increase the yield of high-value carbon products (>$0.3 per kg) and reduce the cost of hydrogen 

production (for distributed production applications) 

•	 Conduct system integration studies to increase power density of the pyrolytic reformer and reduce its 

capital cost 

Introduction 

Conventional hydrogen production processes 

(e.g., steam methane reforming) produce large 

amounts of CO2 emissions. One alternative to 

conventional processes is a single-step 

thermocatalytic decomposition (TCD) (or pyrolysis) 

of natural gas (NG) or other hydrocarbon fuels into 

hydrogen and carbon: 

CH4 → C + 2H2 ∆Ho= 75.6 kJ/mol (CH4) 

Due to the absence of oxidants (e.g., H2O and/or 

O2), no carbon oxides are formed during the process, 

thus obviating the need for water gas shift and CO2 

removal stages, which significantly simplifies the 

process. Pure carbon is produced as a valuable 

byproduct that can be marketed, thus reducing 

hydrogen production cost. The technical goals of 

this research effort are to (1) determine efficient 

carbon catalysts for methane decomposition process; 

(2) conduct process engineering development 

studies, including reactor modeling and scale-up; and 

(3) characterize carbon byproducts of the process and 

evaluate their market value. 

Approach 

The approach is based on TCD of hydrocarbon 

fuels over high surface area carbon catalysts. The 

important feature of the process is that the reaction is 

catalyzed by carbon particulates produced in the 

process (no external catalyst is required, except for 

the start-up operation). Carbon catalyst particles 

circulate between a reactor and a heater, both 

operating in a fluidized bed regime (similar to 

industrial fluid coking process). Carbon catalysts 

exhibit high temperature and sulfur resistance. Due 

to low endothermicity of the process, the overall CO2 

emissions from the process could be drastically 

reduced (compared to conventional processes). 

Results

 The effect of carbon catalyst activation (with 

small amounts of steam) on the rate of methane 

decomposition was determined. Figure 1 illustrates 

the effect of steam treatment of carbon catalyst on its 

catalytic activity toward methane decomposition. It 

is evident that the steam treatment of carbon particles 

resulted in a drastic increase in both catalyst surface 

area and methane decomposition rate. 

It was determined that the presence of small 

amounts of impurities (H2S/CH3SH, CO2, nitrogen 

and moisture) potentially present in industrial 

hydrocarbon fuels is not detrimental to the catalyst 

activity and process efficiency. These impurities 

may result in contamination of hydrogen with trace 

Figure 1.	 TCD of Methane over Carbon Catalyst in 

Cyclic Pyrolysis-Activation Process. 

Tpyr.=850o

, Tact.=900oC (x-axis shows 

pyrolysis time only) 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

amounts of CO and H2S that can be efficiently 

removed from hydrogen gas via catalytic 

methanation and ZnO scrubbing techniques. 

A 3-kWth thermocatalytic reactor for production 

of hydrogen-rich gas and carbon from industrialgrade feedstocks (pipeline NG and commercial 

propane) was fabricated and tested (Figure 2). The 

average concentration of hydrogen in the pyrolysis 

gas was 45-72 v.% (the balance, predominantly 

methane), depending on the feedstock and 

temperature. After methanation, CO/CO2 

concentrations in H2 dropped to <10 ppm level. 

The studies on modeling and scale-up of the 

fluidized bed reactor were conducted (in cooperation 

with Reaction Engineering International—REI). A 

three-phase model to describe bubbling fluidized bed 

reactor containing carbon particles was developed 

(Figure 3). The model predictions were in 

reasonable agreement with the experimental 

measurements. 

Collaborative efforts with industry (MER 

Corporation, Universal Oil Products—UOP) and 

national labs (Lawrence Livermore National 

Laboratory—LLNL) in evaluating markets and 

identifying potential application areas for carbon 

products were conducted. The market for carbon 

products was estimated at 4-5 million ton/year level 

with carbon selling price at approximately $300/ton. 

Conclusions 

It was demonstrated that the catalyst activity 

toward methane decomposition and process 

sustainability could be significantly improved via 

continuous activation of carbon catalysts in the 

presence of small amounts of steam (the activation 

occurs outside the pyrolyzer). The process was 

designed where carbon particulates circulate between 

a hydrocarbon pyrolyzer and a catalyst heater, both 

operating in fluidized bed regime (similar to 

industrial fluid coking process). The impurities 

(CO2, H2S/CH3SH, moisture) present in commercial 

hydrocarbon fuels are not detrimental to catalyst 

activity and process efficiency, and could be 

efficiently removed from hydrogen gas. A 3-kWth 

thermocatalytic reactor for CO/CO2-free production 

of hydrogen-rich gas was designed, fabricated and 

tested using pipeline NG and commercial propane as 

feedstocks. The market for carbon products was 

estimated at 4-5 million ton/year level with carbon 

selling price at approximately $300/ton. FSEC 

participated in several collaborative research efforts 

with industry, national labs and universities (MER 

Figure 3.	 Modeling of Three-Phase Bubbling Fluidized 

Bed Reactor Containing Carbon 

Particles 

Figure 2. Experimental Set-up with 3-kWth
 

Thermocatalytic Reactor
 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Corporation, REI, National Renewable Energy 

Laboratory, UOP, LLNL, Florida Institute of 

Technology). 

FY 2003 Publications/Presentations 

1. Muradov, N. “Emission-free Fuel Reformers for 

Mobile and Portable Fuel Cell Applications”, 

Journal of Power Sources, v.118, 1-2, 320-324 

(2003) 

2. Muradov, N. “On-site Production of Hydrogen 

from Hydrocarbon Fuels with Minimal 

Greenhouse Gas Emissions”, Symposium: 

Hydrogen Energy for 21st Century, Amer. Chem. 

Soc. Meeting, New Orleans, 2003 

3. Muradov, N. “Catalytic Conditioning of 

Sulfurous Hydrocarbon Fuels for Fuel Cell 

Applications”, Symposium: Fuel Clean-up 

Considerations for Fuel Cells, Amer. Chem. Soc. 

Meeting, New Orleans, 2003 

4. Muradov, N., T-Raissi, A. “Hydrogen Production 

via Catalytic Reformation of Low-quality 

Methane Containing Feedstocks”, HYPOTHESIS, 

Italy, 2003 

5. Muradov, N., Smith, F. “Thermocatalytic 

Hydrogen Production from Natural Gas with 

Drastically Reduced CO2 Emissions”, 

HYPOTHESIS, Italy, 2003 

 FY 2003 Progress Report 

6. Muradov, N. and Schwitter, A. “Formation of 

Conical Carbon Structures on Vapor-grown 

Carbon Filaments”, Nano Letters, v.2, 673 (2002) 

7. Muradov, N. “Low-emission Fuel Reformers for 

Fuel Cell Applications”, 14th World Hydrogen 

Energy Conference, Montreal, Canada, 2002 

8. Muradov, N. “Emission-free Fuel Reformers for 

Fuel Cell Applications”, Fuel Cells, Science and 

Technology 2002, Amsterdam, Netherlands, 2002 

9. Muradov, N. “Thermocatalytic CO2-free 

Production of Hydrogen from Hydrocarbon 

Fuels”, DOE Annual Hydrogen Prog. Rev. 

Meeting, Golden, 2002 

Special Recognitions & Awards/Patents 

Issued 

1. University of Central Florida Research Incentive 

Award, 2003 

2. Muradov, N. U.S. Patent Application No. 60/ 

194,828 “Thermocatalytic Process for CO2-free 

Production of Hydrogen and Carbon from 

Hydrocarbons” (2002) 

3. Linkous, C., Muradov, N. U.S. Patent No. 

6,572,829 B2 “Closed Cycle Photocatalytic 

Process for Decomposition of Hydrogen Sulfide 

to its Constituent Elements” (2003) 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Analysis of Solar Thermochemical Water-Splitting Cycles for Hydrogen 

Production 

Ali T-Raissi 

University of Central Florida 

Florida Solar Energy Center (FSEC) 

Cocoa, FL 32922-5703 

Phone: (321) 638-1446; Fax: (321) 638-1010; E-mail: ali@fsec.ucf.edu 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax:(202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Objectives 

•	 Analyze thermochemical water-splitting cycles (TCWSCs) suitable for solar interface from the 

viewpoint of thermodynamics, chemical process engineering, costs and their potential environmental 

impact. 

•	 Develop a more precise method for determining the thermal efficiency of TCWSCs. 

•	 Build chemical process engineering flowsheets for prospective solar-driven TCWSCs. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 V. High- and Ultra-High-Temperature Thermochemical Technology 

•	 W. High-Temperature Materials 

•	 Y. Solar Capital Cost 

Approach 

•	 Review all published papers, reports, patents, etc. in the past 25+ years that relate to thermochemical 

water-splitting cycles, in general, and solar driven cycles, in particular. 

•	 Use FactSageTM program to perform chemical equilibrium calculations. 

•	 Employ HYSYS/ASPEN Plus chemical process simulation (CPS) program for developing process 

flowsheet, process analyses and optimization. 

•	 Compare the performance characteristics and costs of the University of Tokyo-3 (UT-3) and sulfuriodine (S-I) TCWSCs. 

•	 Identify processes that especially benefit from the solar interface. 

•	 Use chemical process flowsheet analysis to identify new processes/cycles or modifications of the 

existing cycles that improve performance and facilitate better interface with solar heat source. 

Accomplishments 

•	 Examined cycle efficiency calculation methods and developed a technique based on chemical process 

simulation flowsheet (see list of publications). 

•	 Used HYSYS CPS to analyze the sulfuric acid decomposition process of a solar driven sulfur-iodine 

TCWSC. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Developed two new flowsheets for decomposing sulfuric acid in the solar based S-I cycle (see list of 

publications). 

•	 Completed flowsheet simulation of sulfuric acid purification and decomposition using HYSYS steadystate processor. 

•	 Evaluated kinetic models for sulfur trioxide decomposition using HYSYS simulation tool. 

•	 Performed thermodynamics analyses of the decomposition of sulfuric acid and sulfur trioxide at 

various temperatures and pressures (see list of publications). 

•	 Developed a new Sulfur-Ammonia (S-A) TCWSC based on sulfuric acid decomposition. 

Future Directions 

•	 Develop and optimize a completed flowsheet for the S-I cycle and precisely determine its thermal 

efficiency and costs. 

•	 Analyze purification process of aqueous hydroiodic acid (HI) solution. 

•	 Carry out Aspen Plus process flowsheet analysis of separation of HI and H2SO4 and investigate the 

possibility of a newer and simpler process scheme. 

•	 Perform thermodynamic calculations involving HI decomposition and the SO2 + I2 reaction. 

•	 Determine phase equilibrium involving HI and H2SO4. 

Introduction 

In the course of the past several decades, many 

thermochemical cycles have been devised for 

production of hydrogen from water. It has been 

shown that thermochemical water splitting cycles 

(TCWSCs) have potential to deliver overall system 

efficiencies in excess of 40%. Among the most 

studied TCWSCs are sulfur-halogen cycles. Figure 1 

depicts a simple schematic diagram of the sulfurhalogen TCWSCs. Presently there are two potential 

high temperature heat sources available for use with 

thermochemical processes. They are solar thermal 

concentrator and central receiver systems, and 

nuclear reactors (i.e. high temperature gas-cooled 

reactors, HTGR). The U.S. DOE, under the Nuclear 

Energy Research Initiative (NERI) Program, has 

funded several efforts aimed at hydrogen production 

using nuclear power. 

One major program is underway at General 

Atomics (GA) Corp., in collaboration with the 

University of Kentucky (UK) and Sandia National 

Laboratories (SNL), to assess the technoeconomics 

of H2 production using HTGR. GA/UK/SNL reports 

provided a starting point for this evaluation of 

thermochemical water-splitting cycles suitable for 

solar interface and capable of providing efficient and 

cost-effective means of H2 production from water. 

After analyzing more than 100 different 

thermochemical water splitting cycles, the GA/UK/ 

SNL study narrowed the prospective cycles to two; 

namely, the University of Tokyo’s UT-3 and GA's 

Sulfur-Iodine cycle. At FSEC, we have selected and 

analyzed, in detail, three thermochemical processes. 

They are 1) sulfur family cycles, especially GA's S-I 

cycle; 2) the UT-3 cycle; and 3) the SynMet process 

developed at the Paul Scherrer Institute (PSI), 

Switzerland. 

Approach 

Our approach was to develop detailed flowsheets 

of the candidate TCWSCs and processes. We have 

considered the following systems: 

i. Bunsen reaction involving iodine and thermal 

decomposition of HI. As depicted in Figure 1, in 

addition to the sulfuric acid decomposition step, the 

following reactions are employed: 

SO2 + I2 + 2H2O = 2HI(aq) + H2SO4 (aq) 

followed by thermal decomposition of 

hydroiodic acid: 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

2HI = H2 + I2 

This is the General Atomics process with the 

revised cycle having improved energetics and an 

overall efficiency of about 50%. A variation of this 

TCWSC is the so-called Bowman-Westinghouse 

cycle that employs a reaction involving bromine 

(instead of iodine) and electrolysis of hydrobromic 

acid (in lieu of thermal decomposition of HI). The 

electrolytic decomposition of HBr requires a cell 

voltage of about 0.80 V (for acid concentration of 75 

wt%). 

One problem with the Westinghouse cycle 

involves the pH effects during electrolysis of sulfur 

dioxide in aqueous solution. At low solution pH, 

sulfur forms instead of hydrogen. To avoid sulfur 

formation, one has to maintain a high solution pH 

that requires a reduction in acid concentration in the 

solution. Low acid flow rates translate into low 

hydrogen evolution rates. In summary, we note that 

the hydrogen production rate depends on the solution 

pH, while pH is dependent on sulfur dioxide 

concentration. To avoid sulfur formation, the 

electrolytic process has to maintain low acid 

concentration levels to keep pH levels high. This in 

turn leads to a decrease in H2 production rate. Low 

sulfuric acid concentration will also require a more 

intensive and costly acid separation and 

concentration step, reducing the efficiency of H2SO4 

decomposition to sulfur dioxide and oxygen (see 

Figure 1). The acid decomposition step consumes a 

major portion of the input energy to the cycle. 

ii.UT-3 thermochemical cycle. This 

thermochemical hydrogen production cycle has been 

developed by Kameyama and Yoshida (at the 

Figure 1. Schematic Diagram of Sulfur-Halogen Cycle 

(X= iodine or bromine) 

University of Tokyo). The UT-3 process is one of the 

most studied thermochemical hydrogen production 

cycles in the world. It should be noted that the UT-3 

process is being developed for coupling to nuclear 

power reactors. The reported cycle efficiency is in 

the range of 40 to 50%. The cycle involves the 

following four gas-solid reactions: 

CaBr2 (s) + H2O (g) = CaO (s) + 2HBr (g)(1170 K)(1) 

CaO (s) + Br2 (g) = CaBr2 (s) + 1⁄2 O2 (g)(700 K) (2) 

Fe3O4 (s) + 8HBr (g) = 3FeBr2 (s) + 4H2O (g) + Br2 (g)(130 K) (3) 

3FeBr2 (s) + 4H2O (g) = Fe3O4 (s) + 6HBr (g) + H2 (g)(810 K) (4) 

Reaction (1) has been the slowest step, 

kinetically, amongst the four reactions; thus, it is 

rate-limiting for the whole cycle. Since it is 

necessary that all of the reactions proceed at the same 

rate for continuous operation of the cycle, the slow 

rate of hydrolysis of calcium bromide adversely 

affects the whole process efficiency. Another 

undesirable feature of the UT-3 cycle is that it is a 

gas-solid type process consisting of a pair of 

hydrolysis (endothermic) and Br reduction 

(exothermic) reactions that occur in four series 

reactors. In order to conduct these processes as in 

fixed bed reactors, the gases must alternatively flow 

in opposite directions. In other words, a given 

reactor must run an endothermic reaction in one 

direction for about two hours and then an exothermic 

one in the opposite direction for the next two hours, 

and so forth. 

The UT-3 cycle has been investigated 

extensively for almost 25 years since it was first 

proposed in 1978. It has also been fully detailed in 

flowsheets, and many issues related to the reaction 

chemistry and kinetics of individual processes, as 

well as the process separation issues, have been 

studied in detail. The overall efficiency of the 

improved adiabatic UT-3 process has been reported 

as 40% to 50%. However, difficulties remain with 

UT-3 cycle requiring further improvements. 

Examples include 1) heat-transfer and temperature 

control - reactions 1 and 4 are hydrolytic reactions, 

which require energy input, while reactions 2 and 3 

are exothermic, requiring heat removal from the 

reactors; 2) steady-state operation - circulation time 

period for the UT-3 cycle has been reported to be two 

hours; 3) separation issues - to cool down exothermic 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

reactors and sweep the reaction products out of 

reaction zones, excess steam is needed; 4) packed 

reactor design; 5) process lifetime issues; etc. 

iii. Zn/ZnO process. This is the so-called "SynMet" 

process developed at PSI. The process combines 

ZnO-reduction and CH4-reforming within a solar 

reactor. It consists of a gas-particle vortex flow 

confined to a solar cavity receiver that is exposed to 

concentrated solar irradiation. A 5-kW reactor has 

been built at PSI and subjected to tests in a high-flux 

solar furnace. Natural gas is used as a reducing agent 

to process ZnO according to the following overall 

reaction: 

ZnO + CH4 = Zn + 2H2 + CO(5) 

The process reforms methane in the absence of 

catalysts and is being optimized to produce syngas 

especially suited for methanol synthesis, and coproduction of Zn and syngas avoids CO2 emissions 

in the traditional carbothermal reduction of ZnO. 

Even though the PSI process is the only system 

developed for direct solar interface, it is not, 

however, a typical TCWSC, per se. 

Results 

In order to mitigate problems discussed above, a 

new sulfur-ammonia cycle has been conceived that is 

a better fit to solar power source and does not suffer 

from acid solubility issues. A schematic diagram of 

the cycle is depicted in Figure 2. A flowsheet of the 

cycle is given in Figure 3. Ammonium sulfite is fed 

to a photocatalytic reactor, where sulfite ions are 

oxidized into sulfate ions while water is reduced to 

H2. Ammonium sulfate is then decomposed into 

Figure 2. Schematic Diagram of Sulfur-Ammonia Cycle 

 FY 2003 Progress Report 

ammonia gas and, at the same time, water also boils 

off. Through the decomposer, liquid sulfuric acid is 

introduced into the acid vaporizer to generate 

gaseous sulfur trioxide and water. The product 

sulfuric trioxide is then reduced to produce sulfur 

dioxide gas and oxygen in a reduction reactor. Small 

amounts of sulfuric acid remaining can be separated 

from the gaseous mixture containing sulfur dioxide, 

oxygen and water with an acid separator. Sulfuric 

acid so separated is then recycled, and sulfur dioxide 

and oxygen are mixed with ammonia and chemically 

adsorbed to produce ammonium sulfite, which is 

then fed into the photocatalytic reactor to begin a 

new cycle. 

In the adsorption unit, oxygen is separated from 

the stream. The chemical reactions involved in the 

proposed sulfur-ammonia cycle are: 

(NH4)2SO3(a) +H2OÆ (NH4)2SO4(a)+H2(g) 80oC 

(photocatalytic step)(6) 

(NH4)2SO4(a) Æ 2NH3(g) + H2SO4(l) 350oC 

(thermochemical step)(7)
 

H2SO4(l) Æ SO3(g) + H2O(g)400oC 

(thermochemical step)(8)
 

SO3(g)Æ SO2(g) + 1/2O2(g)850oC 

(thermochemical step)(9)
 

SO2(g)+2NH3(g) + H2O Æ (NH4)2SO3(a) 25oC 

(chemical adsorption)(10) 

Figure 3. Process Flowsheet for the Proposed SulfurAmmonia Cycle 

4 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Among these reactions, Reactions (6), (7) and 

(10) are unique to this new cycle. Reactions (8) and 

(9) are common to all sulfur family cycles. 

If reaction (6) is carried out at a temperature of 80 

~ 90o

C, the concentration of ammonium sulfate is 

about 50 wt% (assuming complete conversion of 

sulfite to sulfate ions). This concentration is six times 

higher than in the Bowman-Westinghouse cycle. 

Since pH in ammonium sulfate or ammonium sulfite 

solutions is higher than that of pure sulfuric acid or 

sulfurous acid at the same concentration of anions, 

sulfite ion oxidation can be conducted in a higher 

concentration solution without elemental sulfur 

repercussion. Furthermore, higher sulfuric acid 

concentration will ease acid separation and 

concentration as well as improve process energetics. 

Moreover, increased acid concentration will increase 

the sulfite ion oxidation rate. Interestingly, the 

solubilities of sulfite and sulfate ions are comparable 

at 30o

C. However, at temperatures higher than 30oC, 

ammonium sulfite has higher solubility in water than 

ammonium sulfate. If reaction (6) is operated at 80o

C, 

the concentration of sulfite ions becomes higher than 

sulfate ions, thus increasing the oxidation rate. 

The energy required to separate the products of 

reaction (7), i.e. ammonia and sulfuric acid, can be 

provided by reaction (10), so there is no net energy 

input. This is not, however, the case with the S-I 

cycle that requires energy input for HI 

decomposition. The S-A cycle is well suited to solar 

input as a heat source and ultraviolet (UV) light. The 

UV part of solar spectrum is of great value for the 

photolytic and/or photocatalytic redox reactions. In 

the photocatalytic reactor, sulfite ions are oxidized to 

sulfate ions while hydrogen is generated. The 

photoreactor consists of two segments. The first 

layer adsorbs UV light, promoting a redox reaction. 

Because neither sulfite nor sulfate can adsorb visible 

light, a second under-layer can be used to adsorb 

concentrated long wavelength light, heating and 

decomposing sulfur trioxide to sulfur dioxide. 

Conclusions 

TCWSCs employing solar energy as a heat 

source can be attractive due to their relatively higher 

efficiency. The UT-3 cycle is a pure thermochemical 

process that has been under investigation for close to 

25 years. Bowman-Westinghouse sulfur is a hybrid 

cycle in which an electrolytic process and a thermal 

decomposition of sulfuric acid are combined to coproduce hydrogen and oxygen. The main drawback 

of the Bowman-Westinghouse cycle is that the 

electrolysis step requires low concentration of 

sulfuric acid, leading to higher energy consumption 

in the acid concentration and separation process. A 

new sulfur-ammonia thermochemical cycle was 

proposed for decomposing water into hydrogen and 

oxygen. The cycle consists of three steps: 1) 

photocatalytic oxidation of ammonium sulfite to 

generate ammonium sulfate while water is reduced to 

hydrogen utilizing both thermal and UV portion of 

the solar spectrum; 2) ammonium sulfate 

decomposition into ammonia and sulfuric acid, with 

the latter undergoing the same reduction process as 

that in the Bowman-Westinghouse sulfur cycle; and 

3) chemical co-adsorption of ammonia and sulfur 

dioxide to produce ammonium sulfite, which is then 

recycled to produce H2 and ammonium sulfate. 

The new cycle has the potential for achieving 

high overall efficiency by using readily available and 

inexpensive chemicals. Solar energy is used as a 

heat source, and UV portion is utilized for a 

photocatalytic redox reaction. Prior experimental 

results obtained at FSEC indicate that photolytic and/ 

or photocatalytic oxidation of sulfite ions occurs at 

acceptable rates with no occurrence of side reactions. 

FY 2003 Publications/Presentations 

1. Muradov, N.Z. and A. T-Raissi, "Hydrogen 

Production via Catalytic Reformation of 

Unconventional Methane Containing Feedstocks," 

Paper submitted for presentation and publication 

at the HYPOTHESIS Symposium held in Porto 

Conte, Italy, September 7-10, 2003. 

2. T-Raissi, A. "Photocatalytic Oxidation of Terpenic 

VOCs," Invited paper submitted for presentation 

at the 2nd AOP (II EPOA) International 

Conference held at Campinas, Brazil, August 25-

27, 2003. 

3. T-Raissi, A. " Hydrogen Storage in Ammonia and 

Aminoborane Complexes," Presentation at the 

2003 Hydrogen Program Annual Review, 

Berkeley, CA , May 21, 2003. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

4. T-Raissi, A. "System Analysis of H2 Production 

and Utilization at KSC," Presentation at the 

NASA Hydrogen Review Meeting at Tampa, FL, 

January 15, 2003. 

5. T-Raissi, A. "Analysis of Alternate Hydrogen 

Production Processes," Presentation at the NASA 

Hydrogen Review Meeting at Tampa, FL, January 

15, 2003. 

6. T-Raissi, A. "Hydrogen Storage in Amine Borane 

Complexes," Presentation at the NASA Hydrogen 

Review Meeting at Tampa, FL, January 15, 2003. 

7. T-Raissi, A. and C. Huang, "Technical Analysis of 

Hydrogen Production," A semi-annual contract 

report to U.S. DOE under DEFC3600GO10603, 

February 2003. 

8. T-Raissi, A., et al. "Task IV-2, System Analysis of 

Hydrogen Production and Utilization at KSC," 

Interim contract report on NASA NAG3-2751, 

January 2003. 

9. Huang, C. and A. T-Raissi, "Task IV-6, Analysis 

of Alternative Hydrogen Production Processes," 

Interim contract report on NASA NAG3-2751, 

January 2003. 

10.T-Raissi, A., et al. "Task III-3, Hydrogen Storage 

in Amine Borane Complexes, Part II - Molecular 

Modeling of Hydrogenation of Borazine to 

Cyclotriborazane," Interim contract report on 

NASA NAG3-2751, January 2003. 

 FY 2003 Progress Report 

11.T-Raissi, A. "Cryogenics Tasks, NASA KSC 

Update and System Analysis, and Analysis of 

Alternate Hydrogen Production Processes," 

Presentation at the NASA-GRC Program Review 

Meeting, Cleveland, OH, September 3-4, 2002. 

12.T-Raissi, A. "Chemical Storage - Overview," 

Keynote speech at the DOE Hydrogen Storage 

Workshop, Argonne National Laboratory, 

Argonne, IL, August 14, 2002. 

13.T-Raissi, A. "System Analysis of H2 Production 

Concepts - Overall System Analysis," 

Presentation at the NASA-Hydrogen Research at 

Florida Universities Program Review Meeting 

held at FSEC, July 16-17, 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. T-Raissi, A., et al. "Apparatus for decoupled 

thermo-photocatalytic pollution control," U.S. 

Patent No. 6,551,561, April 22, 2003. 

2. T-Raissi, A., et al. "Apparatus and method for low 

flux photocatalytic pollution control," U.S. Patent 

No. 6,531,035, March 11, 2003. 

3. Recipient of 2002-03 I&C Award for Excellence 

in Research, UCF. 

4. Director of the FSEC's Hydrogen R&D Division 

as of August 31, 2002. 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Composite Tank Project 

Neel Sirosh (Primary Contact), Ray Corbin, Alan Niedzwiecki 

Quantum Fuel System Technologies Worldwide Inc. 

17872 Cartwright Road 

Irvine, CA 92614 

Phone: (949) 399-4698; Fax: (949) 399-4600; E-mail: nsirosh@qtww.com 

DOE Technology Development Manager: Tony Bouza 

Phone: (202) 586-4563; Fax: (202) 586-9811; E-mail: Antonio.Bouza@ee.doe.gov 

Objectives 

•	 Develop and validate 5,000 psi storage tanks - tank efficiency: 7.5 - 8.5 wt% 

•	 Validate 5,000 psi in-tank pressure regulators - system efficiency: 5.7 wt% 

•	 Develop and validate 10,000 psi storage tanks - tank efficiency: 6 - 6.5 wt% 

•	 Develop and validate 10,000 psi storage systems - system efficiency: 4.5 wt% 

•	 Optimize designs and processes to achieve the DOE cost targets 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

• A. Cost 	 

•	 B. Weight and Volume 

•	 D. Durability 

•	 E. Refueling Time 

•	 H. Sufficient Fuel Storage for Acceptable Vehicle Range 

•	 K. Balance-of-Plant (BOP) Components 

Approach 

•	 Learn from the successful 100-year history of pressure vessels (industrial, aerospace, CNG) 

•	 Optimize materials, design, and process to improve weight efficiency (5,000 psi tanks) 

•	 Develop & validate volumetrically efficient storage systems (10,000 psi tanks) 

•	 Improve system efficiency (in-tank regulator, balance-of-plant components) 

•	 Validate and certify components (codes & standards, regulatory approvals) 

•	 Work towards cost reduction (technology, economies of scale) 

Accomplishments 

•	 Designed industry's first hydrogen 10,000 psi (700 bar) tanks 

•	 Successfully completed validation per European Integrated Hydrogen Project (E.I.H.P.) (Draft 7) and

obtained certification (TÜV German Pressure Vessel Code DBV P.18) 

•	 Designed and developed industry's first hydrogen 10,000 psi (700 bar) in-tank pressure regulation 

system, pressure relief device, manual valve and other balance-of-plant components 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Delivered fully-validated 10,000 psi hydrogen storage systems for automotive original equipment 

manufacturer (OEM) use 

•	 Demonstrated fast refueling at the rate of 1 kg/minute 

Future Directions 

•	 Perform further structural optimization of 10,000 psi tanks in view of improving gravimetric and 

volumetric efficiencies 

•	 Evaluate lower cost materials to reduce cost 

•	 Evaluate the application of integrated sensors for in-situ structural monitoring 

•	 Evaluate other means of improving volumetric efficiency 

Introduction	 Approach 

Possible approaches to hydrogen storage include 

compression, liquefaction, chemical storage, metal 

hydrides, and adsorption. Although each storage 

method has desirable attributes, no approach 

currently satisfies all the efficiency, size, weight, 

cost, durability and safety requirements for 

transportation use. Research continues in these 

areas, with progress being made in all approaches. 

Improvements in the energy densities of hydrogen 

storage systems, reductions in cost, and increased 

compatibility with available and forecasted systems 

are required before viable hydrogen energy use will 

be realized. 

The objective of this hydrogen composite tank 

project was to design, develop, validate, fabricate, 

and manufacture hydrogen fuel tanks and in-tank 

regulators along with vehicle integration brackets 

and isolators and have them delivered to Virginia 

Tech University and Texas Tech University in 

support of the Future Truck competition. The 5,000 

and 10,000 psi systems developed in this project 

provide an attractive near-term and possibly 

medium-term solution for hydrogen storage. The 

currently validated QUANTUM "TriShield" tank 

technology meets the usable specific energy, usable 

energy density, cycle life, refueling rate and limit of 

loss of hydrogen targets of the DOE for 2005 and 

approaches the targets for 2010. While cost 

remains challenging, significant cost reductions are 

possible with further optimization coupled with 

economies of scale. 

The QUANTUM advanced composite tank 

technology incorporates a "TriShieldTM" design 

philosophy. The QUANTUM Type IV TriShieldTM 

cylinder, as illustrated in Figure 1, is comprised of a 

seamless, one piece, permeation resistant, crosslinked, ultra-high molecular weight polymer liner 

that is over wrapped with multiple layers of carbon 

fiber/epoxy laminate and a proprietary external 

protective layer for impact resistance. TriShieldTM 

hydrogen tanks feature a single-boss opening to 

minimize leak paths. The path to achieving high 

gravimetric efficiency is optimization in materials, 

design and processes. 

The TriShieldTM hydrogen tank is designed to 

accommodate QUANTUM's patented in-tank 

regulator, which confines high gas pressures within 

Figure 1. QUANTUM Compressed Hydrogen Storage 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

the tank and, thus, eliminates high-pressure fuel lines volumetric advantages without significant energy 

downstream of the fuel storage subsystem. The penalty (see Figure 4). 

system cost can be significantly reduced by 

combining a check valve to assist tank filling, fuel 

filtering, fuel tank pressure and temperature 

monitoring, pressure relief device and tank lock-off 

in the regulation module. Figure 2 shows a complete 

storage system including storage tanks and balanceof-plant components. 

Results 

The 5,000 and 10,000-psi tanks developed by 

QUANTUM Technologies have been validated to 

meet the requirements of DOT FMVSS304, NGV2­

2000 (both modified for hydrogen) and draft E.I.H.P 

standard. To ensure safety and reliability in an 

automotive service environment, a number of 

performance tests have been completed: Burst Tests 

(2.35 safety margin), Fatigue (45,000 pressure cycles 

at ambient temperature), Extreme Temperature, 

Hydrogen Cycling, Bonfire, Severe Drop Impact 

Test, Flaw Tolerance, Acid Environment, Gunfire 

Penetration, Accelerated Stress, Permeation and 

Material Tests. The developed "in-tank regulators" 

meet the requirements of NGV3.1 and E.I.H.P. 

Figure 3 shows the relevance of various 

components to system-level efficiencies at 5,000 and 

10,000 psi storage pressure. It is clear that 

optimization of the balance-of-plant components is 

critical to achieve system-level gravimetric 

efficiency, especially when multiple tanks are 

utilized. Storage at 10,000 psi provides important 

Table 1 shows the DOE FreedomCAR targets 

for 2005 and 2010, in relation to the current status 

of 10,000 psi storage. It can be seen that the biggest 

challenge is cost, which needs to be reduced by a 

factor of 20. It is anticipated that cost reduction 

will include optimization through technology (50 to 

75% reduction), followed by economies of scale 

(factor of 10). 

Figure 3. System-Level Weight Efficiency 

Figure 2. Compressed Hydrogen Storage System 

Figure 4.	 Volumetric Efficiency: 5,000 psi vs 10,000 

psi Storage 

Table 1. DOE FreedomCAR Targets vs. Status 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Conclusions 

•	 The 5,000 psi and 10,000 psi compressed 

hydrogen storage systems developed and 

validated in this project provide a convenient 

near-term solution, and are currently available 

and successfully deployed on fuel cell vehicles. 

•	 DOE 2005 performance targets are achievable. 

•	 Storage is a significant cost factor in overall fuel 

cell system cost. 

•	 Carbon fiber and stainless steel hardware costs 

represent over 90% of the costs. 

•	 Design and process improvements to address 

storage tank costs are on-going. 

FY 2003 Publications/Presentations 

1. Andris R. Abele, "Advanced Hydrogen Storage 

Systems", Hydrogen and Fuel Cells 2003 

Conference and Trade Show, Vancouver (June 

2003). 

2. Brian Jenkins, "Advanced Hydrogen Fuel 

Systems for Fuel Cell Vehicles", 1st International 

Conference on Fuel Cell Science & Energy 

Technology (April 2003). 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Compressed Hydrogen Gas Integrated Storage System 

(CH2-ISS) for Fuel Cell Vehicles 

Mr. John Wozniak 

Johns Hopkins University Applied Physics Laboratory 

11100 Johns Hopkins Road 

Laurel, Maryland 20723-6099 

Phone: (240) 228-5744; Fax: (240) 228-5512; E-mail: john.wozniak@jhuapl.edu 

DOE Technology Development Manager: Tony Bouza 

Phone: (202) 586-4563; Fax: (202) 586-9811; E-mail: Antonio.Bouza@ee.doe.gov 

Subcontractor: General Dynamics Armament & Technical Products (GDATP), Lincoln, Nebraska 

Objectives 

Advance the technology elements required to develop a semi-conformal, Compressed Hydrogen Gas 

Integrated Storage System (CH2-ISS) for light-duty fuel cell electric vehicles (FCEV) by conducting 

engineering research as follows: 

•	 Develop materials and treatments to reduce hydrogen gas permeation through tank liners 

•	 Develop an optimized carbon fiber/epoxy resin tank overwrap to support storage tank design with 

improved gravimetric energy density construction 

•	 Determine alternative methods and materials for manufacture of the integrated storage system 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 	 

•	 B. Weight and Volume 

•	 H. Sufficient Fuel Storage for Acceptable Vehicle Range 

• I. Materials 	 

•	 K. Balance-of-Plant (BOP) Components 

Approach 

•	 Develop baseline CH2-ISS design consistent with packaging and driving range requirements 

•	 Develop tank liner materials and surface treatments and measure hydrogen gas permeation 

•	 Build and performance test all-carbon overwrap tanks with alternative toughened epoxy resin 

formulations 

•	 Evaluate alternative materials and designs for production of the ISS shell and unitary gas control module 

•	 Develop CH2-ISS vehicle packing interface design for notional FCEV applications 

Accomplishments 

•	 Continued evaluation of low permeation tank liner materials and developed a test unit for accurately 

measuring gas permeation 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Continued work on improving tank gravimetric energy density through development of toughened 

epoxy resins 

•	 Continued evaluation of alternative materials for constructing the CH2-ISS outer shell; purchased 

material coupons and developed preliminary design of test fixture 

•	 Continued work on the unitary gas control module (UGCM); downselected one of two alternative 

designs for prototype development 

•	 Initiated storage system-vehicle interface technology task; developed idea of storage-to-vehicle 

attachment system (Crash Management System) that both preserves vehicle "crumple zone" while 

reducing impact load to the storage unit; established CH2-ISS size and operating pressure to support 

FCEV with 300+ mile driving range 

Future Directions 

•	 Build and evaluate performance of storage tanks with improved gravimetric energy density 

•	 Conduct flammability and impact tests on alternative CH2-ISS outer shell materials; select optimum 

•	 Design, build, test and evaluate unitary gas control system 

•	 Design the CH2-ISS with sufficient fuel storage for 300+ mile driving range 

•	 Detail storage-to-vehicle interface Crash Management System design 

Introduction 

The storage of compressed hydrogen gas (CH2) 

poses challenges in the areas of relatively low energy 

density, system cost, crashworthiness, and vehicle 

packaging. A solution to these challenges is offered 

by the Integrated Storage System (ISS) technology 

(U.S. Patent No. 6,257,360 issued July 2001) jointly 

developed by Johns Hopkins University Applied 

Physics Laboratory (JHU/APL) and General 

Dynamic Armaments and Technical Products 

(GDATP) (formerly Lincoln Composites). Under 

DOE Cooperative Agreement DE-FC36-01G011003, 

the ISS technology is being advanced to support 

development of a 5,000 and/or 10,000 psi service 

pressure semi-conformal gas storage system that 

provides sufficient fuel storage for 300+ mile driving 

range without impacting passenger and cargo space 

or compromising vehicle safety, and that is able to be 

mass produced at DOE target storage cost. 

Approach 

ISS uses Type IV all-composite tanks 

constructed with a high-density polyethylene 

(HDPE) thermoplastic liner structurally overwrapped 

with carbon fiber and epoxy resin. The tanks are 

encapsulated within a high-strength outer shell 

unitizing the individual cylinders into a single 

container and providing protection from 

environmental exposure. Additional physical 

protection of the tanks is provided by urethane foam 

surrounding the tank dome region (location of 

highest stress concentration during impact). A 

unitized gas control module (UGCM) is incorporated 

into the ISS package and provides all necessary gas 

flow control and safety features. Figure 1 is a 

Figure 1. Assembly View of the CH2-ISS 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

computer-aided design (CAD) image of the CH2-ISS 

design. The objective of the DOE Cooperative 

Agreement is to advance the technologies needed to 

support developing and safety certifying a CH2-ISS. 

There are five specific tasks: (1) HDPE treatment 

and alternative tank liner materials for hydrogen gas 

permeation reduction; (2) epoxy resin toughness 

enhancement to improve tank gravimetric energy 

density; (3) materials and process evaluation for 

manufacturing the ISS protective shell; (4) 

engineering of an optimized unitary gas control 

module; and (5) development of vehicle interface 

technologies to support storage system packaging 

requirements and system crashworthiness objectives. 

Within the timeframe covered in this report, JHU/ 

APL had only received 35% of DOE committed FY 

2003 funding. The progress reported herein 

therefore represents only approximately 35% of the 

plan activities. As a result of the delayed 

commitment of funds, the completion date for FY 

2003 tasks was negotiated to March 31, 2004. 

Results 

Task (1): ISS uses Type IV high-pressure gas 

storage tanks constructed with a thermoplastic liner 

overwrapped with carbon fiber and epoxy resin. The 

liner serves as a permeation barrier, mechanical 

interface to aluminum bosses, and a stable mandrel 

for the filament winding process. The main focus of 

the permeation task has been to quantify and control 

the hydrogen gas permeation rate through the 

thermoplastic liner. In addition, two alternative 

secondary seal designs at the plastic liner/metal boss 

interface were explored. To accurately measure gas 

permeation, GDATP developed a test unit. This unit 

utilizes a hydrogen mass spectrometer in 

combination with a 2500 L vacuum chamber. A 

mass spectrometer as the instrument of measurement 

provides real-time data acquisition and evaluation. 

Permeation testing to date has been performed using 

a non-flammable 5% H2 / 95% N2 (by volume) gas 

composition. A proprietary surface treatment on the 

existing HDPE (High Density Polyethylene) lined 

tanks reduced permeation by 80% compared to the 

untreated HDPE. Two alternative proprietary liner 

materials were also tested, and they showed a 90% 

reduction in the permeation rate over untreated 

HDPE. More materials have been prepared but had 

not been tested at the time of this report. 

 FY 2003 Progress Report 

Task (2): Decreasing tank weight (to improve 

gravimetric density) and reducing tank fabrication cost 

are key technology advancement goals. In FY 2002, 

GDATP established that increasing epoxy resin 

toughness with toughening agents formulated into 

GDATP's standard resin led to successful gunfire test 

for an all-carbon fiber overwrap at a 2.25 factor of 

safety (FOS) design. However, the specific 

toughening agents tested also modified the resin by 

lowering its glass transition temperature (impacting 

tank service temperature) and increasing its viscosity 

(impacting the tank winding process). Despite these 

shortcomings, the work was very encouraging and led 

to the hypothesis that if the right additive(s) was 

found, tanks could be manufactured without any loss 

in performance or higher fabrication cost. In addition, 

further tank weight reduction might be achieved if 

built with a factor of safety less than the regulatory 

2.25 minimum. Current federal and international 

standards for Type IV tanks dictate the minimum 

allowable factor of safety 2.25. The minimum FOS 

was derived by industry and the government for 

natural gas vehicle tanks and accounts for material and 

manufacturing variations and physical/environmental 

abuse tolerance. In the ISS application, the tanks are 

fully protected by an unstressed outer shell and impact 

protection foam; consequently, the 2.25 FOS may not 

be needed to field a fully safe system. To explore this, 

we are embarking on a systematic examination of 

modern epoxy resin toughening agents and screening 

them for their effect on toughness, tank service 

temperature, the tank winding process, cost and other 

factors. During this reporting period, plans have been 

developed to have Dr. Giuseppe Palmese at Drexel 

University perform the resin screening study. There 

was insufficient DOE funding, in the timeframe 

covered by this report, to initiate the resin study. 

Task (3): The ISS uses a high-strength, 

lightweight shell/cover in conjunction with flexible 

urethane impact-absorbing foam to encapsulate and 

protect the individual tanks into a single unitized 

container. In FY 2002, a manufacturing study was 

performed addressing alternative means for 

constructing, at low-cost and in high volume, the 

CH2-ISS outer shell and protective cover. The study 

identified a number of candidate materials and 

manufacturing processes used for high volume 

automotive reinforced plastic parts. These included 

compression molding with sheet molding compound 

3 
 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

(SMC), structural reaction injection molding 

(SRIM), injection molding, and resin transfer 

molding (RTM). Both SMC and SRIM were 

determined to be good candidates. There remained, 

however, issues of part strength in the required 

bonfire test and impact strength for the drop test, that 

needed to be fully answered before making the final 

selection. To that end, material coupon tests are 

planned, and representative SMC and SRIM coupons 

were purchased. A special coupon test fixture is 

being devised that incorporates a load applied to the 

shell coupons under the conditions of the bonfire test 

simulated with heat lamps. Load bearing capability 

and qualitative condition of the coupons will be used 

to assess the results of the test for each sample. 

There was insufficient DOE funding, in the 

timeframe covered by this report, to initiate the test 

panel testing. 

Task (4): The CH2-ISS is treated as a single, 

inseparable container, requiring only one manual 

service valve, one solenoid, and one thermally 

activated pressure relief device (PRD), all 

incorporated into a unitary gas control module 

(UGCM). The added cost and complexity of 

redundant components when using multiple 

separable tanks in a vehicle installation is avoided by 

this approach. The gas control system is safeguarded 

from physical damage with impact absorbing foam 

within a high-strength protective cover. In FY 2002, 

two alternative UGCM notional designs were 

developed with differing approaches to transferring 

heat, from a potential under-vehicle fire, to the 

thermally activated PRD. In FY 2003, work 

continued with particular focus on system 

crashworthiness, and the heat pipe option of heat 

transfer was selected as the safest design. For added 

safety, the UGCM design was refined to eliminate 

hard-mounting to a tank for added crashworthiness 

isolation. A non-disclosure agreement was 

established between JHU/APL and Circle Seal Inc. to 

allow interface information to be shared for 

commercial off-the-shelf component integration into 

the UGCM. There was insufficient funding available 

over the timeframe covered by this report to start 

work on finalizing the UGCM design and building a 

prototype unit for service, safety and reliability 

testing. 

Task (5): With the need to develop FCEVs with 

driving ranges comparable to today's ICE (internal 

 FY 2003 Progress Report 

combustion engine) vehicles, work began on a vehicle 

interface technology task to explore options to 

increase hydrogen capacity at practical temperatures 

and pressures without compromising cargo and 

passenger space. The focus of this work has been a 

point design on a class of light-duty vehicles (i.e., carbased sport utility vehicles) to increase space in the 

vehicle under chassis to house a larger capacity CH2-

ISS unit, without impacting passenger or cargo 

volume or reducing ground clearance, all while 

notionally meeting vehicle crashworthiness goals. 

The point design study led to the idea of a breakaway, 

four-bar linkage Crash Management System (CMS) to 

secure the CH2-ISS and to tip and guide the unit into 

the under carriage in the event of a high-speed rear end 

collision. This is done to preserve the all-important 

vehicle "crumple zone," thus protecting the 

passengers, and to control the impact energy imparted 

to the CH2-ISS to reduce the likelihood of physical 

damage. A patent disclosure for the CMS concept was 

developed and filed. A scaling analysis was 

performed that included the parameters of storage unit 

size and service pressure. The analysis showed that 

the 300+ mile driving range goal is possible with a 

properly sized and packaged CH2-ISS unit while 

meeting all other vehicle utility and safety objectives. 

Conclusions 

Some progress has been made in developing a 

high energy density, near-rectangular, safety-certified 

and affordable container for the onboard storage of 

compressed hydrogen gas for use in fuel cell electric 

vehicles. The work has focused on hydrogen tank 

gravimetric energy density improvement and 

permeation reduction, refining the design of a unitary 

gas control module and exploring means of achieving 

driving ranges comparable to today's vehicles 

without compromising vehicle utility or safety. Due 

to the slow dispersion of DOE funding, the FY 2003 

planned work will not be completed until the revised 

phase completion date of March 31, 2004. 

FY 2003 Publications/Presentations 

1. "Development of a Compressed Hydrogen Gas 

Integrated Storage System (CH2-ISS) for Fuel 

Cell Vehicles - Peer Review Presentation CD/ 

ROM Report", May 20, 2003 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Next Generation Hydrogen Storage 

Andrew Weisberg 

Lawrence Livermore National Laboratory 

P.O. Box 808, L-270 

Livermore, CA 94551 

Phone: (925) 422-7293; Fax: (925) 424-3731; E-mail: weisberg1@llnl.gov 

DOE Technology Development Manager: Tony Bouza 

Phone: (202) 586-4563; Fax: (202) 586-9811; E-mail: Antonio.Bouza@ee.doe.gov 

Objectives 

• Adapt derivative technology from today's tanks to reduce cost by ~50% 

• Improve performance of tanks by incorporating new high-strength materials 

• Improve useable density of physical hydrogen storage through conformability 

• Develop fundamental understanding of structural storage in various geometries 

• Demonstrate safety innovations as components in ongoing burst experiments 

• Contribute expertise to regulatory processes reflecting the results of research 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 

• B. Weight and Volume 

• F. Codes and Standards 

• H. Sufficient Fuel Storage for Acceptable Vehicle Range 

• J. Lack of Tank Performance Data 

Approach 

• Gain theoretic understanding of models that combine mass, volume, and cost 

• Conduct scholastic research in University libraries seeking ultra-strong materials 

• Construct test equipment capable of safely burst testing small prototypes 

• Develop mechanical interface that enables assembled (not wound) tanks 

• Adopt Statistical Process Control and Statistical Qualification analyses 

• Collect suitable data to enable statistical engineering of burst probabilities 

Accomplishments 

• Established fundamental new dimensionless formalism that combines mass, volume, and cost 

• Performed first statistical qualification on pressure vessel structural component 

• Adopted Weibull statistical distribution identification method to tank failure 

• Discovered new geometries capable of carrying structure loads through replicates 

• Explored new structural geometries ideal for mass production with composites 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Prototype new structural geometries ideal for mass production with composites 

• Extend statistical methods to burst testing of small pressure vessel prototypes 

• Match dimensionless theory to actual burst performance of replicated structures 

• Acquire data on the unexplored tensor debonding waves in "turn to dust" bursts 

• Learn to engineer tailored elasticity and self-destruction for better crash safety 

Introduction 

Physical containment of hydrogen has been 

accomplished successfully by tanks for the past few 

decades. Compressed hydrogen gas at ambient 

temperature as a means of storing hydrogen is 

already available and getting better. So compressed 

hydrogen storage provides a near-term solution based 

on already-solved problems, with well understood 

limitations. Current and next-generation hydrogen 

tanks are on track to achieve the 2005 and 2010 

targets in the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Multi-Year R,D&D Plan. The 

relative absence of further technical risks in these 

two generations of tanks provides near-term 

opportunities to reduce their costs significantly by 

taking calculated risks on new ways to build them. 

The most advanced (Type IV) hydrogen tanks 

built with current technology have potential cost 

reduction of roughly a factor of two. That potential 

formed the basis for planning advanced tank 

development experiments at LLNL. On the way to 

those experiments, fundamental discoveries emerged 

which foretell several directions for expansion of the 

frontiers of physical containment. Tanks are not the 

only structures suitable for physical storage of 

compressed hydrogen - some of the newly 

discovered containment geometries could do the 

same job better, providing greater range, shapeability, and lower cost. Taking the risks required to 

depart from the prior art in advanced hydrogen tanks 

can make physical containment of hydrogen a strong 

contender for the 2015 Program Plan Objectives. 

Approach 

LLNL advanced tank development efforts 

followed a deliberate plan intended to reduce the cost 

of hydrogen storage tanks twofold. Most of those 

savings are expected to derive from a change in 

qualification methods applied after manufacture. 

Replacing arbitrary safety factors with real failure 

statistics (using a discipline called Statistical Process 

Control, or SPC) can save roughly 30% of costly 

structural mass. Such SPC is applied routinely in 

mass-produced high-technology products like tires 

and semiconductors, and its first application to tank 

components was made in this year's research at 

LLNL (illustrated in Figure 1). 

The composite structural components that were 

tested to failure form the critical assembly interface 

of several new kinds of hydrogen containers (shown 

in Figure 2), which LLNL expects to prototype in the 

next fiscal year as an attractive alternative to 

conventional (wound composite) tanks. These new 

kinds of assembled tanks carry most of the structural 

loads through the internal volume of the container. 

The limitations of physical storage are no longer 

imposed by a highly developed prior art in advanced 

(wound composite) tanks, and must be replaced by 

Figure 1. Statistical Research Based on the Weibull 

Distribution and Real Failure Force Data 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

models based on raw materials structural properties 

and feasible, mass-producible component 

geometries. 

Results 

Attractive geometries and materials options for 

such non-tank hydrogen containers were the target of 

considerable investigation this year. Packing 

replicated structural components together (as 

illustrated in Figure 3) was found to offer statistical 

advantages, comparable mass, and nearly-arbitrary 

conformability. The versatility of shapes into which 

such 'macro-lattices' could be assembled provides a 

Figure 2.	 Various 'Non-Tank' Geometries Assemble 

into 'Macro-Lattices' to Enable Mass 

Production of Nearly-Arbitrary, UltraConformable Shapes 

 FY 2003 Progress Report 

route to 'ultra-conformability' that could roughly 

halve the volume penalty of storing compressed 

hydrogen aboard motor vehicles. 

The mass and volume of tanks and non-tanks can 

be modeled as feasible-technology curves in a 

volume vs. mass plot (shown in Figure 4). A 

fundamental theoretical innovation was developed to 

enable calculation of the performance consequences 

of novel non-tank geometries. Its formulae allow 

designers to trade off mass, volume, and cost, while 

constraining vehicle range, proceeding with full rigor 

to combine dissimilar dimensioned performance 

measures. Figure 4 (volumetric vs. mass density of 

hydrogen storage) forecasts that progress will follow 

calculable paths to the right of the 2005 and 2010 

objectives of DOE's Hydrogen, Fuel Cells and 

Infrastructure Technologies Program Multi-Year 

R,D&D Plan. 

Conclusions 

•	 The frontier of performance for physical hydrogen storage has been re-opened. 

•	 Statistical Process Research has been initially 

demonstrated for hydrogen storage. 

•	 Statistical methods can limit probabilities of failure to required levels (Pfail<10-7). 

•	 Mass production and innovative non-tank structures can provide copious statistics. 

Figure 3.	 Mass Production Advantages of 

Macrolattices, Including a Metaphor to 

Architectural Structures 

Figure 4.	 Advanced Type IV Pressure Vessels on Track 

for Hydrogen Storage Objectives - With Lots 

of Room for Progress 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Hydrogen Storage Using Light Weight Tanks, 

DOE Annual Hydrogen Fuel Cells and 

Infrastructure Program Review, Berkeley, CA, 

May 20, 2003. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Storage in Insulated Pressure Vessels 

Salvador M. Aceves (Primary Contact) 

Lawrence Livermore National Laboratory 

P.O. Box 808, L-644 

Livermore, CA 94551 

Phone: (925) 422-0864; Fax: (925) 423-7914; E-mail: saceves@llnl.gov 

DOE Program Manager: JoAnn Milliken 

Phone: (202) 586-2480; Fax: (202) 586-1637; E-mail: JoAnn.Milliken@ee.doe.gov 

Objectives 

•	 Demonstrate the advantages of insulated pressure vessels in terms of improved packaging, reduced 

evaporative losses and reduced costs. 

•	 Demonstrate safety of insulated pressure vessels by conducting certification tests. 

•	 Write standards for assuring the safety of insulated pressure vessels. 

•	 Demonstrate insulated pressure vessel technology in two pickup trucks. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

• A. Cost 	 

•	 B. Weight and Volume 

•	 C. Efficiency 

•	 D. Durability 

•	 E. Refueling Time 

•	 F. Codes & Standards 

•	 G. Life-Cycle and Efficiency Analyses 

•	 H. Sufficient Fuel Storage for Acceptable Vehicle Range 

•	 J. Lack of Tank Performance Data 

• K. BOP Components 	 

•	 L. Hydrogen Boil-Off 

Approach 

•	 Conduct experiments to verify safety of insulated pressure vessels. 

•	 Conduct analysis to verify safety of insulated pressure vessels. 

•	 Study existing standards for hydrogen storage in vehicles. 

•	 Test performance of two insulated pressure vessels on pickup trucks. 

Accomplishments 

•	 Performed SAE cryogenic drop and bonfire tests. The insulated pressure vessels successfully passed 

both tests. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2002 Progress Report 

•	 Signed a contract with the South Coast Air Quality Management District (SCAQMD) for $800,000 in 

complementary funding to conduct a demonstration. 

•	 Generated an overall fuel system design for a truck at SunLine Transit. 

•	 Studied current standards for hydrogen tanks. We have generated a preliminary list of tests for 

insulated pressure vessel certification based on current standards for hydrogen tanks. 

•	 Tested 5000-psi vessels at cryogenic temperature. The pressure vessels were burst tested after cycling, 

and they met the required burst pressure criterion. 

•	 Prepared a preliminary procedure for insulated hydrogen pressure vessel certification and submitted it 

to Structural Composites Industries (SCI) and the SCAQMD (our industrial and state government 

project partners). 

•	 Wrote a comprehensive summary of hydrogen storage technologies to be published in the 

"Encyclopedia of Energy." 

Future Directions 

•	 Conduct a demonstration project at SunLine Transit where the insulated pressure vessels will be 

installed in two trucks. 

•	 Conduct a fundamental study of conformal cryogenic compatible pressure vessels and analyze 

desirable shapes as well as desirable pressure ratings. 

•	 Build conformal cryogenic compatible pressure vessels with optimum characteristics as identified in 

the fundamental study. 

Introduction 

The goal of this project is to develop a hydrogen 

storage technology that can satisfy light-duty vehicle 

storage needs in a cost-effective way. This high 

pressure, low temperature vessel has the packaging 

advantages of liquid hydrogen tanks (low weight and 

volume), with much reduced evaporative losses, 

infrastructure flexibility, lower energy consumption, 

lower cost, enhanced user convenience, and safety. 

less-energy-intensive ambient temperature hydrogen 

for daily driving. The high-pressure capability of the 

pressure vessel and the thermodynamic properties of 

hydrogen result in virtually zero boil-off losses for 

insulated hydrogen pressure vessels. Finally, due to 

their high-pressure capability, insulated hydrogen 

pressure vessels never run out of hydrogen after a 

long period of parking. This may be a major issue 

for liquid hydrogen tanks that can lose all their 

hydrogen due to evaporation. 

For reduced cost and complexity it is desirable to 

use commercially available aluminum-fiber pressure 

vessels for insulated hydrogen pressure vessels. 

However, commercially available pressure vessels are 

not designed for operation at cryogenic temperature. 

We plan to demonstrate insulated hydrogen 

pressure vessels that have packaging characteristics 

similar to liquid hydrogen (LH2) tanks and are 

superior to ambient temperature pressure vessels. 

Compared with liquid hydrogen tanks, insulated 

hydrogen pressure vessels give increased flexibility 

to the fueling infrastructure, since the vehicle can be 

fueled with liquid hydrogen for long trips, or with 

Approach 

We are conducting experiments and analysis to 

verify that insulated hydrogen pressure vessels are a 

safe technology for vehicular storage of hydrogen. 

We have conducted a long list of Department of 

Transportation (DOT), International Standards 

Organization (ISO) and Society of Automotive 

Engineers (SAE) tests, and our pressure vessels have 

successfully met the passing criteria for all of them. 

We are planning a demonstration to prove the 

feasibility of insulated hydrogen pressure vessels in 

vehicles. To accomplish this task, we have secured 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

$800,000 of complementary funding from the South 

Coast Air Quality Management District, SCI and 

SunLine Transit. 

Results 

During this year, we completed the two final 

certification tests for insulated hydrogen pressure 

vessels. These are the SAE cryogenic drop test 

(Figure 1) and the SAE cryogenic bonfire test (Figure 

2). These tests were successfully conducted, and our 

vessels met the required passing criteria. 

We are also working on demonstrating the safety 

and advantages of insulated hydrogen pressure 

vessels by installing two of these vessels in pickup 

trucks owned by SunLine Transit. As a part of our 

work for demonstrating the insulated hydrogen 

pressure vessels in the pickup trucks, we have 

 FY 2003 Progress Report 

designed a system for fueling the truck engine with 

hydrogen from the vessel. We have selected and 

purchased all required components (valves, 

regulators, connectors, and safety devices). These 

components will be mounted into the pickup trucks 

in the near future. 

We have also designed a computerized control 

system that will operate our fueling system for the 

pickup trucks. This system uses a MatLab-based 

program that runs on a laptop computer that will be 

carried in the vehicle. 

We have prepared a draft certification procedure 

for insulated hydrogen pressure vessels. This 

procedure is considered to be guidance to 

manufacturers who may want to commercialize this 

technology in the future. The certification procedure 

includes 28 tests that have been selected from 

existing standards for ambient temperature pressure 

vessels (DOT, ISO) and for cryogenic vessels (SAE, 

European Integrated Hydrogen Program). 

We wrote a comprehensive summary of 

hydrogen storage technologies. This will be 

published in the "Encyclopedia of Energy." This 

paper offers a new perspective on the characteristics 

of hydrogen storage technologies, including weight, 

volume, cost, safety and energy required for fuel 

processing. 

 Figure 1. Insulated Hydrogen Pressure Vessel Being Figure 2. Insulated Hydrogen Pressure Vessel Being 

Subjected to the SAE Cryogenic Drop Test Subjected to the SAE Cryogenic Bonfire Test 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

Insulated hydrogen pressure vessels are being 

developed as an alternative technology for storage of 

hydrogen in light-duty vehicles. Insulated hydrogen 

pressure vessels can be fueled with either liquid 

hydrogen or compressed hydrogen. This flexibility 

results in advantages compared to conventional 

hydrogen storage technologies. Insulated hydrogen 

pressure vessels are lighter than hydrides, more 

compact than ambient-temperature pressure vessels, 

and require less energy for liquefaction and have less 

evaporative losses than liquid hydrogen tanks. 

A series of tests have been carried out to verify 

that commercially available pressure vessels can be 

operated at cryogenic temperature with no 

performance losses. All analysis and experiments to 

date indicate that no significant damage has resulted. 

Future activities include a demonstration project in 

which the insulated hydrogen pressure vessels will be 

installed and tested on two vehicles. Future work 

will address the possibility of optimum space 

utilization inside the vehicle through the use of 

cryogenic-compatible conformal pressure vessels. 

 FY 2002 Progress Report 

FY 2002 Publications/Presentations 

1. Certification Testing and Demonstration of 

Insulated Pressure Vessels for Vehicular 

Hydrogen and Natural Gas Storage, Salvador 

M. Aceves, Joel Martinez-Frias and Francisco 

Espinosa-Loza, Randy Schaffer, William Clapper, 

Proceedings of the 8th International Conference 

and Exhibition on Natural Gas Vehicles, 

Washington, DC, October 8-10, 2002. 

2. Hydrogen Storage and Transportation, Gene 

Berry, Joel Martinez-Frias, Francisco EspinozaLoza, Salvador Aceves. Invited article submitted 

to the Encyclopedia of Energy, 2003. 

Special Recognitions & Awards/Patents 

Issued 

Project will be featured in a 4-page article in 

"Science and Technology Review" magazine in June 

2003. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low Permeation Liner for Hydrogen Gas Storage Tanks 

Paul A. Lessing (Primary Contact)
 

Idaho National Engineering & Environmental Laboratory (INEEL)
 

P.O Box 1625 

Idaho Falls, ID, 83415-2218 

Phone: (208) 526-8776; Fax: (208) 526-0690; E-mail: pal2@inel.gov 

DOE Technology Development Manager: Lucito Cataquiz 

Phone: (202) 586-0729; Fax: (202) 586-9811; E-mail: Lucito.Cataquiz@ee.doe.gov 

INEEL Technical Advisor: Raymond P. Anderson 

Phone: (208) 526-1623; Fax: (208) 526-9822; E-mail: anderp@inel.gov 

Subcontractor: University of California at Los Angeles (UCLA), Los Angeles, CA 

Objectives 

•	 Develop a polymer liner that greatly limits hydrogen losses from commercial, light-weight, composite, 

high-pressure hydrogen tanks 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 	 

•	 B. Weight and Volume 

•	 C. Durability 

•	 I. Materials 

Approach 

•	 Select and fabricate polymeric materials with the necessary electron and proton conducting properties 

to form an electrochemical tri-layer barrier to hydrogen permeation through polymer tank-liners 

•	 Fabricate “bench-top” models of the tri-layers on polymer substrates 

•	 Demonstrate the successful functioning of the bench-top model devices at low and high pressures 

•	 Demonstrate a successful prototype of an active, electrochemical hydrogen barrier system within a 

high-pressure, polymer-lined, composite hydrogen storage tank 

Accomplishments 

•	 Filed U.S. Patent Application on concept (# 10,253,265 in Sept. 2002) 

•	 Negotiated and signed Cooperative Research and Development Agreement (CRADA) (No. 03-CR-07) 

with a major manufacturer of composite, high-pressure gas storage tanks 

•	 Fabricated initial tri-layer coatings, overcame wetting problems, and began electrical characterization 

of the individual layers and tri-layers 

•	 Synthesized Pt/Au nanoparticle catalyst that will be added into the poly-3,4-ethylenedioxythiophene 

(PEDOT) electrodes 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Designed and built a low-pressure hydrogen permeability device at UCLA 

•	 Designed a high-pressure hydrogen permeability device at INEEL 

Future Directions 

•	 Test tri-layers on coupons of polymers within low-pressure permeability device 

•	 Conduct further electrical characterization of the tri-layers 

•	 Test tri-layers with various catalysts at electrode interfaces using the low- pressure permeability device 

and select successful combinations 

•	 Fabricate the high-pressure permeability device 

•	 Test successful tri-layers on coupons within the high-pressure permeability device 

•	 Test perfected tri-layers within commercial high-pressure composite gas storage tanks 

Introduction 

State-of-the-art high-pressure gas storage tanks 

consist of an inner liner, made from a polymer such 

as cross-linked polyethylene or nylon, overlaid with 

a continuous graphite fiber/epoxy reinforcement 

layer. These tanks have successfully stored highpressure methane gas. It is desired to extend the 

application of this type of tank to high-pressure 

hydrogen. However, hydrogen has a significantly 

higher permeability rate through these polymer liners 

than methane. Permeation not only leads to a gradual 

loss of hydrogen pressure, but the hydrogen is 

thought to damage and weaken the reinforcement 

layer which could lead to cyclic fatigue or other 

failures of the tank. 

This project was recently begun to develop a 

hydrogen diffusion barrier that can be applied to the 

interior of the polymer liner. The barrier will have 

the following attributes: (1) low permeability of 

hydrogen, (2) adhere well to the polymer liner, (3) 

stiffness (modulus) of the coating should match the 

underlying polymer to avoid cracking when the tank 

is pressurized, (4) the application method should 

allow for coating inside a tank with a narrow neck 

and result in hermetic (gas-tight) coatings that are 

devoid of pin-holes, (5) the material and coating 

method should not appreciably add to the overall cost 

or weight of the tank. 

Approach 

An electrochemically "active" hydrogen 

barrier, fabricated from polymers, is being 

developed. A schematic of this barrier is shown 

in Figure 1. The hydrogen partial pressure 

established by the voltage is extremely low at 

the underlying polymer interface. The hydrogen 

partial pressure can be calculated using the 

Nernst equation, as shown in Figure 1. An 

appropriate level of voltage will be calculated 

and experimentally verified. 

The development plan includes the following: 

1. The barrier is to be constructed of three layers of 

polymers consisting of a proton-conducting 

electrolyte (electronic insulator) sandwiched inbetween electronically conductive polymer 

electrodes. Candidate polymer compositions were 

selected based upon existing knowledge. If this 

Figure 1. Schematic Showing Tri-layer Hydrogen 

Barrier Concept 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

knowledge is not sufficient, new or modified 

compositions will be developed. Appropriate 

catalyst materials will be added at the electrolyte/ 

electrode interfaces. 

2. The methods to manufacture the layers are being 

adapted from existing techniques or developed 

during the project. This could include dip coating 

or spraying of monomers followed by 

polymerization. Other possibilities will be 

explored, and successful manufacturing 

technologies will be developed. 

3. The device is designed as a galvanic-type device 

that functions to prevent hydrogen permeation 

through application of a small direct current (dc) 

voltage using small currents. Methods to provide 

attachment of the dc voltage are being developed. 

Results 

Significant progress was made in all four task 

areas: selection of materials, fabrication of tri-layer 

coatings, characterization of coating layers, and 

experimental verification of hydrogenation 

protection. 

The first set of candidate materials were 

fabricated as a tri-layer prototype barrier. The 

material selected for the electrodes was highlyconductive H-PEDOT polymer (PEDOT + a small 

amount of alcohol). The addition of an alcohol (e.g., 

ethylene glycol) has been shown to increase the 

electronic conductivity of ordinary PEDOT by up to 

three orders of magnitude. The material selected for 

the electrolyte layer was PAMPAS [Poly (2-

acrylamino-2-methyl-1-propanesulfonic acid-costyrene)]. Tri-layers of these materials were first 

made by spin-coating on glass. Later, the layers were 

spin-coated on polymer substrates. However, the 

non-polar surface of the PAMPAS electrolyte 

resulted in a high contact angle while spin-coating 

the second layer of PEDOT. To avoid this problem, 

the PAMPAS film was subjected to an ultravioletozone treatment to modify the surface. The contact 

angle was greatly reduced, and a good second layer 

of PEDOT was then obtained. 

Electrical characterizations were then conducted 

on the tri-layer devices shown as a schematic 

diagram in Figure 2. These included I-V (current/ 

voltage) characteristics of the device and complex 

impedance measurements. Aluminum layers of 100 

nm thickness were evaporated on the two H-PEDOT 

layers to form electrical contacts. I-V tests showed 

that the device was a good electronic insulator 

because of the insulating PAMPAS electrolyte. The 

device showed a very low current (< 10-8 mA) under 

an applied bias (0-3 Volts), as shown in Figure 3. 

The complex impedance results will be reported in 

later reports or papers. 

Figure 4 shows the completed low-pressure 

permeability apparatus. Figure 5 shows an initial 

permeability test without a barrier and with a barrier 

(biased and unbiased). Significant reduction in 

permeation was shown with addition of the tri-layer 

Figure 2. Schematic of Fabricated Tri-layer 

Figure 3. I-V Characteristic Plot for the Tri-layer 

Barrier 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 4. Low-pressure Hydrogen Permeability 

Apparatus Fabricated at UCLA Figure 6.	 Cyclic Voltammetry of PEDOT Electrodes 

plus Pt/Au Nano-particles (Electrodes in 1 M 

HCl + 1 M NaCl solution) 

Figure 5. First Permeability Tests Using Low-Pressure 

Hydrogen 

barrier. However, there is little difference between 

the biased and unbiased cases. Therefore, as 

previous planned, a catalyst will be necessary (as 

with proton exchange membrane type lowtemperature fuel cells) to enable hydrogen reduction/ 

oxidation at the electrode/electrolyte interfaces. 

Platinum/gold (Pt/Au) is being investigated as a 

catalyst. This material was synthesized as nanoparticles in our laboratories. The material shows 

good catalytic reduction of hydrogen as shown in 

Figure 6. The nano-catalyst will be incorporated into 

PEDOT electrodes to enable the hydrogen reduction 

and oxidation reactions at the electrolyte interface, 

and additional hydrogen permeability tests will be 

conducted. 

Conclusions 

•	 Good progress has been made toward the final 

goal of developing a polymer liner that greatly 

limits hydrogen losses from commercial, lightweight, composite, high-pressure hydrogen 

tanks. 

•	 All of the milestones that were set for this time 

period have been achieved. Materials were 

selected, and prototype tri-layer electrochemical barriers have been fabricated and characterized for electrical properties. 

•	 Preliminary testing indicated that fine catalyst 

particles will be necessary at the electrode/electrolyte interfaces to reduce the high free energy 

of the hydrogen oxidation and reduction reactions. 

•	 Nanoparticles of Pt/Au catalyst have been synthesized, and good catalytic reduction of hydrogen has been observed. Therefore, we are well 

positioned to test the tri-layer barriers (with catalyst) in the low-pressure permeability apparatus that was designed and fabricated. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Publications/Presentations 

1. “Low Permeation Liner for H2 Gas Storage 

Tanks”, Paul A. Lessing, Y.Yang, L.P. Ma, F.C. 

Chen, V. Shrotriya, N. Sirosh, M.J. Warner, 

Hydrogen, Fuel Cells & Infrastructure 

Technologies Program, 2003 Merit Review and 

Peer Evaluation Meeting, May 19-22, 2003, 

Berkeley, California. 

 FY 2003 Progress Report 

Special Recognitions & Awards/Patents 

Issued 

1. U.S. Patent Application: Paul A. Lessing, 

“Polymeric Hydrogen Diffusion Barrier, HighPressure Storage Tank so Equipped, Method of 

Fabricating a Storage Tank, and Method of 

Preventing Hydrogen Diffusion”, September, 

2002. 

5 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low Cost, High Efficiency, High Pressure Hydrogen Storage 

(New FY 2004 Project) 

Dr. Neel Sirosh 

QUANTUM Technologies, Inc. 

17872 Cartwright Road, Irvine CA 92614 

Phone: (949) 399-4698; Fax: (949) 399-4600; E-mail: nsirosh@qtww.com 

DOE Technology Development Manager: Tony Bouza 

Phone: (202) 586-4563; Fax: (202) 586-9811; E-mail: Antonio.Bouza@ee.doe.gov 

Objectives 

Deliver a cost-effective and safe high-pressure hydrogen storage system that will meet all of the DOE 

goals for compressed hydrogen storage 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 

• B. Weight and Volume 

• E. Refueling Time 

• H. Sufficient Fuel Storage for Acceptable Vehicle Range 

• I. Materials 

Approach 

QUANTUM will develop and test an advanced, 

cost-effective, and safe high-pressure hydrogen 

storage system. The first task will be to choose the 

most appropriate fiber from which to construct the 

tank. The 3-dimensional or tri-axial composite 

material strength values will be generated for the 

baseline material. Small composite test bottles will 

be fabricated and burst tested. Strain gages will be 

mounted on the bottles to correlate burst pressure 

and composite wall stresses and strains. A detailed 

axisymmetric finite element analysis of each test 

bottle will be completed to correlate to the strain 

gage data obtained from the bottle burst tests. 

Composite specimens will be fabricated and tested 

to obtain the cross-ply compressive strength of the 

material. 

that includes the metallic parts will be completed to 

assess the stress/strain state in the composite shell 

and metallic parts. Up to three tanks will be 

fabricated and burst tested to finalize the tank design 

for 10,000 psi. Three tanks will be fabricated and 

tested to demonstrate the scale-up capabilities of the 

material characterization and optimization. One tank 

will be burst tested, and two tanks will be cycle 

tested and burst tested at the end of cycle testing. 

QUANTUM will work with Oak Ridge National 

Laboratory to identify a robust and cost-effective 

stress sensor technology that is suitable for 

integration on tanks. This sensor will allow the tank 

to operate at reduced stress ratios with the benefit of 

lighter weight. 

A review of current tank Design Failure Modes 

and Effects Analysis will be completed to assess the 

A representative tank will be designed for 10,000 critical issues and validation tests of a tank. Three 

psi service pressure. A detailed finite element model tests will be specified to demonstrate the strength and 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

life capabilities of the tanks. The three tests will be 

completed, and it is anticipated that the tests will 

include pressure cycling at ambient and elevated 

temperatures. 

Tests will be conducted to better understand the 

thermodynamics of the tank charging and 

discharging process and to capitalize upon that 

understanding by optimizing fuel temperature and 

pressure and how that relationship is affected by 

additional insulation on the tank, on-board 

refrigeration, heat-sink technologies, fuel 

consumption rate and thermal load. 

The analysis portion of the project will establish 

a working foundation upon which the development 

of a refueling refrigeration system design, on-board 

refrigeration system design, heat-sink system design, 

and tank insulation system design will be made. The 

analysis is meant to serve as both a guide for 

development as well as a means by which the 

fundamental thermal characteristics of the fuel and 

tank system can be understood and predicted. Most 

of the analysis will be built from first-principles. 

 FY 2003 Progress Report 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Catalytically Enhanced Hydrogen Storage Systems 

Craig M. Jensen (Primary Contact), Dalin Sun, Sesha Srinivasan, Ping Wang, Keeley Murphy, 

Zhaohui Wang, Michael Eberhard, Ali Naghipour, John Linzi, and Walter Niemczura 

University of Hawaii 

Department of Chemistry 

Honolulu, Hawaii 96822 

Phone: (808) 956-2769; Fax: (808) 956-5908; E-mail: jensen@gold.chem.hawaii.edu 

DOE Technology Development Manager: JoAnn Milliken 

Phone: (202) 586-2480; Fax: (202) 586-9811; E-mail: JoAnn.Milliken@ee.doe.gov 

Objectives 

•	 Determination of the chemical nature of the titanium species responsible for the enhanced kinetics of 

Ti-doped NaAlH4 . 

•	 Determination of the mechanism of action of the dopants in the dehydrogenation and re-hydrogenation 

processes. 

•	 Development of hydrogen storage materials based on complex aluminum hydrides that meet the 

FreedomCAR hydrogen storage targets of cost, specific energy, and energy density. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan. 

•	 B. Weight and Volume 

•	 C. Efficiency 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

Approach 

•	 Determination and quantification of effective dopant through electron paramagnetic resonance (EPR) 

and magnetic susceptibility studies. 

•	 Elucidation of the effects of doping directly on hydrogen by neutron diffraction, inelastic neutron 

scattering (INS), solid state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. 

•	 Determination of the dependence of plateau pressure on doping level. 

•	 Synthesis and evaluation of advanced alanates suggested by the insight gained by fundamental studies. 

Accomplishments 

•	 Verification that doping NaAlH4 with Ti dopant precursors generates Ti(III) dopants that persist 

through dehydrogenation and repeated hydrogen cycling. 

•	 First accurate determination of the location of the hydrogen atoms in NaAlH4 through a neutron 

diffraction study of NaAlD4. 

•	 Observation of the bulk perturbation of the [AlH4]

-

 anion upon doping through 2H NMR and IR 

spectroscopy studies. 

1 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Measurement of changes in plateau pressure resulting upon variation in level of Ti substitution in 

NaAlH4. 

•	 Development of a method for the removal of sodium salt by-products from doped NaAlH4. 

Future Directions 

•	 Continue characterization and quantification of titanium species in doped NaAlH4 by combination of 

EPR and magnetic susceptibility and determine whether kinetic enhancement is due to Ti(III) or Ti(IV) 

species. 

•	 Continue IR, NMR, and INS spectroscopic studies and obtain Raman spectra to elucidate the influence 

of doping on the dynamics of the [AlH4]

- anion and their relationship to hydrogen cycling kinetics. 

•	 Determine the hydrogen cycling properties of doped NaAlH4 from which doping by-product(s) have 

been removed. 

• Probe whether the purification method can be extended to hydride containing high (>10 mol %) 

doping levels and Li- and Mg-based alanates. 

Introduction 

We have developed methods of doping sodium 

aluminum hydride, NaAlH4, with titanium and/or 

zirconium that give rise to state-of-the-art hydrogen 

storage materials. During the initial dehydrogenation 

reaction seen in equation 1, NaAlH4 rapidly evolves 

3 NaAlH4 ----------> Na3AlH6 + 2 Al + 3 H2 (1) 

temperatures upon doping with 2 mole percent 

Ti(On

Bu)4 by our methods. At 100°C, hydrogen 

flow rates of 0.01 g H2/s per kg under a constant 

pressure of 1 atm have been observed. This 

performance is adequate to meet the demands of a 

fuel cell operating under practical conditions. We 

have also found that NaH and Al doped with 2 mole 

percent Zr absorbs 4.4 weight percent hydrogen 

within 15 minutes at 120°C under 125 atm of 

hydrogen pressure. However, despite this progress in 

enhancing the dehydrogenation and re-hydrogenation 

processes, it has not yet been demonstrated that ~5 

weight percent hydrogen can be reversibly released 

from these materials under conditions that are 

required for the practical operation of an onboard 

fuel cell. Most notably, the rate and equilibrium 

plateau pressures of the second dehydrogenation 

reaction, seen in equation 2, are 

Na3AlH6 ----------> 3 NaH + Al + 3/2 H2 (2) 

impractical for hydride that is doped with titanium, 

and improved variations of this material must be 

produced to achieve commercial viability. To guide 

our development of advanced alanates, we have 

sought to gain a fundamental understanding of the 

nature of the dopants and the structural effects they 

exert on the hydride. 

Approach 

It was initially speculated that the remarkable 

enhancement of the hydrogen cycling kinetics in 

doped NaAlH4 was due to surface-localized catalytic 

sites. However, we obtained X-ray crystallographic 

data that revealed that the doping of the hydride 

results in bulk lattice distortions. These observations 

have led us to develop a new model of the doped 

hydrides in which Na+ ions are substituted by M4+ 

and/or M3+ dopant ions and the generation of the 

requisite number of Na+ vacancies in the hydride 

lattice to maintain charge neutrality. Spin isolated 

Ti(III) has been identified in the EPR spectroscopy. 

This finding is consistent with the presence of the 

Ti3+ cations in the doped hydride as predicted by our 

“substitution model” of doped NaAlH4. It also raises 

the question of whether the enhanced hydrogen 

cycling kinetics in the doped hydride are the result of 

substitution of Na+ by M3+ or M4+ or both. In a 

collaborative study with Dr. Sandra Eaton of the 

University of Denver, we are endeavoring to resolve 

this ambiguity through further EPR studies in 

conjunction with quantification of the density of the 

paramagnetic M3+ through magnetic susceptibility 

experiments. 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Although x-ray diffraction and EPR studies 

showed that the doping of NaAlH4 results in bulk 

structural changes, these techniques cannot yield 

reliable information about the structural environment 

of the hydrogen atoms. Thus, in order to determine 

what changes occur in the structural environment of 

the hydrogen atom upon doping the hydride, neutron 

diffraction, INS, solid state NMR, and infrared 

spectroscopic studies are being conducted. We have 

established collaborations with Dr. Hendrick Brinks 

and Dr. Bjorn Hauback, Institute for Energy 

Technology, Kjeller, Norway (neutron diffraction); 

Terry Udovic, National Institute of Standards and 

Technology (INS); Dr. Juergen Eckert, Los Alamos 

National Laboratories (INS); and Prof. Klaus Yvon 

and Dr. Sandrine Gomes, University of Geneva (IR) 

for these efforts. 

The doping process generates by-products that 

constitute “dead weight” in the kinetically enhanced 

hydride. For example, doping with TiCl3 or TiCl4 

results in the formation of segregated NaCl byproduct. Thus, the increased kinetic enhancement at 

higher doping levels results in a capacity loss due to 

the weight of both the Ti dopant and the by-product. 

Additionally, the earlier “redox” model of the doped 

hydride predicts a 3-4 equivalent loss in hydrogencarrying Al upon doping. By contrast, our 

“substitution” model of the doped hydride predicts all 

Al remains available for hydrogen binding. This is an 

important distinction as only the newer model 

suggests that removal of “dead weight” doping byproduct might lead to materials having both increased 

hydrogen capacity as well as the highly acceptable 

kinetics that are achieved at high doping levels. 

Additionally, the “substitution” model, unlike the 

redox model, predicts that plateau pressure, a 

thermodynamic property, should be significantly 

altered at high doping levels. Thus, we are probing the 

effect of doping on the equilibrium plateau pressures 

of the hydride. We are also developing methods of 

removing the inert, “dead weight” by-products that are 

generated in the doping process and are measuring the 

hydrogen cycling capacities and kinetics of these 

purified materials. 

Results 

Electron Paramagnetic Spin and Magnetic 

Susceptibility Studies: Preliminary electron 

paramagnetic resonance studies were conducted in 

collaboration with Dr. Sandra Eaton, University of 

Denver, and Dr. Karl Gross and Eric Majoub, Sandia 

National Laboratory. The EPR spectrum of a sample 

NaAlH4 doped with 2 mol % Ti(OBu)4 is seen in 

Figure 1. The very sharp, singlet signal that 

dominates the spectrum can be readily assigned to 

spin isolated Ti(III). Very similar spectra were 

obtained from a variety of samples that were doped 

with either Ti(III) or Ti(IV) precursors. This finding 

lends strong support for our “substitution” model of 

doped NaAlH4. Continuing collaborative studies 

with the University of Denver group have shown that 

the spin isolated Ti(III) dopants persist through 

dehydrogenation and in repeated hydrogen cycling of 

the material. While the EPR studies provide strong 

support for the substitution of Ti3+, into the bulk 

hydride lattice, it does not preclude the possibility 

that EPR silent, diamagnetic Ti4+ is also present. In 

order to explore this possibility, we have begun 

efforts to quantify the amounts of Ti(III) present in Ti 

doped hydride through magnetic susceptibility 

measurements. At this point we have completed the 

measurement of χ (magnetic susceptibility) values 

for a series of standards containing known amounts 

of Ti(III) and generated a standard plot of χ vs. moles 

Ti(III)/cc. Quantification of the amount of Ti(III) 

present in samples of the doped hydride can now be 

accomplished by comparison of their measured χ

Figure 1. EPR Spectrum NaAlH4 Doped with 2 mol % 

Ti(OBu)4 

3 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

values to the standard plot. If the level of Ti(III) 

present is less than the Ti doping level, it can be 

inferred that the unaccounted titanium is present as 

diamagnetic, Ti(IV). Determination of the amounts 

of Ti(III) and Ti(IV) in the doped hydride will allow 

us to determine if the kinetic enhancement resulting 

upon doping tracks the level of substitution of Na+ 

by Ti3+, Ti4+, or both. 

Neutron Diffraction: In order to undertake a 

neutron structure determination, we had to develop a 

method for the synthesis of high purity NaAlD4. 

This was accomplished through the reaction of 

LiAlD4 with NaF in the presence of an aluminum 

alkyl catalyst. Neutron diffraction data were 

collected at the Institute for Energy Technology in 

Kjeller, Norway, from a sample of NaAlD4 that was 

prepared through this method. Final refinement of 

this data gave the structure of the hydride seen in 

Figure 2. The deuterium atoms were well located, 

giving a structure with two unique Al-D distances of

1.627(2) and 1.626(2) Å, and two unique D-Al-D 

angles of 107.30(1) and 113.90(1). 

Infrared Spectroscopy: Preliminary infrared 

spectroscopic studies have been carried out. No new 

vibrational modes or changes in absorption 

frequencies can be detected upon comparison of 

doped and undoped samples of NaAlH4. However, 

there is a dramatic broadening of the infrared 

absorptions in the samples of the doped hydride. 

This finding indicates that while the bonding in the 

[AlH4]

-

 anion is unperturbed upon doping, the 

Figure 2. Crystal Structure of NaAlD4 

 FY 2003 Progress Report 

changes that occur upon bulk Ti3+ substitution in the 

lattice result in a broader allowable range of 

orientation of the anions in the lattice. 

Solid State Nuclear Magnetic Resonance 

Spectroscopy: Comparison of the solid state 2

H 

spectra of doped and undoped samples of NaAlD4 

show a significant broadening of the dipolar doublet 

upon doping. This finding is in agreement with our 

interpretation of the IR studies: the changes that 

occur upon bulk Ti3+ substitution in the lattice result 

in a broader allowable range of orientation of the 

anions in the lattice. 

Effect of Doping Level on Plateau Pressures: The 

equilibrium hydrogen pressure has been determined 

for samples of NaAlH4 that were doped with 1.3 – 

2.0 mole % Ti(OBu)4. The plateau pressure was seen 

to increase linearly from 3.0(2) to 4.7(2) Mpa over 

the range of doping levels. 

Purification of Doped Materials: A proprietary 

method has been developed for the removal of the 

contaminant sodium salts resulting upon Ti doping of 

NaAlH4. X-ray diffraction has shown that the 

removal of the by-products is >95% complete. 

Conclusions 

We have, for the first time, accurately determined 

the location of the hydrogen atoms in NaAlH4 

through a neutron diffraction study of NaAlD4. Our 

EPR, IR, and NMR studies provide additional 

support for our “substitution” model of doped 

NaAlH4 that was initially proposed on the basis of xray diffraction data. The ERP studies lend strong 

support to our hypothesis that Ti doping of the 

hydride results in the substitution of Ti3+ into the 

bulk hydride lattice that persists through repeated 

cycles of dehydrogenation/re-hydrogenation. The IR 

and solid state 2

H NMR studies also provide clear 

evidence that bulk changes occur in the hydride upon 

doping. Moreover, the changes in the equilibrium 

plateau pressures that are predicted by the 

“substitution” model have been verified. Thus, 

prospects seem bright for the possibility of tailoring 

an alanate material with thermodynamic properties 

well suited for utilization as an onboard hydrogen 

carrier for PEM fuel cell applications. Furthermore, 

we have developed a method for the removal of the 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

“dead weight” by-products that result from the 

doping process. Thus, it may be possible to obtain 

mixed Na/Ti alanates that contain up to 6 wt % 

available hydrogen and exhibit superior hydrogen 

cycling kinetics. 

Publications (5/02-6/03) 

1. D. Sun, H.T. Takeshita, T. Kiyobayashi, N. 

Kuriyama, and C.M. Jensen, “X-ray Diffraction 

Studies of Titanium and Zirconium Doped 

NaAlH4: Structural Basis of the Enhanced 

Hydrogen Storage Properties Resulting Upon 

Doping”, J. Alloys Compd. 2002, 337, 8. 

2. K.J. Gross, C.M. Jensen, and G.J. Thomas, 

“Catalyzed Alanates for Hydrogen Storage”, J. 

Alloys Compd. 2002 330-332, 683. 

3. G. Sandrock, K. Gross, G. Thomas, C. Jensen, D. 

Meeker, and S. Takara, “Engineering 

Considerations in the Use of Catalyzed Sodium 

Alanates for Hydrogen Storage”, J. Alloys Compd. 

2002, 330-332, 696. 

4. G.J. Thomas, K.J. Gross, N.Y.C. Yang, C.M. 

Jensen, “Microstructural Characterization of 

Catalyzed NaAlH4 “, J. Alloys Comp. 2002, 

330-332, 702. 

5. B.C. Hauback, H. W. Brinks, C.M. Jensen, K. 

Murphy, and A.J. Maeland, “Neutron Diffraction 

“Structure Determination of NaAlD4 ” J. Alloys 

Comp. 2003, 358, 142. 

6. S.S. Eaton, K. Gross, E. Majzoub, K. Murphy, and 

C.M. Jensen, “EPR Studies of Titanium Doped 

NaAlH4: Fundamental Insight to a Promising 

New Hydrogen Storage Material”, Chem. 

Commun., in press. 

7. T. Kiyobayashi, S.S. Srinivasan, D. Sun, and C.M. 

Jensen, “Kinetic Study and Determination of the 

Enthalpies of Activation of Titanium and 

Zirconium Doped NaAlH4 and Na3AlH6 ” J. Phys. 

Chem., in press. 

Invited Presentations (May 2002 – June 2003) 

1. 5/13/02 Symposium on Hydrogen Storage 

Materials and Hydrogen Generators, 201st 

meeting of the Electrochemical Society, 

Philadelphia, PA. 

2. 8/13/02 Universal Oil Products Research Center, 

Des Plaines, Illinois. 

3. 9/05/02 International Symposium on Metal 

Hydrogen Systems, Annecy, France. 

4. 9/13/02 California Institute of Technology. 

5. 3/18/03 Research Association for the 

Development of Advanced Metal Hydrides 

meeting, Osaka, Japan 

6. 6/11/03 European Materials Research Society 

2003 Meeting, Symposium on Nanoscale 

Materials for Energy, Strasbourg, France. 

FY 03 Patents 

1. Craig M. Jensen and Ragaiy. A. Zidan, “Hydrogen 

Storage Materials and Method of Making by Dry 

Homogenation”, 2002, US patent 6,471,935. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydride Development for Hydrogen Storage 

Karl J. Gross (Primary Contact), Weifang Luo, Eric Majzoub, Greg Roberts, Scott Spangler, Daniel 

Dedrick, Terry Johnson, Jennifer Chan 

Sandia National Laboratories 

P.O. Box 969 

Livermore, CA 94551 

Phone: (925) 294-4639; Fax: (925) 294-3410; E-mail: kjgross@sandia.gov 

DOE Technology Development Manager: JoAnn Milliken 

Phone: (202) 586-2480; Fax: (202) 586-9811; E-mail: JoAnn.Milliken@ee.doe.gov 

Objectives 

•	 Develop new complex hydride materials with >6 weight percent system hydrogen capacity at below 

100°C. 

•	 Improve the kinetics of absorption and desorption and thermodynamic plateau pressures of Ti-doped 

sodium alanate metal hydrides. 

•	 Improve processing and doping techniques of Ti-doped sodium alanate to lower cost. 

•	 Help develop state-of-the-art hydrogen storage/delivery systems by determining important materials 

engineering properties of these complex hydrides. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

On-Board Hydrogen Storage 

• A. Cost 	 

•	 B. Weight and Volume 

•	 C. Efficiency 

•	 D. Durability 

•	 E. Refueling Time 

•	 F. Codes and Standards 

•	 G. Life Cycle, and Efficiency Analyses 

Reversible Solid-State Material Storage Systems (Regenerated On-Board) 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

•	 O. Test Protocols and Evaluation Facilities 

•	 P. Dispensing Technology. 

Approach 

We employ a parallel approach through work in each of the following areas: 

•	 Investigate new complex hydrides to achieve higher capacities. 

•	 Develop new doping process to improve both rates and capacity. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Experimentally characterize the material properties using analytic techniques such as X-ray and 

neutron diffraction, electron spin resonance (ESR), nuclear magnetic resonance (NMR), etc. 

•	 Determine the hydriding mechanisms through experimental analysis and modeling. 

•	 Determine important engineering materials properties of the alanates to ensure that complex hydrides 

are on track for eventual commercialization. 

Accomplishments 

•	 Ti-doped Mg2FeH6 has been investigated as an analog to the alanate system. 

•	 Preliminary investigation of Li-based complex hydrides has been performed. 

•	 Using Sandia’s direct synthesis and doping approach, it was found that Ti-halides (Cl, F, Br) all 

successfully enhance kinetics with TiCl2 providing the best results. 

•	 It was also determined that non-reactive precursors (TiH2 and pre-reacted halides) improve kinetics, 

opening up new routes to improve capacity. 

•	 Through collaborations with universities and other labs, we have performed in-depth NMR, neutron 

diffraction, and ESR measurements studies. These have aided in furthering our understanding of the 

Ti-doping mechanism. 

•	 Pressure composition temperature isotherm (PCT) measurements have been performed on Na alanate. 

These measurements indicate that Ti-doping modifies the thermodynamic stability of the materials as 

well as the kinetics of hydrogen sorption. 

•	 Detailed pressure- and concentration-dependent kinetics measurements have been made. This 

provided the basis for a more complete kinetics model that now allows the calculation of hydrogen 

sorption behavior over a broad range of conditions. 

•	 Instrumentation has been completed and experimental work has been started to measure engineering 

materials properties of the complex hydrides, including thermal and electrical conductivity, volume 

expansion, and porosity. This work is critical for the ultimate commercialization of this technology. 

Future Directions 

•	 New complex hydrides: Continue work to achieve higher hydrogen storage capacities with reasonable 

kinetics compared with current sodium alanates. 

•	 Search for new AlH6-based alanates: Achieve higher hydrogen storage capacities by discovering new 

highly coordinated aluminum-hydrogen compounds. 

•	 Structure properties and mechanisms of Ti-doped sodium alanates: Continue work to fully understand 

how transition metal doping affects the bulk structure properties that lead to enhanced kinetics of 

sodium alanates. 

•	 Materials synthesis improvements and scale-up: Improve materials synthesis processes for the scaleup and commercialization of the state-of-the-art alanates. 

•	 Effect of contaminants on performance of complex hydrides: Determine the degree to which lowlevel contaminants in a hydrogen gas supply will impact the performance of complex hydride 

storage materials. 

•	 Materials compatibility and safety studies: Ensure materials compatibility of the complex hydride 

storage systems. 

•	 Engineering material properties characterization: Experimentally investigate and report material 

properties of current state-of-the-art Ti-doped sodium alanates to enable engineering design solutions 

for hydrogen storage systems. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Complex hydride systems life cycle analysis: Investigate the technology scale-up effects of potential 

systems used for solid-state hydrogen storage. 

Introduction 

The purpose of this project is to develop and 

demonstrate the next generation of practical 

hydrogen storage materials. This task will focus on 

complex metal hydrides with high reversible 

hydrogen storage capacities and novel approaches to 

on-board hydrogen storage. 

This research is based on achievements that 

Sandia has made in developing advanced Ti-doped Na 

alanates [1]. The discovery of enhanced hydrogen 

sorption by Ti-doped alanates opened up an entirely 

new prospect for lightweight hydrogen storage [2-3]. 

These materials have nearly ideal equilibrium 

thermodynamics, high capacities, and moderate 

kinetics. However, while the hydrogen capacity is 2 to 

3 times better than commercial low-temperature 

hydrides, it does not meet the DOE/FreedomCAR 

storage capacity targets. Thus, other higher capacity 

reversible complex hydrides must be developed. At 

the same time, Na alanates continue to provide a good 

working model to better understand reversible 

hydrogen sorption in complex hydrides. Sandia's 

direct synthesis process and new Ti-doping methods 

have led to a dramatic improvement in the reversible 

hydrogen capacity and hydrogen absorption and 

desorption rates. These methods will be employed to 

seek out advanced complex hydrides with larger 

hydrogen storage capacities and better performance. 

Approach 

Ti-doped alanate samples were prepared by 

direct synthesis from NaH and Al powders doped 

with 4 mol.% of TiCl3. These powders were 

mechanically milled for 30 minutes in an argon 

atmosphere. Samples were prepared, transferred and 

measured without exposure to air. 

Thermodynamic measurements were performed 

on a fully automated commercial PCT instrument. 

Absorption and desorption kinetics measurements 

were obtained volumetrically using manual Sieverts’ 

apparatus and a cylindrical 316 SS reactor (1.3 cm 

outer diameter by 0.12 cm wall thickness and length 

of 12 cm) containing about 1.5 g of catalyzed 

samples. A thermocouple well in the center of the 

vessel allows for accurate temperature measurements 

during cycling. Data were recorded via computer, 

and measurements lasted from minutes to several 

days, depending on the TiCl3, level test pressure, and 

temperature conditions. 

Results 

Thermodynamics of Ti-doped alanates. Our most 

recent measurements of the thermodynamic 

properties of the current generation of 4 mol.% Tidoped alanates were performed using an automated 

PCT instrument (Figure 1). These measurements 

show the two plateau regions associated with the 

formation and decomposition of the NaAlH4, the 

Na3AlH6 phases. Absorption and desorption 

measurements of the NaAlH4 phase were made at 

135, 150 and 170°C. These clearly show two distinct 

regions. One portion has a flat pressure plateau and 

the other is sloping. These results suggest that 

sample is composed of an inhomogeneous 

distribution of material with dissimilar kinetic and 

thermodynamic properties. One hypothesis is that 

Figure 1.	 PCT measurements of Hydrogen Absorption 

and Desorption of NaAlH4 and Na3AlH6 at 

135, 150 and 170°C 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

the Ti is not homogeneously distributed in the 

sample. If that is the case, then there is a direct link 

between the presence of Ti and a change in the 

thermodynamics of alanate formation. 

Thermodynamics being a bulk property, this could 

only happen through introduction of Ti into the 

crystal lattice. Knowing whether Ti is at the surface 

or present in the bulk is fundamental to solving the 

mystery of the mechanism of the Ti-enhanced 

sorption properties. These preliminary results are 

being followed up with a more detailed analysis. 

Kinetics of Ti-doped alanates. Hydrogen sorption 

rates of Ti-doped Na-alanate were measured at 

various temperatures, pressures, and hydrogen 

concentrations. Rate equations have been derived 

from this data to calculate the formation and 

decomposition kinetics of both NaAlH4 and 

Na3AlH6. It was found that, in addition to 

temperature, the pressure differential (applied 

pressure vs. equilibrium pressure) and composition 

have a strong impact on the sorption rates. These 

equations provide important information that is 

needed for alanate performance modeling. Using 

these equations, the optimum temperature can be 

estimated for hydrogen absorption at a given applied 

pressure. For example, the best temperature for 

hydrogen absorption using 100 bar of hydrogen is 

140oC, not 160oC (Figure 2). These equations can 

also be used to estimate the lowest temperature 

needed for desorption at a given rate and pressure. 

We intend to extend this approach to the kinetics of 

other hydrogen storage materials. 

Fundamental studies of Ti-doped alanates. The 

structure of Ti-doped sodium aluminum deuteride 

has been determined using Rietveld refinement of Xray and neutron powder diffraction data and 

compared to that of undoped NaAlD4 and NaAlH4. 

Neutron powder diffraction data were taken at the 

National Institute of Standards and Technology 

(NIST) Center for Neutron Research (NCNR) with T. 

Udovic (Figure 3). Refinement of the diffraction 

data for deuterium atom positions of NaAlD4 was 

complicated due to the four phases present in the 

sample: the tetra-deuteride NaAlD4, the hexadeuteride Na3AlD6, NaCl, and Al. Due to the small 

level of Ti-doping (4 at.%), the presence of Ti-Al 

compounds could not be conclusively determined, 

and no attempt was made to include any Ti-Al phases 

in the refinements [6]. The refined lattice parameters 

for the tetragonal NaAlD4 structure are found to be 

a=5.010 angstroms and c=11.323 angstroms. Results 

of first-principles calculations of the lattice 

parameters are within a few percent of the Rietveldrefined values. The generalized gradient 

approximation (GGA) is found to produce 

significantly better agreement with the experimental 

data than the local-density approximation (LDA), 

which is attributed to a very inhomogeneous 

distribution of electronic density in the alanates. The 

Rietveld refinement, LDA, and GGA results for the 

Figure 2.	 Calculated Hydrogen Absorption Rates for 

NaAlH4 as a Function of Pressure at Different 

Temperatures 

Figure 3. Rietveld Refinement of Powder Neutron 

Diffraction Data of a Ti-doped Alanate Sample 

4 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Al-H bond length in NaAlD4 are 1.626, 1.634, and 

1.631 angstroms, respectively. Refined values of the 

Al-H bond lengths in Na3AlD6 are in agreement 

within 2% of earlier work on undoped Na3AlD6 [5]. 

Improvements in materials synthesis. Our 

previous work raised questions about the importance 

of the Ti halide to Na halide decomposition reaction 

on the overall Ti-induced enhanced kinetics. It is this 

reaction that is responsible for most of the hydrogen 

capacity loss on Ti-doping the alanates. For this 

reason, an indirect doping process was tested. A 

sample was prepared in which TiCl2 was pre-reacted 

with LiH by mechanical milling. The resulting 

powder was then milled in a 6 mol.% ratio with NaH 

and Al to form a pre-alanate mixture in which the Tihalide had not been directly reacted with NaH. From 

a mechanistic point of view, this method should 

indicate whether or not the Ti halide and Na reaction 

is necessary for Ti-enhanced kinetics. From a 

practical perspective, this method may also provide 

an incremental improvement in capacity at higher 

doping levels due to the formation of the lighter LiCl 

byproduct rather than NaCl. The mixture was 

subjected to a series of hydriding / dehydriding 

cycles. The measurements showed an activation 

process that is much more profound than in the direct 

Ti halide doped materials. An Arrhenius plot (Figure 

4) of desorption rates vs. temperature indicates 

Figure 4.	 Arrhenius Plot Comparing NaAlH4 Desorption 

Rates of Generation II, III-D, and III-E 

Alanates (rates: II on a total weight basis, III-D 

and III-E on a NaH + Al weight basis) 

 FY 2003 Progress Report 

similar activation energies for both the direct and the 

indirect doping methods. Thus, directly reacting Ti 

halides with sodium (hydride or metal) is beneficial 

for initially rapid kinetics, but not necessary for long 

cycle-life materials. 

Extending the above notion that Ti-diffusion/ 

substitution may be possible without using a Ti 

halide or organic precursor, a sample was tested 

using only TiH2. Once again, the desorption rates are 

nearly identical to those of the indirect doped 

material and the 2 mol.% TiCl3-doped alanates. 

From an applications perspective, TiH2 as a dopant 

precursor should overcome the problem of capacity 

loss associated with the formation to Na halides 

when using Ti halide precursors. 

New complex hydrides. We have been investigating 

other complex hydrides besides the Na alanates. 

These include Li alanates and Mg alanates. So far, 

neither system could be made to reversibly absorb 

hydrogen under moderate conditions (100 bar and up 

to 300°C). We have also investigated the Mg-Fe-H 

system through our International Energy Agency task 

17 collaboration with the University of Geneva, 

Switzerland. Using our direct synthesis approach, 

we started with MgH2 and Fe powders, which were 

mechanically milled together. The second absorption 

cycle showed activity beyond the formation of 

MgH2. X-ray diffraction measurements showed both 

MgH2 (about 41 wt%) and Mg2FeH6 (about 15 wt%) 

along with Fe (about 44 wt%) (Figure 5). We also 

tested the material prepared in the same manner but 

doped during the milling process with 4 mol.% 

TiCl3. This preparation appears to have an effect on 

the rehydriding kinetics. Notably, there is rapid 

hydrogen absorption associated with the formation of 

MgH2 even below 100oC. The study of the Mg-Fe-H 

system is important because it is an analog to the Na 

alanate system. Demonstration of doping-enhanced 

reversibility in the Mg-Fe-H system will provide 

more clues as to the role of Ti and other transition 

metal dopants. In addition, it will demonstrate the 

possibility that a wider class of complex hydrides can 

be modified through doping. Detailed measurements 

are being performed at this time. 

Engineering material properties. Engineering 

material properties investigations of Ti-doped 

sodium alanates is currently underway. The selection 

of the properties and the associated parameter space 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 4.	 X-ray Diffraction Patterns of MgH2 + Fe 

Before and After Hydriding Showing Presence 

of Mg2FeH6 

focuses on hydrogen-storage application needs. For 

example, the characterization of the thermal 

conductivity of complex hydrides is critical for 

advanced design and modeling of hydride-based 

hydrogen storage systems. The thermal conductivity 

test hardware has been built and calibrated. A finite 

element model was used to determine optimum 

instrument design geometry as well as to validate the 

experimental method used to determine thermal 

conductivity. The model helped to minimize the 

mass of sodium alanate necessary to achieve accurate 

and measurable results. Testing on various 

calibration materials has provided consistent and 

repeatable results. Thermal properties testing of 

sodium-alanate as a function of phase composition 

and hydrogen gas pressure is in progress. In 

addition, a test cell has been constructed that can 

measure the pressure exerted on a wall by 

constraining the sodium aluminum hydride, and an 

electrical-properties cell has been built for measuring 

DC and AC response of the alanate material. All 

instrumentation has been designed to be used in the 

future to characterize new hydrogen storage 

materials as they are developed. 

Conclusions 

The results presented above demonstrate that 

solid progress is being made on the development of 

light-weight complex hydrides for hydrogen storage 

applications. 

References 

1. Gross, K.J., Majzoub, E., Thomas, G.J., and 

Sandrock, G. 2002. “Hydride development for 

hydrogen storage”, in Proceedings U.S. DOE 

Hydrogen Program Review, NREL/CP-610­

32405. Golden, CO. 

2. Bogdanovic’, B. and Schwickardi, M. 1997. “Tidoped alkali metal aluminum hydrides as potential 

novel reversible hydrogen storage materials”, J. 

Alloys and Compounds, 253:1. 

3. Bogdanovic’, B., Brand, R.A., Marjanovic’, A., 

Schwikardi, M., and Tölle, J. 2000. “Metaldoped sodium aluminum hydrides as potential 

new hydrogen storage materials”, J. Alloys and 

Compounds, 302:36. 

4. Zidan, R.A., Takara, S., Hee, A.G., and Jensen, 

C.M. J. Alloys and Compounds, 285 (1999) 119. 

5. Ronnebro, E., Noreus, D., Kadir, K., Reiser, A, 

Bogdanovic’, B., J. Al. Comp., 299 (1-2):101-6, 

2000. 

6. Majzoub, E., Gross, K., Proceedings of the 

International Symposium on Metal Hydrogen 

Systems, Annecy, France, 2-6 Sept. 2002, in press 

J. Al. Comp. 2003. 

FY 2003 Publications 

1. Gross, K.J., Majzoub, E.H., Spangler, S.W.	 “The 

effects of titanium precursors on hydriding 

properties of alanates”, Submitted J. Alloys and 

Comps 2002 

2. Gross, K.J., Thomas, G.J., Jensen, J. Alloys and 

Comps, 2002; v.330, p.683-690 

6 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

3. Majzoub, E.H., Gross, K.J. “Titanium-halide 

catalyst-precursors in sodium aluminum 

hydrides”, Submitted J. Alloys and Comps 2002 

4. Majzoub, E.H. and Ozolins, V., “Rietveld 

refinement and ab initio calculations of NaAlD4”, 

In preparation. 

5. Eaton, S., Gross, K.J., Majzoub,E.H., Murphy, K. 

and Jensen, C.M. “EPR studies of titanium doped 

NaAlH4: Fundamental insight to a promising new 

hydrogen storage material”, Submitted Chemical 

Communications 2003 

6. Sandrock, G., Gross, K., Thomas, G, J.	 Alloys and 

Comps 2002; v.339, no.1-2, p.299-308 

7. Thomas, G.J., Gross, K.J., Yang, NYC, Jensen, C. 

J. Alloys and Comps 2002; v.330, p.702-707 

8. Majzoub, E.H., Somerday, B.P., Goods, S.H., 

Gross, K.J., "Interactions between sodium 

aluminum hydride and candidate containment 

materials", Proceedings Conf. Hydrogen Effects 

on Material Behavior and Corrosion Deformation 

Interactions, to be published 

9. Sandrock, G., Gross, K., Thomas, G., Jensen, C., 

Meeker, D., Takara, S. J. Alloys and Comps 2002; 

v.330, p.696-701 

10. Gross, K.J., Sandrock, G., Thomas, G.J.	 J. Alloys 

and Comps 2002; v.330, p.691 

FY 2003 Publications 

1. “The Reversible Hydrides Solution for Hydrogen 

Storage”, K.J. Gross, presented at the G-CEP 

Hydrogen workshop, Stanford University, Palo 

Alto, CA, 2003 

 FY 2003 Progress Report 

2. “The Reversible Hydrides Solution for Hydrogen 

Storage”, K.J. Gross, E. Majzoub, National 

Hydrogen Association's 14th Annual U.S. 

Hydrogen Conference, Washington, D.C., 2003 

3. “Hydrogen Storage In Metal Hydrides”, K.J. 

Gross, presented at the Hydrogen 2002 

International Workshop on Hydrogen in Materials 

& Vacuum Systems, 2002 Jefferson Lab, Newport 

News, VA. 

4. “Titanium-Halide Catalyst-Precursors in Sodium 

Aluminum Hydrides,” E. Majzoub, K.J. Gross, 

presented at the International Conference on 

Metal Hydride Systems, Annecy France, 2002 

5. “Sodium Alanates: From Principle to Practice,” 

K.J. Gross, E. Majzoub, presented at the
 

International Conference on Metal Hydride
 

Systems, Annecy France, 2002
 

6. “New Reversible Complex Hydrides for Practical 

Hydrogen Storage”, K.J. Gross, E. Majzoub, 

World Hydrogen Energy Conference, 2002, 

Montréal, Canada 

Special Recognitions & Awards/Patents 

Issued 

1. Sandia National Laboratories internal funding 

through Laboratory Directed Research and 

Development grants: 1) Alanate-hydride fuel cell 

demonstration project (Gross), 2) Transition metal 

catalyzation of sodium aluminum hydrides 

(Majzoub) 

7 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Complex Hydrides for Hydrogen Storage 

Darlene K. Slattery (Primary Contact), Michael D. Hampton 

Florida Solar Energy Center, University of Central Florida 

1679 Clearlake Road 

Cocoa, Florida 32922 

Phone: (321) 638-1449; Fax: (321) 638-1010; E-mail: dkslatt@fsec.ucf.edu 

DOE Technology Development Manager: Carole Read 

Phone: (202) 586-3152; Fax: (202) 586-9811; E-mail: Carole.Read@ee.doe.gov 

Objectives 

•	 Identify complex hydrides containing greater than 6 wt% hydrogen 

•	 Obtain or prepare target compounds 

•	 Investigate hydrogen release and reversibility of target compounds 

•	 Maximize kinetics and reversible content of most promising materials 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

•	 B. Weight and Volume 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

Approach 

•	 Select target compounds with greater than 6 wt% hydrogen 

•	 Purchase or synthesize target compounds 

•	 Determine hydrogen release/uptake characteristics of pure compounds 

•	 Determine effects of ball milling on hydrogen release/uptake characteristics of pure compounds 

•	 Determine effects of catalysts on hydrogen release/uptake characteristics 

Accomplishments 

•	 Identified alanates and borohydrides with greater than 6 wt% hydrogen 

•	 Obtained or synthesized most promising compounds 

•	 Studied solvent-free synthetic procedures 

•	 Identified lithium alanate as a promising candidate 

•	 Completed in-depth study of hydrogen release characteristics of lithium alanate 

•	 Identified ball milling as the cause of lowered dehydriding temperature 

•	 Studied effects of incorporation of Ti, TiCl3, TiCl4, TiH2 AlCl3, Ni, Fe, FeCl3, C, and V on lithium 

alanate hydrogen release 

•	 Found that Ti and TiH2 caused minimal decrease in hydrogen content 

•	 Discovered that elemental titanium, ball milled with sodium alanate, facilitates rehydriding 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Complete investigation of exothermic decomposition of lithium alanate 

• Study the reversibility of catalyzed lithium alanate 

• Synthesize solvent-adduct free magnesium alanate 

• Investigate decomposition products and reversibility of borohydrides 

Introduction 

Studies involving complex hydrides of 

aluminum so far reported in the literature have been 

primarily restricted to sodium aluminum hydride 

with a smaller amount of work reported involving 

lithium aluminum hydride. While these studies are 

important from a fundamental and mechanistic point 

of view, they do suffer two serious limitations. One 

limitation is that the reversible hydrogen capacity of 

sodium aluminum hydride falls short of the hydrogen 

content required for practical application. A second 

limitation arises from the very complex nature of the 

alanates. Progress in understanding the mechanisms 

of hydrogen uptake and release and catalyst function 

in these systems is hampered by data interpretation 

based on questionable chemistry. For example, in 

one study,1

 it was reported that the ball milling of 

TiCl3 with NaAlH4 resulted in the reduction of 

titanium by the Na in NaAlH4. This conclusion was 

supported by the comparison of the TiCl3-NaAlH4 

system to an industrial process in which TiCl4 is 

reduced by hot elemental Na. These two systems are 

not comparable. In NaAlH4, Na is in the Na+ form 

and is incapable of reducing anything. The industrial 

process utilizes elemental sodium, an excellent 

reducing agent. This form of sodium is capable of 

functioning as a reducing agent because it has an 

electron to lose, forming Na+ in the process. The 

work described in that report is excellent from a 

physics, solids, and materials point of view. 

However, the mechanistic error punctuates the need 

for multidisciplinary teams, including chemists as 

well as physicists and materials scientists, to solve 

the hydrogen storage problem. 

While the recent advances in hydride storage by 

the research groups of Bogdanovic,2 Jensen,3 

Zaluski,4 and Gross5 have illustrated the reversibility 

of select complex hydrides, none have been shown to 

contain the required amount of hydrogen. 

Additionally, some of the contradictions and 

inaccuracies in the published work illustrate the need 

for more in-depth investigations from a chemical 

viewpoint. Because of the low reversible hydrogen 

content in the compounds that others are studying, 

this work has purposely targeted complex hydrides 

that theoretically contain hydrogen at a higher level 

than does the sodium aluminum hydride. 

Approach 

The literature was surveyed for known complex 

hydrides of aluminum and boron that contain greater 

than 6% hydrogen. Of the compounds revealed, 

those that were commercially available were 

purchased. Those with reported literature syntheses 

were prepared according to those methods. For those 

without reported syntheses, procedures were 

developed. Both wet chemical and solvent free 

synthetic procedures were investigated. 

The compounds were subjected to a baseline study 

to determine the onset temperatures and rates of 

hydrogen release, and the reversibility of the process 

in the uncatalyzed form. This part of the work 

revealed the need for additional study of lithium 

alanate due to its unusual characteristic of exothermic 

dehydrogenation and large hydrogen content. 

Following the baseline study, the effects of 

catalysts on the reversibility of the dehydrogenation 

were studied. Because the catalysts were 

incorporated using a high-energy ball milling, the 

effects of ball milling alone were also investigated. 

Results 

The primary goal of this project was to 

investigate a series of complex hydrides of aluminum 

and/or boron, with large hydrogen contents, as 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

hydrogen storage media. The compounds originally 

considered contain a minimum of 7.5% hydrogen by 

mass. While some of these hydrides have been 

reported to decompose to compounds that still 

contain one or more hydrogens, the numbers shown 

below reflect total hydrogen content. A secondary 

goal was to identify a catalyst for each hydride that 

facilitates decomposition while enabling 

rehydrogenation. 

The hydrides originally considered were NaAlH4 

with 7.5% H, Ca(AlH4)2 with 7.7% H, Zr(BH4)3 

with 8.8% H, Ti(AlH4)4 and Mg(AlH4)2 both with 

9.3% H, NaBH4 and LiAlH4 both with 10.5% H, 

Ca(BH4)2 with 11.4% H, Fe(BH4)3 with 11.9% H, 

Ti(BH4)4 with 12.9% H, Mg(BH4)2 with 14.8% H, 

LiAlH4(BH4)4 with 15.2% H, LiBH4 with 18.2% H, 

and Al(BH4)3 with 20.0% H. 

Because dehydriding is typically endothermic, 

we decided to investigate the observed exothermic 

dehydrogenation of LiAlH4. The thermogram for 

LiAlH4, Figure 1, shows that three exothermic 

events, with onset temperatures of 139°C, 157°C, 

Figure 1.	 Thermogram (top) and Pressure Plot 

(bottom) for the Thermal Decomposition of 

LiAlH4 

 FY 2003 Progress Report 

and 169°C, respectively, were associated with the 

decomposition of LiAlH4. The pressure data indicate 

that gas release, most likely hydrogen, began at 

approximately 110°C but reached a maximum rate at 

a temperature corresponding to the onset temperature 

of the first exothermic event in the thermogram. This 

release continued until approximately 4% of 

hydrogen was released. Then, the hydrogen release 

sharply slowed at approximately 170°C, 

corresponding to the onset temperature of the third 

exothermic event in the thermogram. This slower 

hydrogen release continued until approximately 

6.3% hydrogen was lost. The first and third 

exothermic events in the thermogram were thus 

associated with hydrogen release, and the second 

event was most likely a phase change that occurs 

with no gas release. 

Catalyst studies were begun with titanium using 

the mechanical incorporation method suggested by 

Jensen, et al.3

 Ball milling LiAlH4 with TiCl4 did 

decrease the temperature required for 

dehydrogenation, as was reported by Jensen in his 

study of NaAlH4. As was also reported by Jensen in 

his work with NaAlH4, the hydrogen content was 

significantly decreased due to the fact that the Ti4+ 

was reduced during the ball milling process, causing 

loss of a portion of the stored hydrogen. The 

reducing agent for this process must have been the 

alanate ion, AlH4-, since neither Li+ nor Na+ is 

capable of such a reaction. The resulting NaCl was a 

difficult-to-remove, non-hydriding contaminant, 

further decreasing hydrogen capacity. 

The pressure plots obtained by dehydriding 

undoped LiAlH4, LiAlH4 milled alone, and LiAlH4 

samples doped with Ti, TiCl3, TiCl4, and TiH2 can be 

seen in Figure 2. Doping with titanium(III) chloride 

and with titanium(IV) chloride both result in a greatly 

decreased hydrogen release due to the loss of the first 

hydrogen release step. Doping with TiH2 or with 

elemental titanium causes only a slight decrease in the 

amount of hydrogen released and does not eliminate 

the first step of hydrogen release. Thus, it is hoped 

that incorporation of either of these catalysts will 

result in allowing lithium alanate to reversibly bind 

hydrogen while retaining a large hydrogen content. 

Ball milling alone results in about the same 

decrease in the amount of hydrogen released as doping 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

with either TiH2 or Ti. Most interesting is the fact that 

ball milling alone causes the same reduction in the 

temperature of hydrogen release as does doping. 

Figure 3 shows the differential scanning 

calorimetry (DSC) pressure data for the thermal 

decomposition of LiAlH4 samples that were ball 

milled with AlCl3, Ni, Fe, FeCl3, carbon black, and 

with V. Nickel caused a small decrease in the 

amount of hydrogen released, while vanadium 

caused a larger decrease. The effect of nickel 

Figure 2.	 DSC Pressure Data for Dehydriding of 

LiAlH4 Doped with Ti, LiAlH4 Doped with 

TiCl3, LiAlH4 Doped with TiCl4, LiAlH4 

Doped with TiH2, and LiAlH4 Ball Milled 

without Doping 

Figure 3.	 DSC Pressure Data for the Thermal 

Decomposition of LiAlH4 Samples That 

Were Ball Milled with AlCl3, Ni, Fe, FeCl3, 

Carbon Black, and with V 

 FY 2003 Progress Report 

appeared to be limited to the first step of hydrogen 

release, while vanadium appears to have decreased 

the amount of hydrogen released from both steps of 

the decomposition. Incorporation of aluminum 

chloride or elemental iron produced the same effect 

on the temperature of hydrogen release. However, 

the iron also appears to have caused a decrease in the 

amount of hydrogen released in the first step. 

Iron(III) chloride caused a reduction in the hydrogen 

release temperature. However, this temperature 

decrease was accompanied by a significant decrease 

in the amount of hydrogen released in both 

decomposition steps. 

Conclusions 

•	 Synthesis of a number of alanates and borohydrides investigated 

- Wet chemical methods used for synthesis of 

magnesium alanate, magnesium borohydride, 

and calcium borohydride 

- Solvent free methods used for Mg(AlH4)2, 

Mg(BH4)2, a magnesium hydride/titanium 

hydride mixture, Ti(AlH4)4 and Ti(BH4)4 

- Synthesis of Mg(AlH4)2 solvent adduct 

accomplished 

- Wet chemical methods yielded solvent adducts 

that decomposed upon solvent removal 

- Solvent free synthetic methods identified as 

having greatest potential 

•	 Lithium alanate is a potentially viable hydrogen 

storage compound 

- Large hydrogen capacity 

- Decomposition is exothermic 

- Decomposition mechanism varied with 

material manufacturer 

- Decomposition of ball milled Lancaster sample 

resembles Aldrich sample 

- Improved kinetics and reduced dehydriding 

temperature result from ball milling 

•	 Effects of catalysts on dehydrogenation of lithium alanate studied 

- Addition of TiCl3, TiCl4, or FeCl3 results in 

large reduction of hydrogen content 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- Addition of V results in the same decrease in 

hydrogen release temperature but with smaller 

loss in hydrogen capacity 

- Addition of Fe, AlCl3, Ni, C, Ti, or TiH2 

results in a decrease in the temperature of 

hydrogen release without a significant loss of 

H2 capacity 

• Temperatures similar to those of 

undoped, ball milled material 

•	 Mechano-chemical synthetic procedures for 

complex hydrides studied 

References 

1. G. Sandrock, K.J. Gross, G. Thomas, J. Alloys 

Comp. 339, 299 (2002). 

2. B. Bogdanovic, R.A. Brand, A. Marjanovic, M. 

Schwickardi, and J. Tolle, J. Alloys and 

Compounds, 302, 36 (2000). 

3. C.M. Jensen, R. Zidan, N. Mariels, A. Hee, and C. 

Hagen, Int. J. Hydrogen Energy, 24, 461 (1999). 

4. L. Zaluski, A. Zaluska, and J.O. Ström-Olsen, J. 

Alloys and Compounds, 290, 71 (1999). 

5. K.J. Gross, G.J. Thomas, and C.M. Jensen, J. 

Alloys and Compounds, 330-332, 683 (2002). 

FY 2003 Publications/Presentations 

1. Slattery, D.K.; Hampton, M.D., "Complex 

Hydrides for Hydrogen Storage," presented at 

the Alanate Working Group meeting at Argonne 

National Lab, August 15, 2002. 

2. Slattery, D.K.; Hampton, M.D.; Lomness, J.K.; 

Najafi-Mohajeri, N.; Franjic, M., "Hydrogen 

Storage Using Complex Hydrides," Presented at 

the 225th National Meeting of ACS, New 

Orleans, LA, March 25, 2003. 

3. Slattery, D.K.; Hampton, M.D., "Complex 

Hydrides for Hydrogen Storage," Proceedings of 

the 2003 U.S. DOE Hydrogen and Fuel Cells 

Annual Program/Lab R&D Review, Berkeley, 

CA, May 19-22, 2003. 

4. Slattery, D.K.; Hampton, M.D.; Lomness, J.K.; 

Najafi-Mohajeri, N.; Franjic, M., "Hydrogen 

Storage Using Complex Hydrides," Fuel 

Chemistry Division Preprints, 2002, 48(1), 277. 

5. Franjic, M.; Lomness, J.; Gilbert, J.; Hampton, 

M.; Slattery, D., "Effect of Ti Catalyst on 

Hydrogen Storage Properties of LiAlH4," 67th 

Annual Meeting Florida Academy of Sciences, 

Orlando, FL, March 21-22, 2003. 

6. Hampton, M.D.; Slattery, D.K.; Jafafi-Mohajeri, 

N.; Franjic, M.; Lomness, J.K., "Complex 

Hydrides as Hydrogen Storage Media," 

Symposium P1, "Hydrogen Electrochemistry and 

Generating Systems," Proceedings of the 203rd 

Meeting of the Electrochemical Society, Paris, 

France, April 27 - May 2, 2003. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based 

Complex Compound Hydrides 

Donald L. Anton (Primary Contact), S.M Opalka & D.A. Moser 

United Technologies Research Center 

411 Silver Lane 

E. Hartford, CT, 06108 

Phone: (860) 610-7174; Fax: (860) 610-7253; E-mail: antondl@utrc.utc.com 

DOE Program Manager: JoAnn Milliken 

Phone: (202) 586-2480; Fax: (202) 586-1637; E-mail: JoAnn.Milliken@ee.doe.gov

 Subcontractors: 

Hydrogen Components Inc., Littleton, CO 

QuesTek, LLC, Evanston, IL 

Objectives 

•	 Improve the charging and discharging rates of the NaAlH4 based hydrogen storage medium. 

Specifically, in collaboration with other efforts:
 

- Increase the reversible weight fraction of hydrogen stored to 7.5% from the current 5.5% 

- Enhance the hydrogen evolution rate from 0.1 wt%/hr at 80°C to 0.55 wt%/hr to meet fuel cell 

demands 

- Increase the regeneration rates from the documented 0.5 wt%/hr to 90 wt%/hr to achieve the five 

minute refill requirement 

•	 Determine the safety and risk factors associated with enhanced compositions 

•	 Design, develop and evaluate a hydrogen storage system having a 5 kg hydrogen capacity and 

installation capability in a fuel cell powered mid-size sedan
 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

•	 B. Weight & Volume 

•	 D. Durability 

•	 E. Refueling Time 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

Approach 

•	 Create combined atomistic/thermodynamic models of the NaAlH4 system to determine catalyzed 

compositional ranges, sorption mechanisms and the effects various catalyst additions have on these 

mechanisms. 

•	 Cyclically evaluate selected Complex Compound Hydride (CCH) compositions to determine 

degradation mechanisms and ameliorations as well as compatibility with construction materials. 

•	 Conduct standardized safety testing related to the classification of hazardous materials. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Develop preliminary designs through the evaluation of existing systems, generation of weight/volume/ 

cost improvements, and high level optimization to balance automotive demands. 

•	 Perform heat and mass flow modeling for detailed optimization of the required system volume, mass 

and hydrogen sorption characteristics. Evaluate methods to enhance heat conduction into the CCH 

powder. 

•	 Fabricate and evaluate 1 kg H2 and 5 kg H2 capacity hydrogen supply systems. 

•	 Conduct preliminary system performance modeling analyses of the combined proton exchange 

membrane fuel cell (PEMFC)/H2 storage system under steady state and transient conditions to 

establish system optimization and dynamic control requirements. 

Accomplishments 

•	 Applied atomistic/thermodynamic modeling to complex compound hydrides successfully. 

•	 Completed safety experiments resulting in no change in transportation packing class for these 

materials from their unmodified condition.
 

•	 Characterized two alanate compositions for sorption kinetics. 

•	 Identified preliminary design and materials of construction based on volume, mass and cost estimates. 

•	 Completed sub-component models and trials. 

Future Directions 

•	 Complete design of the first 1 kg hydrogen 

storage system designated CCHS#1. 

•	 Identify catalyzed NaAlH4 media 

composition from characterized
 

compositions.
 

•	 Complete fabrication, media catalyzation 

and loading of CCHS#1. 

•	 Evaluate system operating characteristics, 

hydriding and dehydriding rates, and system 

volumetric and gravimetric densities 

utilizing laboratory supplied heat and 

hydrogen. 

•	 Initiate system modeling efforts based on 

previously understood fuel cell and balanceof-plant models. 

Introduction 

One of the most significant barriers to the 

widespread application of hydrogen-based 

propulsion is the development of on-board storage 

systems which can provide the needed quantity of 

hydrogen with acceptable volume, weight, cost and 

safety risk. The major classes of established 

hydrogen storage methods - compressed gas, liquid, 

metal hydrides and chemical hydrides - all have 

advantages and disadvantages, but none is clearly 

superior for automotive transportation. In particular, 

a disadvantage of metal hydrides is their low 

hydrogen capacities of less than 2 wt% for alloys 

with discharge temperatures such that the waste heat 

of a PEMFC (~ 90 °C) can be used to release the 

hydrogen. Many chemical hydride materials, while 

having high capacities, are classified as irreversible, 

which requires that the entire material be replaced 

during refueling rather than simply charged with 

hydrogen gas. This project is focusing on the 

reversible chemical hydride, NaAlH4, with a 

theoretical hydrogen capacity of 5.5 wt%, and seeks 

to enhance the material for improved charging and 

discharging rates as well as increased capacity. 

Safety studies of the enhanced material will be 

conducted to support the technology as it is driven 

toward commercialization. 

The project also seeks to apply this material in 

the development of a system which will reversibly 

store a high wt% of hydrogen at low pressure for an 

indefinite amount of time. The storage system which 

contains the CCH powder must serve two primary 

functions: (1) exchange heat between the powder and 

a working liquid to drive the absorption/desorption of 

hydrogen; (2) support elevated hydrogen pressure 

during refueling. These functions must be performed 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

with a minimum of weight, volume and cost. In 

addition, there are other secondary characteristics 

such as (i) allowing for significant volumetric change 

of the powder, (ii) exchanging hydrogen without the 

loss of the fine CCH powder particles, (iii) 

maintaining chemical compatibility with the CCH 

powder and hydrogen, (iv) producing minimal 

impurities going to the PEMFC, and (v) fitting into a 

conformable volume. 

Approach and Results 

Atomistic models were created utilizing the Figure 1. Atomistic Model Depicting Insertion of Ti+3 

Vienna Ab-initio Simulation Package (VASP) of Cation into NaAlH4 Super-Cell Substituting 

NaAlH4, Na3AlH6 and NaH using known lattice for Al+3 Cation after Volume and Energy 

Relaxation parameters and atomic occupation sites. Full volume 

and site relaxations were allowed with resulting 

structures nearly identically replicating literature 

values. Catalyst substitutions of Ti+3, V+3, Zr+4 and 

Li+1 were made in both the NaAlH4 and Na3AlH6 

structures with transition metal substitution for Al+3 

cations and alkaline metal substitutions for Na+1 

cations showing the lowest lattice energy, by far (see 

Figure 1). Lattice enthalpy (DH) calculations were 

performed on various "compositions" of catalysts 

from which thermodynamic calculations utilizing 

ThermoCalc were able to determine free energy of 

formation, DG. From the free energy determinations, 

the vant Hoff plots for various compositions of 

catalyst were calculated, see Figure 2. The results of 

these calculations indicate catalyst additions modify 

the thermodynamics of hydrogen sorption and thus 

play a far more significant role than simple 

heterogeneous catalysis as referred to in the 

literature. 

An equation depicting the rate of a chemical temperature, and pressure, respectively. Figure 3 

reaction as a function of temperature, pressure and depicts the modeled rates of reaction and 

composition taken from Reference 1 which was first experimental verification of the model with very 

implemented in modeling of LaNi5 hydrogen storage good agreement resulting. These equations can be 

beds is defined as: solved simultaneously for the sorption rates of 

Figure 2. Vant Hoff Plot of Calculated Pressure 

Equilibria for 2 & 6 m% Ti+3 Substituted 

NaAlH4 and Na3AlH6 

NaAlH4 and Na3AlH6 respectively. Given these 





Pe − P 



 



dC1 exp 



−

where Ci is the composition; Pe,i is the plateau 

E1
 

RT
 

rates of reaction and the heats of reaction developed 

elsewhere, a spatially resolved temperature 

















 ( )χ1 C2 

,1 =
 A1 

*
 *

dt r 1  Pe,1  distribution can be modeled utilizing a finite element 

method (FEM) code. These calculations were 

carried out using various preliminary system designs, 

pressure for composition i; Ai, Ei and Ci are heating fluid temperatures, etc. Figure 4 shows the 

experimentally determined constants for reaction i; results of three such simulations for differing 

and t, R, T and P are the time, gas constant, numbers of heat transfer fluid conduits. 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Comparison of Calculated and Measured 

Hydrogen Absorption and Desorption Figure 5. Time/Temperature Plot of Partially 

Discharged Material Heated to 100°C in Air 

Showing Various Oxidation Events 

Figure 4. Temperature Distribution at 1400 sec. after 

Charging at 100 Bar H2 

A series of experiments were conducted to 

measure the reactivity of the catalyzed CCH media in 

contact with either water or air. Experimental details 

were taken from two sources: DOT/UN Doc., 

Recommendations on the Transport of Dangerous 

Goods, Manual of Tests and Criteria [Reference 2], 

and from ASTM E1226, Dust Explosion Testing. 

Tests were conducted in three materials states: fully 

charged, primarily NaAlH4; partially discharged, 

composed of a mixture of Na3AlH6 and Alo powder; 

and fully discharged, composed of NaH and Alo 

powders. Various combinations of water and air 

contact and ambient and elevated temperatures were 

included in the testing protocols. The results of these 

tests confirmed that these compounds are water and 

humidity reactive, but their packaging and handling 

classifications do not change with the addition of 

catalysts. The hexa-hydride materials were 

somewhat more reactive in spontaneous ignition and 

burn rate testing than either of the other 

compositions. 

The results of one test are depicted in Figure 5 

where the partially discharged material was packed 

into a 25 cm3

 cube, loaded into a furnace and heated 

in air to 100°C. The temperature vs. time plot given 

in Figure 5 shows the development of oxidation 

reactions in which a thermocouple is inserted into the 

powder. Two reactions are clearly observed, one 

initiating at approximately 200°C which is thought to 

be dehydrogenation of the Na3AlH6 compound, and 

the other initiating at ~850°C thought to be 

dehydrogenation of NaH. Oxidation of Nao and Alo 

metals proceeds exothermically to temperatures 

greater than 1200°C where the thermocouple failed. 

Conclusions 

1. Numerous experiments were carried out on 

catalyzed NaAlH4 in various phases of 

decomposition. The results indicate these 

materials to be flammable when in contact with 

water or water vapor in the air. The partially 

discharged material containing a mixture of 

Na3AlH6 and aluminum powder was found to be 

somewhat more reactive than the fully charged 

material, but in all cases, the packing 

classification did not change. 

4 
 

 

Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

2. Significant advances have been made in modeling 

of the media utilizing a combination of atomistic 

and thermodynamic methods which has proven to 

be state-of-the-art in its methodology and 

enlightening in its results. If the catalytic 

additions can be made to stay within the host 

structure, upon repeated sorption cycles, the full 

5.5 wt% of hydrogen should be accessible at 

pressures above 1 bar. 

3. An analytical expression for hydrogen sorption 

rates was identified in the literature and utilized in 

conjunction with known thermodynamic values to 

predict temperatures in simulated hydrogen 

storage systems. 

References 

1. M.A. El Osairy, I.A. El Osairy, A.M. Metwally 

and M.M. Keshik, On the Optimization and 

Convective Hydrogen Storage Bed Model Using 

LaNi5H6 or FeTiH1.6, Int. J. Hydrogen Energy, 17, 

17, pp.961-64 (1992). 

2.	 DOT/UN Doc., Recommendations on the Transport of 

Dangerous Goods, Manual of Tests and Criteria, 3rd 

Revised Ed., ISBN 92-1-139068-0, (1999). 

FY 2003 Publications/Presentations 

1. D.L. Anton, High Density Hydrogen Storage 

System Development, IEA Task XVII, Fall 2002, 

Geneva. 

2. D.L. Anton, High Density Hydrogen Storage 

System Development, IEA Task XV, Spring 2003, 

Stockholm. 

3. D.L. Anton, Hydrogen Desorption Kinetics in 

Transition Metal Modified NaAlH4, MH2002, 

Annecy, France, Sept. 2002. 

4. S.M. Opalka, First Principles Study of SodiumAluminum-Hydrogen Phases, MH2002, Annecy, 

France, Sept. 2002. 

5. D.L. Anton, Hydrogen Desorption Kinetics in 

Transition Metal Modified NaAlH4, J. Alloys & 

Compounds, (in press). 

6. S.M. Opalka and D.L. Anton, First Principles 

Study of Sodium-Aluminum-Hydrogen Phases, J. 

Alloys & Compounds, (in press). 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Discovery of Novel Complex Metal Hydrides for Hydrogen Storage through 

Molecular Modeling and Combinatorial Methods (New FY 2004 Project) 

Dr. David Lesch 

UOP Research Department 

25 E. Algonquin Road 

Des Plaines, IL. 60017-5017 

Phone: (847) 391-3894; Fax: (847) 391-3550; E-mail: dalesch@uop.com 

DOE Technology Development Manager: Carole Read 

Phone: (202) 586-3152; Fax: (202) 586-9811; E-mail: Carole.Read@ee.doe.gov 

Objectives 

To discover complex metal hydrides for hydrogen storage that contain 6% or more of hydrogen and can 

reversibly desorb hydrogen between -40 and 90oC 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 	 

•	 B. Weight and Volume 

•	 M. Hydrogen Capacity and Reversibility 

Approach 

The objective of the proposed project is to 

discover complex metal hydrides for hydrogen 

storage which contain 6% or more of hydrogen and 

can reversibly desorb hydrogen between -40 and 

90oC. The project will combine molecular modeling 

with high-throughput combinatorial material 

synthesis, testing and characterization, large-scale 

materials testing, and system engineering studies to 

produce prototype commercially viable hydrogen 

storage systems. 

The focus of the first project year is to establish, 

validate and demonstrate the combinatorial tools and 

molecular modeling approach, while initiating 

materials discovery experiments. Specific first year 

objectives include: 

•	 Refine technical requirements 

•	 Develop and validate medium-throughput (parallel) synthesis, screening and characterization tools 

•	 Design and implement the high-throughput solution and solid-phase synthesis, screening and 

characterization tools 

•	 Develop theoretical methods to predict equilibrium structures of complex hydrides 

•	 Finalize material classes for the second year 

screening studies 

•	 Begin screening experiments on complex metal 

hydrides in the medium-throughput system 

The focus throughout the second year will 

include screening studies of candidate hydrogen 

storage materials. Screening will continue in the 

medium-throughput system while validating the 

high-throughput system, after which both systems 

will be used. Detailed modeling and characterization 

studies will guide screening toward materials likely 

to have thermodynamics required to meet the DOE 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

technical targets. Modeling and characterization and 

the results from the screening studies will be used to 

identify mechanisms of action in new materials. 

Specific second year objectives include: 

•	 Validate the high-throughput synthesis and testing system 

•	 Perform screening studies (medium and high 

throughputs) on expanded classes of complex 

metal hydrides 

•	 Perform modeling studies to predict the thermodynamics of novel complex hydrides 

•	 Conduct detailed characterization studies on 

promising candidates 

•	 Advance mechanistic understanding of new 

complex metal hydrides 

•	 Evaluate and select most promising classes/candidates for optimization studies in the third year 

 FY 2003 Progress Report 

The goal of the third project year is to produce an 

economical hydrogen storage system by optimizing 

hydride catalyst combinations, scaling them up for 

commercial testing, and performing analyses to 

assess the economic value of the resulting hydrogen 

storage system. Specific third year objectives 

include: 

•	 Predict phase diagrams of candidate materials 

from empirical data and theoretical predictions 

•	 Optimize hydride/catalyst combinations 

•	 Demonstrate successful scale-up and design prototype hydrogen storage systems 

•	 Conduct engineering analyses to verify suitability to meet DOE technical targets 

•	 Analyze economic factors to establish commercial viability 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Sub-Nanostructured Non-Transition Metal Complex Grids for Hydrogen Storage 

(New FY 2004 Project) 

Orhan Talu, Ph.D. 

Chair and Professor, Department of Chemical Engineering 

Stilwell Hall Room 466 

1960 East 24th Street 

Cleveland, Ohio 44115-2425 

Phone: (216) 687-3539; Fax: (216) 687-9220; E-mail: o.talu@csuohio.edu 

DOE Technology Development Manager: Carole Read 

Phone: (202) 586-3152; Fax: (202) 586-9811; E-mail: Carole.Read@ee.doe.gov 

Objectives 

To grow sub-nanostructured metal grids for hydrogen absorption in storage applications 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Storage section of the Hydrogen, 

Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• M. Hydrogen Capacity and Reversibility 

Approach The major tasks involved in this project are: 1) 

zeolite growth and treatment, 2) cathode preparation, 

The primary goal of this project is to grow sub- 3) electrochemical growth, 4) physical 

nanostructured metal grids for hydrogen absorption characterization, 5) chemical characterization and 

in storage applications. Sub-nanostructuring will: performance evaluation. 

1. Increase hydrogen molecule dissociation rate 

on the active sites 

2. Increase hydrogen atom transport rate into the 

metal 

3. Decrease performance degradation by cycling 

caused by decrepitation 

4. Increase heat transfer in the metal matrix 

5. Increase hydrogen uptake 

This novel approach involves electrochemically 

growing the metal phase, an atom at a time, in a subnanostructured “mold.” The mold will be made from 

known zeolites including the recently discovered 

titanium silicate, which has unique structural 

characteristics. The energy required for the growth is 

minimal; it is equal to the electron charge (times the 

valence) per metal atom. 

Task 1. Zeolite Growth and Treatment: It is 

necessary to grow zeolite crystals with the required 

morphology to obtain a uniform film on the cathode. 

Normal growth of zeolites involves hydrothermal 

synthesis between 150-300o

C under autonomous 

pressure in autoclaves. The crystal morphology is 

controlled by the solution chemistry (which may 

include inert additives) and time-temperature 

combination. The alumina/silica ratio of zeolites is 

controlled during synthesis to optimize the density of 

exchangeable cations. In addition to morphology, the 

formulations must be optimized for optimum cation 

density and for ease of zeolite mold removal after the 

metal grids are grown. 

Task 2. Cathode Preparation: Cathode 

preparation is the most significant technical hurdle in 

this project. The cathode coated with zeolites must 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

not have any macroscopic pathway for cations to 

diffuse. This requires mechanical compacting and/or 

polymer patching and/or in-situ growth of the zeolite 

around the electrode. We will start with readily 

available powders in our labs to gain experience in 

cathode preparation. Later, we will switch to 

specially grown powders in Task 1 to minimize the 

macropores. 

Task 3. Electrochemical Growth: This is the 

heart of the process, where the metal grid is 

electrochemically grown in the zeolite micropores 

one atom at a time. We will start electrochemical 

growth with electrodes prepared by mechanical 

compaction with readily available powders to gain 

experience with electrochemical growth. Later, we 

will switch to specially prepared electrodes. In all 

cases, the growth kinetics will be closely monitored. 

Task 4. Physical Characterization: The metal 

grids will be first physically characterized by using 

standard techniques such as optical and scanning 

electron microscopy for morphology, x-ray 

fluorescence for non-destructive and wet-chemistry 

including atomic absorption as destructive elemental 

analysis, atomic force mocroscopy/scanning 

tunneling microscopy for nano-structure analysis, 

 FY 2003 Progress Report 

and simple density measurements. Only samples that 

show acceptable nano-structure will be chemically 

characterized after zeolite mold removal. 

Task 5. Chemical Characterization and 

Performance Evaluation: Analysis of equilibrium 

and kinetic data coupled with physical property data 

enable hydrogen storage performance calculations 

including mass balances, energy balances, estimated 

charge/discharge times (under isothermal 

conditions), etc. The performance calculations will 

be based on the packing material rather than the 

overall system. The performance will be compared 

to available data for other approaches and to the 

target values. 

During the first year of the project, it will be 

determined whether pure metal grids can be grown 

that have equilibrium and/or kinetic performance 

better than the same metal in bulk phase. In the 

second year, the cathode preparation method will be 

finalized, and sub-nanostructured non-transition 

metal complex grids will be grown. In the third year, 

anode preparation and electrolyte chemistry will be 

finalized, an analysis will be completed of projected 

hydrogen storage, and an evaluation/cost estimate 

will be completed. 

2 
________________________________________________________________________ 

III.B.7. Complex Hydride Compounds with Enhanced Hydrogen 

Storage Capacity (New FY 2004 Project) 

Don Anton 

United Technologies Research Center 

411 Silver Lane 

East Hartford, CT 06108 

Phone: (860) 610-7174; Fax: (610) 610-7879; E-mail: antondl@utrc.ut.com 

DOE Technology Development Manager: Carole Read 

Phone: (202) 586-3152; Fax: (202) 586-9811; E-mail: Carole.Read@ee.doe.gov 

Objectives 

• Develop a reversible, 7.5 hydrogen wt.% capacity complex hydride with the kinetics 

required for automotive PEM fuel cell operation, which can be cyclically discharged 

and recharged for 500 cycles. 

• Prepare such a storage media in sufficient quantities to enable evaluation in a 

subscale hydrogen storage system. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of 

the Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Weight and Volume 

• M. Hydrogen Capacity and Reversibility 

• N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

Approach 

The goal of the project is to develop a new 

complex hydride compound capable of 

reversibly storing hydrogen with capacity 

greater than 7.5 wt.% for 500 regeneration 

cycles with 100% efficiency. The project 

will develop, prepare and deliver such a 

storage media in sufficient quantities to 

enable evaluation in a sub-scale hydrogen 

storage system being developed under the 

DOE contract “High Density Hydrogen 

Storage System Demonstration Using 

NaAlH4 Based Complex Compound 

Hydrides.” 

The objective of this project is to discover 

new reversible high hydrogen content 

complex hydride compounds of the structure 

NayM+ix(AlH4)y+ix, in the quaternary phase 

space between sodium hydride (NaH), alane 

(AlH3), transition metal or rare earth (M) 

hydrides (MHz, where z= 1-3) and molecular 

hydrogen (H2). This project will encompass 

all of the technology development stages for 

identifying, developing and commercializing 

complex hydride compound hydrogen 

storage media to meet the DOE technical 

targets. The team will accelerate the 

discovery of new complex hydride 

compounds and guide experimentation with 

first principles modeling. Simultaneously, 

the team will apply multiple synthetic 

methodologies to isolate new hydrides, and 

couple thermodynamic predictions and 

structural characterizations to verify 

structures of newly identified phases. The 

team will conduct three levels of 

performance evaluations to select 

compositions for further development, 

optimize dehydrogenation and 

hydrogenation catalysis with spectroscopic 
mechanistic studies and first-principles 

screening simulations, develop 

manufacturing processes to reduce cost and 

scale-up production, and develop business 

analyses for the commercialization of 

hydrogen storage systems integrated with 

fuel cell power plants. 

The following tasks are planned for year 1. 

Task 1.0 First Principles Modeling 

• Predict new quaternary complex hydride 

compositions to recommend for 

synthesis targets 

• Evaluate the theoretical phase stability 

and reversible hydrogen content of the 

best quaternary complex hydride 

candidates, and identify new catalyzed 

quaternary compositions with decreased 

dehydrogenation activation barriers. 

• The compilation of a candidate structure 

list for ground state screening 

simulations from the structural and 

thermodynamic parameters of analogous 

compounds will be completed. 

• Present compositional section phase 

diagrams and pressure-compositiontemperature diagrams established to 

evaluate the phase stability and 

reversible hydrogen content of high 

capacity systems 

Task 2.0 Synthesis 

• Materials will be synthesized via three 

distinct processing routes: solid state 

processing, molten-state processing and 

solute based processing. Synthesis 

attempts will be performed on lithium 

and titanium alanate compounds and 

mixed sodium/lithium/titanium 

compounds. Following identification 

and synthesis of such phases, 5-10 g 

samples will be synthesized for 

performance evaluations. 

• Synthesis attempts will be performed on 

compounds and mixed sodium 

compounds, which are hypothesized to 

exist based on high catalytic activity and 

solubility in NaAlH4 

• Initial samples will be analyzed and 

processing iterated to synthesize 5-10 g 

samples for performance evaluation. 

• Analyses will yield data on the 

temperature and preliminary thermal 

properties of dehydrogenation reactions 

Task 3.0 Analysis 

• Thermodynamic variables will be 

determined for a selected number of 

compounds, which hold promise for 

enhanced hydrogen storage capability. 

This information will be used for abinitio model verification. 

• Once a new phase has been identified 

and a process developed to synthesize it 

in reasonable purity, it will be tested 

using a Sievert's apparatus specifically 

designed to measure solid/gas reaction 

kinetics. Each sample will be prepared 

identically to yield a comparative base 

between current state-of-the-art NaAlH4 

compounds under development and the 

new high hydrogen capacity materials 

being developed in this project. 

• Thermodynamic variables will be 

determined for a selected number of 

compounds, which hold promise for 

enhanced hydrogen storage capability. 

This information will be used for abinitio model verification. 

Task 4.0 Performance 

• Measure solid/gas reaction kinetics; 

confirm capacity 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Storage in Carbon Single-wall Nanotubes 

A.C. Dillon, K.E.H. Gilbert, P.A. Parilla, C. Horbacewicz, J.L. Alleman, K.M. Jones, and M.J. Heben 

(Primary Contact) 

National Renewable Energy Laboratory 

1617 Cole Blvd. 

Golden, CO 80305 

Phone: (303) 384-6641; Fax: (303) 384-6655; E-mail: michael_heben@nrel.gov 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Objectives 

•	 Develop reproducible hydrogen capacity measurements and sample preparation methods. 

•	 Meet the DOE hydrogen storage goals of 4.5 wt% H2, 1.2 kWh/L by 2005. 

•	 Optimize scalable methods for the production and purification of carbon single-wall nanotubes 

(SWNTs) and other nanostructured carbons for hydrogen storage. 

•	 Gain better understanding of the hydrogen adsorption mechanisms for carbon nanotube/metal 

composites, particularly the importance of how, and in what form, the metal is incorporated into the 

SWNTs. 

•	 Develop new methods for controlled metal incorporation in purified, cut SWNT samples. 

•	 Probe other carbon systems for potential high hydrogen storage capacities at near ambient conditions. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Cost 	 

•	 B. Weight and Volume 

•	 C. Durability 

•	 D. Refueling Time 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Physisorption and Chemisorption 

•	 O. Test Protocols and Evaluation Facilities 

•	 P. Dispensing Technology 

Approach 

•	 Establish Carbon Materials Working Group (CMWG) to develop sample handling and measurement 

protocols and improve reproducibility of capacity measurements. 

•	 Improve purification technique to efficiently remove graphite-encapsulated metal particles present in 

SWNT materials generated by a wide variety of techniques. 

•	 Develop a low-cost, gas-phase, continuous process for carbon nanotube production employing hot 

wire chemical vapor deposition (HWCVD). 

•	 Fabricate carbon nanotube samples containing iron particles of differing sizes and occurring at different 

but specific sites and determine the hydrogen storage properties of these highly specific samples. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Employ TiI4 vapor transport to deposit small Ti particles in purified, cut SWNT samples. Employ 

thermal evaporation of Ti to deposit thin metallic films on purified, cut SWNT samples. 

•	 Analyze the hydrogen storage properties of conducting carbon polymers supplied by Prof. Alan 

MacDiarmid at the University of Pennsylvania. 

•	 Analyze the hydrogen storage properties of HWCVD generated nano-crystalline graphite doped with 

iron nanoparticles. 

Accomplishments 

•	 Incorporated a CO2 oxidation step in the purification process to remove graphite-encapsulated metals 

more completely. 

•	 Developed a low-cost, scalable HWCVD technique for the continuous production of carbon multi-wall 

nanotubes (MWNTs) and demonstrated the potential of the same technique for SWNT production. 

•	 Discovered that the activation of hydrogen storage on carbon nanotubes at near ambient conditions is 

dependent on the incorporation of small metal particles in highly intimate contact with the tube structure. 

•	 Determined barriers to Ti incorporation via both vapor transport and evaporation, but gained 

significant knowledge to focus on efforts with higher likelihood of success in future investigations. 

•	 Discovered unanticipated hydrogen storage capacities on HWCVD generated nano-crystalline graphite 

doped with iron nanoparticles. 

•	 Performed preliminary assessment of the adsorption of hydrogen on conducting polymer samples 

provided by Prof. Alan MacDiarmid of the University of Pennsylvania. 

Future Directions 

•	 Establish, contingent upon DOE's approval, a DOE-sponsored Virtual Center of Excellence for the 

study and advancement of carbon-based hydrogen storage materials. The Center plans to bring 

together experts from national labs, universities and industry, including Nobel Laureate, Prof. Richard 

Smalley of Rice University, and Dr. Guido Pez of Air Products and Chemicals, Inc. 

•	 Gain a better understanding of the mechanistic processes associated with hydrogen binding on 

nanostructured carbon materials. 

•	 Develop reproducible methods to activate materials to high, room-temperature capacities (>4 wt%). 

•	 Utilize computational chemistry to provide a link to and guidance for experimental efforts. 

•	 Establish high-throughput experimental methods to rapidly evaluate nanostructured carbon hydrogen 

storage materials. 

•	 Use knowledge obtained from this year's research to establish a better method for the controlled 

incorporation of metal into nanostructured carbon materials. 

•	 Continue exploring alternative nanostructured carbon materials for room-temperature hydrogen 

storage, including aromatic cage compounds containing transition-metal ions. 

Introduction 

The decreasing fossil fuel supply and the 

growing number of densely populated metropolitan 

cities with poor local air quality have spurred an 

initiative to develop an alternative to petroleum 

motor fuels. Hydrogen, which may be produced 

from renewable sources, has emerged as one of the 

most promising candidates for the replacement of the 

current carbon-based energy services. Although 

hydrogen could supply all of the world’s vehicular 

energy demands1

, a major impediment to the 

implementation of this new fuel is the lack of a 

convenient, cost-effective on-board storage system. 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Compact, lightweight carbon adsorbent materials 

have become potential candidates for use in a 

hydrogen storage system. Of particular interest are 

the “engineered” nanostructured carbons such as 

carbon single-wall and multi-wall nanotubes 

(SWNTs and MWNTs) and graphitic nanoparticles or 

cages. Interestingly, the presence of small quantities 

of transition metals has been shown to enhance the 

hydrogen adsorption capacities of graphitic 

materials2 . The long-term goal of the project is to 

enable efficient adsorption of hydrogen at ambient 

temperature and pressure on nanostructured carbon 

materials at system energy densities specified by 

DOE (4.5 wt% H2, 1.2 kWh/L by 2005). 

Approach 

Laser-vaporization3 and a simple purification 

technique4

 have been employed to generate SWNTs 

for hydrogen storage applications. However, the 

current purification process is not effective for the 

removal of graphite-encapsulated metals. Also, the 

laser process is not scalable for industrial production 

of carbon nanotubes. A CO2 oxidation step has been 

added to the purification process in order to aid in the 

removal of graphite-encapsulated metals. Also, a 

continuous and potentially scaleable HWCVD 

technique has been developed for the production of 

carbon nanotubes. 

Building on past research, which has shown that 

transition metal catalysts lead to enhanced 

hydrogen storage capacities on graphitic 

nanostructured materials2, experiments were 

performed to understand the nature of the 

metal/carbon interaction as well as to control 

the incorporation of metal into cut, purified 

carbon SWNT samples. Finally, hydrogen 

storage properties of non-nanotube carbon 

materials were explored in detail. 

Results 

Improvements in SWNT Purification and 

Development of HWCVD Process for Continuous 

Carbon Nanotube Production. Graphiteencapsulated metals are not removed via our current 

purification process (16-hr reflux in 3 M HNO3 

followed by air oxidation at 550°C)4 . By employing 

oxidation in CO2 prior to the dilute acid reflux, a 

 FY 2003 Progress Report 

reduction in the analysis metal content in the final 

purified materials is observed. Figure 1 shows 

thermal gravimetric analysis (TGA) curves for air 

oxidation of a SWNT material following the 3 M 

HNO3 reflux and the same material subjected to CO2 

oxidation prior to the acid reflux. The weight of the 

material remaining in both TGA curves corresponds 

to the presence of a metal oxide residue. The metal 

oxide residue has been reduced by approximately a 

factor of two in the material that was oxidized in CO2 

prior to the acid reflux. Apparently, this oxidation 

cracks the graphite- encapsulation, allowing for 

better digestion of the metal during the acid reflux. 

If nanostructured carbons are to be employed in 

vehicular hydrogen storage applications, continuous 

and scalable production techniques must be 

developed5

. Hot wire chemical vapor deposition 

(HWCVD) has been adapted to be a continuous 

growth process for high-density carbon multi-wall 

nanotubes (MWNTs). MWNT growth is optimized in 

1:5 CH4:Ar at 150 Torr with reactor temperatures of 

400 and 550°C for static and flowing gases, 

respectively. Ferrocene is employed to provide a gasphase catalyst. Highly graphitic nanotubes can be 

continuously deposited with iron content as low as 15 

wt.% and carbon impurities below TGA detection 

Figure 1.	 TGA Spectra for Air Oxidation of an SWNT 

Material Following the 3 M HNO3 Reflux and 

the Same Material Subjected to CO2 Oxidation 

Prior to the Acid Reflux 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

limits. The MWNTs are simply purified to >99.5 wt.% 

with minimal structural damage and with a 75 wt.% 

yield6 . Figure 2 (top) shows a matt of high purity 

MWNTs produced by this technique. The production 

of isolated SWNTs7 and small bundles of SWNTs 

have also been achieved with a similar HWCVD 

technique without employing an external furnace to 

increase the reactor temperature. Figure 2 (bottom) 

shows isolated SWNTs produced by the HWCVD 

method. Increases in SWNT yields are anticipated 

when a dual catalyst mixture is employed. 

Understanding the Metal/Carbon Interaction 

Required to Observe Hydrogen Adsorption at 

Near Ambient Conditions. Hydrogen adsorption is 

observed at near ambient temperatures on the assynthesized HWCVD MWNTs containing iron 

nanoparticles. No hydrogen adsorption, however, is 

 FY 2003 Progress Report 

observed at near ambient temperatures for the 

purified MWNTs containing <0.5 wt.% iron. Figure 

3 (top) shows temperature programmed desorption 

(TPD) curves of crude and purified MWNT materials 

following a room temperature H2 exposure at 500 

Torr with subsequent cooling to ~190 K and 

evacuation to ~5 x10-8 Torr. Iron nano-particles 

purchased from Alpha Asaer were then incorporated 

in purified MWNTs as well as in μm-sized particles 

of graphite via sonication. 

Figure 3 (bottom) shows TPD curves of these 

sonicated materials following the same hydrogen 

dosing procedure. No hydrogen adsorption was 

observed at near ambient temperatures when iron 

nano-particles were incorporated via sonication. 

Figure 2. TEM Images of Crude HWCVD-Generated 

MWNTs (top) and Isolated SWNTs (bottom) 

Figure 3.	 TPD H2 Desorption Signals of As-Synthesized 

and Purified HWCVD-Generated MWNTs 

(top) and Purified MWNTs and Graphite with 

Iron Nano-Particles Incorporated via 

Sonication (bottom) 

4 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 4 shows high resolution transmission 

electron microscope (TEM) images of the assynthesized MWNTs (top) and the purified MWNTs 

following metal incorporation via sonication 

(bottom). 

Note that in the as-synthesized materials, the iron 

nano-particle is located at the MWNT tip, while in 

the sonicated materials, the iron nano-particle 

randomly overlaps several nanotubes. These results, 

for the first time, conclusively demonstrate that small 

metal nano-particles must be in highly intimate 

contact with carbon nanotubes in order to observe 

hydrogen adsorption at near ambient conditions8 . 

Figure 4.	 TEM Images of As-Synthesized HWCVD 

MWNTs (top) and Purified MWNTs with Iron 

Nano-Particles Incorporated via Sonication 

(bottom) 

 FY 2003 Progress Report 

Controlled Incorporation of Ti into Purified, Cut 

SWNTs. Single-wall carbon nanotubes were 

produced via laser vaporization and subsequently cut 

by an oxidative process that does not introduce a 

metal hydride. The transport of Ti via TiI4 is well 

known (Ti + 2I2 <- -> TiI4 ). TiI4 evaporates at 

377°C (1 atm) and decomposes at higher 

temperatures. TiI4 was vapor transported to purified, 

cut SWNTs at a higher temperature in the presence of 

H2 in an effort to incorporate small particles of TiH2. 

Unfortunately, the formation of TiC is 

thermodynamically favored over the formation of 

elemental Ti or C at all temperatures. Even in the 

presence of H2, the titanium carbide was always 

formed, as shown by x-ray diffraction (XRD) 

measurements. No unusual hydrogen adsorption 

properties were observed for the SWNT samples 

containing titanium carbide. 

Evaporation of thin films of Ti was also 

employed to establish a controlled method of metal 

incorporation in purified, cut SWNTs. Again, 

however, enhanced hydrogen adsorption was not 

observed for these samples. This behavior was 

attributed to the rapid oxidation of the Ti films. In 

the future, Pd evaporation will be explored since Pd 

is not susceptible to air oxidation at ambient 

conditions. Iron evaporation may also be employed 

since oxidation of the iron nano-particles is not 

detected with XRD in the as-synthesized MWNTs, 

even after several weeks of exposure to air. 

Hydrogen Adsorption on Conducting Polymer 

and Non-Nanotube Nanocarbons. The hydrogen 

adsorption properties of several conducting polymers 

supplied by Prof. Alan MacDiarmid were explored. 

Figure 5 (top) shows the TPD spectrum of a PANICSA polymer treated with Triton-x that was 

degassed to 100°C and exposed to hydrogen at 760 

Torr. For comparison, a TDP spectrum of a SWNT 

sample that was degassed to 1000°C and exposed to 

hydrogen at 500 Torr is also shown. In both cases, 

the sample was cooled to ~190 K while the H2 gas 

was evacuated. For the SWNTs, the low-temperature 

“peak” is most likely the tail of a larger peak that 

would dominate if the sample could be cooled to a 

lower temperature while still in the presence of 500 

Torr H2. However, for the polymer sample, a peak 

with two shoulders is clearly observed above the 

5 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

minimum temperature to which the sample is cooled. 

These results indicate that unique, highertemperature hydrogen adsorption sites exist on this 

conducting polymer sample. Adsorption 

experiments conducted with a hydrogen overpressure 

could shift the H2 desorption temperatures for the 

polymer to higher temperature, and these will be 

explored. 

The hydrogen storage properties of nano-carbon 

samples produced by the decomposition of ferrocene 

in the HWCVD chamber were also examined. The 

sample was shown with TGA to contain 42 wt.% 

iron. An H2 TPD curve for this sample following 

degassing in vacuum to 550°C and exposure to 500 

Torr H2 is shown in Figure 5 (bottom). For 

comparison, a TPD spectrum of as-synthesized 

HWCVD generated MWNTs containing 25 wt% iron 

is also shown following the same dosing procedure. 

The nano-carbon sample actually displays a 

hydrogen adsorption capacity at near ambient 

conditions that is ~ 10x greater than that of the 

MWNT sample. Iron is not anticipated to store 

hydrogen at near room temperature. Further, the 

results of Figure 3 (bottom) clearly show that iron 

nanoparticles do not uptake hydrogen under the 

dosing conditions employed here. These results, 

therefore, conclusively show that non-nanotube 

carbons may also be promising candidates for 

vehicular hydrogen storage applications. 

Conclusions 

•	 Graphite-encapsulated metals are more 

easily removed from crude SWNT materials 

if CO2 oxidation is employed prior to the 

conventional purification process. 

•	 HWCVD has been developed as a 

continuous and scaleable technique for the 

production of MWNTs at high density. 

HWCVD has also been demonstrated for 

continuous production of SWNTs. 

•	 Metal assisted hydrogen adsorption at near 

ambient conditions on carbon nanotubes 

only occurs when small metal nano-particles 

are in intimate contact with the tubes. 

•	 The evaporation of Pd instead of Ti onto 

carbon nanotube materials will likely be 

more effective in hydrogen adsorption 

 FY 2003 Progress Report 

Figure 5.	 Hydrogen TPD Spectra of a Conductive Carbon 

Polymer Compared to Purified SWNTs (top) 

and HWCVD-Generated Nano-Carbon and 

Nano-Iron Particles Compared to HWCVD 

MWNTs (bottom) 

catalysis since Pd is not oxidized in air at 

room temperature. 

•	 Both conducting carbon polymers and 

HWCVD-generated Fe-doped nano-carbons 

are promising candidates for vehicular 

hydrogen storage materials. 

References 

1. Rogner, H.-H. Int. J. Hydrogen Energy 1998, 

23(9), 833. 

6 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

2. Heben, M.J.; Dillon, A.C.; Gilbert, K.E.H.; 

Parilla, P.A.; Gennett, T.; Alleman, J.L.; Hornyak, 

G.L.; Jones, K.M. Hydrogen in Materials and 

Vacuum Systems; American Institute of Physics, 

2003; Vol. CP671, 77. 

3.	 Dillon, A.C.; Parilla, P.A.; Alleman, J.L.; Perkins, 

J.D.; Heben, M.J. Chem. Phys. Lett. 2000, 316, 13. 

4. Dillon, A.C.; Gennett, T.; Jones, K.M.; Alleman, 

J.L.; Parilla, P.A.; Heben, M.J. Adv. Mat. 1999, 

11, 1354. 

5. Dillon, A.C.; Mahan, A.H.; Alleman, J.L.; Heben, 

M.J.; Parilla, P.A.; Jones, K.M. Thin Solid Films 

2003, 430, 292. 

6. Dillon, A.C.; Mahan, A.H.; Parilla, P.A.; Alleman, 

J.L.; Heben, M.J.; Jones, K.M.; Gilbert, K.E.H. 

NanoLetters in press. 

7. Mahan, A.H.; Alleman, J.L.; Heben, M.J.; Parilla, 

P.A.; Jones, K.M.; Dillon, A.C. Appl. Phys. Lett. 

2002, 81, 4061. 

8. Dillon, A.C.; Alleman, J.L.; Heben, M.J.; Parilla, 

P.A.; Jones, K.M. in preparation. 

FY 2003 Publications/Presentations 

1. Heben, M.J.; Dillon, A.C.; Gilbert, K.E.H.; 

Parilla, P.A.; Gennett, T.; Alleman, J.L.; Hornyak, 

G.L.; Jones, K.M. “Assessing the Hydrogen 

Adsorption Capacity of Single-wall Carbon 

Nanotube / Metal Composites” in Hydrogen in 

Materials and Vacuum Systems; American 

Institute of Physics, 2003; Vol. CP671, 77. 

2. Dillon, A.C.; Mahan, A.H.; Parilla, P.A.; Alleman, 

J.L.; Heben, M.J.; Jones, K.M.; Gilbert, K.E.H. 

“Continuous Hot Wire Chemical Vapor 

Deposition of High-density Carbon Multi-wall 

Nanotubes” NanoLetters (in press). 

3. Mahan, A.H.; Alleman, J.L.; Heben, M.J.; Parilla, 

P.A.; Jones, K.M.; Dillon, A.C. “Hot Wire 

Chemical Vapor Deposition of Isolated Carbon 

Single-wall Nanotubes” Appl. Phys. Lett., 2002; 

81, 4061. 

 FY 2003 Progress Report 

4. Dillon, A.C., Mahan, A.H., Alleman, J.L.; Heben, 

M.J., Parilla, P.A., Jones, K.M. “Hot Wire 

Chemical Vapor Deposition of Carbon 

Nanotubes” Thin Solid Films, 2003; 430, 292. 

5. Dillon, A.C.; Alleman, J.L.; Heben, M.J.; Parilla, 

P.A.; Jones, K.M. “Understanding the Mechanism 

of Metal Catalyzed Hydrogen Adsorption on 

Carbon Nanotubes” (in preparation). 

6. Dillon, A.C.; Mahan, A.H.; Alleman, J.L.; Parilla, 

P.A.; Heben, M.J.; Jones, K.M., Gilbert K.E.H., 

Heben M.J. “Synthesis of Carbon Nanotube 

Materials for Vehicular Hydrogen Storage” 

plenary speaker for the Claire Boothe Luce 100th 

Birthday Celebration, Mar. 3, 2003, Seton Hall 

University, NJ. (Claire Boothe Luce created a 

major foundation to support women students and 

faculty in science.) 

7. Dillon, A.C.; Parilla, P.A., Gilbert, K.E.H.; 

Alleman, J.L.; Jones, K.M.; Heben, M.J. 

“Evaluating the Purity and Defect Densities in 

Bulk Single-wall Carbon Nanotube Materials” 

invited talk NIST/NASA “Purity and Dispersion 

Measurement Issues in Single-wall Carbon 

Nanotubes Workshop”, Gaithersburg, MD, May 

27, 2003. 

Special Recognitions & Awards/Patents 

Issued 

1. Patent continuation-in-part application: PCT/01­

19 CIP “Hot Wire Production of Multi-Wall and 

Single-Wall Nanotubes.” Dillon, A.C., Mahan, 

A.H. and Alleman J.L., March, 2003. 

2. “Hot Wire Chemical Vapor Deposition of Isolated 

Carbon Single-walled Nanotubes", published in 

Appl. Phys. Lett. 81 (2002) 4061, was selected for 

the November 25, 2002, issue of the Virtual 

Journal of Nanoscale Science & Technology. The 

Virtual Journal is an edited compilation of links to 

articles from participating publishers, covering a 

focused area of frontier research. 

7 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Doped Carbon Nanotubes for Hydrogen Storage 

Ragaiy Zidan (Primary Contact), Apparao M. Rao, Ming Au 

Hydrogen Technology Laboratory 

Savannah River Technology Center (SRTC) 

773-41A/ 247 

Savannah River Site 

Aiken, SC 29808 

Phone: (803) 725-1726; Fax: (803) 725-4129; E-mail: ragaiy.zidan@srs.gov 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Objectives 

Develop reversible high-capacity hydrogen storage material to meet the DOE goals for a hydrogen 

storage system: 

• Hydrogen capacity greater than 6 wt.% 

• Favorable thermodynamic and kinetics suitable for transportation applications 

• Stable with hydriding/dehydriding cycling 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• M. Hydrogen Capacity and Reversibility 

• N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

• O. Test Protocols and Evaluation Facilities 

• P. Dispensing Technology 

Approach 

• Produce large quantities of consistent structure carbon nanotube material 

• Attempt to create a weak covalent hydrogen bond, dihydrogen 

• Dope carbon nanotubes with transition metals and alloys 

• Dope carbon nanotubes with other elements and metal clusters 

• Tune material for hydrogen sorption to occur at desired temperature and pressure 

Accomplishments 

• Synthesis of material was achieved with: 

- Different dopants 

- Different quantities of dopants 

- Different diameters and configurations 

• Thermodynamic and material characterization were conducted by: 

- Setting up a high pressure thermovolumetric (TVA) system 

1 
 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- Measuring the hydriding and dehydriding of material 

- Examining nanotubes with cycling 

- Spectroscopic analysis of product was performed 

Future Directions 

•	 Continue production of nanotubes with different dopants 

•	 Determine thermodynamic characteristics of hydrogen uptake and release 

•	 Identify the type and size of nanotubes and clusters that result in a reversible, high hydrogen 

capacity material 

•	 Tune conditions to result in a high yield of material possessing favorable characteristics 

•	 Utilize theoretical modeling to guide the experiment 

Introduction 

The absence of a practical means for hydrogen 

storage has been a major obstacle in the transition to 

a hydrogen economy. Developing a solid-state 

hydrogen storage system that meets the DOE 

objectives has been the goal of researchers for years. 

Unfortunately, the extensive work in the area of 

conventional metal and intermetallic hydrides did not 

result in materials suitable for on-board hydrogen 

storage. Carbon nanotube technology represents a 

new direction for solid-state hydrogen storage, 

especially if these materials can be altered to store 

large amounts of hydrogen at room temperature. 

Persistent research activities, worldwide, have been 

exploring the use of carbon nanotubes for hydrogen 

storage [1-5]. 

This research is taking into account the barriers 

that face the development of a hydrogen storage 

system in general as well as taking into account 

problems that are inherent to carbon nanotube 

technology. This research is focused on modifying 

carbon nanotube systems in an attempt to enhance 

and tune the hydrogen storage capabilities of the 

nanotubes. The objective of this research has been to 

introduce transition metals and hydrogen bonding 

clusters into the nanotubes. The intent is aimed at 

producing consistent size dopants and structures of 

carbon nanotubes to avoid inconsistency in 

measurements. The success of making doped carbon 

nanotubes with transition metals and alloys can allow 

for a weak covalent bond similar to cases of 

dihydrogen bond that is not restricted to pure 

physisorption or chemisorption bond [6,7]. 

Controlling the type and size of tubes and dopant is 

expected to tune the product for hydrogen sorption to 

occur at desired temperature and pressure. 

Approach 

Our research is focused on modifying carbon 

nanotubes by doping them with different atoms and 

encapsulating metal clusters inside the tubes to make 

them suitable for hydrogen storage. Relying on 

physisorption alone will lead to a bond that is too 

weak, and chemisorption will lead to a bond that is too 

strong. Therefore, our objective is to establish a weak 

covalent bond where the electron donation from the (s) 

orbital of hydrogen to the doped tubes weakens but 

does not break the hydrogen-hydrogen bond. 

The method of producing doped carbon 

nanotubes with controlled characteristics is a method 

developed at SRTC and is in the process of being 

patented. Thermodynamic characterization of 

hydrogen uptake and release will be conducted. 

Different spectroscopic methods are applied to 

identify the type and size of nanotubes and clusters 

that could result in a reversible high hydrogencapacity material. Collaboration with academia and 

other government laboratories has been established. 

Results 

The synthesis of different doped carbon 

nanotubes has been achieved using SRTC technique 

that allowed for controlling the type and amount of 

dopants in the tubes. It was possible to produce large 

quantities of consistent structure carbon nanotube 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

systems (see Figures 1 and 2). Preliminary results of Conclusions 

hydrogen sorption showed 1% by weight hydrogen 

uptake and release. A thermogravimetric (TGA) 

system capable of operating at a wide range of 

temperatures was used to measure hydrogen uptake 

and release. Nitrogen doped carbon nanotubes, with 

average nitrogen content of about 5 wt. %, were also 

synthesized (see Figure 3). 

Figure 1. Consistent Structure Doped Carbon 

Nanotubes 

Figure 2. Tip of a Nanotube with Encapsulated Metal 

Particle 

Although more investigation is needed to 

identify the type of hydrogen bond with the carbon 

nanotubes, the preliminary results look encouraging. 

One of our goals has been to synthesize nanotubes 

containing other elements such as boron or nitrogen, 

largely due to the possibility of fabricating nanotube 

materials with tailored electrical and mechanical 

properties. This goal was achieved as nitrogen doped 

carbon nanotubes were synthesized [8]. 

References 

1. A. C. Dillon, K. M. Jones, T. A. Bekkedahl, C.H. 

Kiang, D. S. Bethune and M.J. Heben Nature, 386 

(1997). 377. 

2. Y. Ye, C.C. Ahn, C. Witham, B. Fultz, J. Liu, A.G. 

Rinzler, D. Colbert, K.A. Smith, and R.E. 

Smalley, Applied Physics Letters 74, 2307 (1999). 

3. C. Liu, Y.Y.Fan., M. Liu, H.T. Cong, H.M. Cheng, 

and M. Dresselhaus, Science 286, 1127 (1999). 

4. P.,Chen, X. Wu, J. Lin, and K.L. Tan, Science 

285, 91 (1999). 

5. R. Chahine and P. Bénard, IEA Task 12: Metal 

Hydrides and Carbon for Hydrogen Storage 2001. 

6. G.J Kubas, R.R. Ryan B. I. Swanson, P.J. 

Vergamini, and .J. Wasserman, J. Am. Chem. Soc. 

106, 451 (1984). 

Figure 3. Nitrogen-doped Carbon Nanotube 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

7. G.J. Kubas, Acc. Chem. Res. 21, 120 (1988). 

8. B.Sadanadan a, T. Savage a, S. Bhattacharya a, T. 

Tritt a, Alan Cassell b, M. Meyyappan b, Z.R. Dai 

c, Z. L. Wang c, R. Zidan d and A. M. Rao a, J. 

nanoscience and nanotechnology, 3 99 (2003). 

FY 2003 Publications/Presentations 

1. "Synthesis and Thermoelectric Power of Nitrogen 

Doped Carbon Nanotubes" 

 FY 2003 Progress Report 

2. B.Sadanadan a, T. Savage a, S. Bhattacharya a, T. 

Tritt a, Alan Cassell b, M. Meyyappan b, Z.R. Dai 

c, Z. L. Wang c, R. Zidan d and A. M. Rao a, J. 

nanoscience and nanotechnology, Volume: 3 

Number: 1, 99 - 103 (2003). 

Special Recognitions & Awards/Patents 

Issued 

1. Patent disclosure has been submitted, on 

producing and controlling the characteristics of 

doped carbon nanotubes 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Storage in Metal-Modified Single-Walled Carbon Nanotubes 

Channing Ahn (Primary Contact) 

California Institute of Technology 

1200 E. California Blvd, MS 138-78 

Pasadena, CA 91125 

Phone: (626) 395-2174; Fax: (626) 795-6132; E-mail: cca@caltech.edu 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Objectives 

•	 Alter adsorption enthalpy of hydrogen on single-walled nanotubes (SWNTs) by use of a potassium 

intercalant. 

•	 Increase number of adsorption sites in SWNTs by increasing the surface area through the use of 

intercalant. 

•	 Improve the hydrogen storage capacity of SWNTs. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Hydrogen Capacity and Reversibility 

•	 N. Lack of Understanding of Hydrogen Physisorption and Chemisorption 

Approach 

•	 Investigate potassium intercalation synthesis procedures and measure sorption behavior of flaked 

graphites. 

•	 Apply synthesis "recipes" to SWNT intercalation. 

•	 Measure hydrogen sorption isotherms using Sieverts apparatus 

Accomplishments 

•	 Optimized synthesis procedures for KC24 and KC8 intercalated graphites. 

•	 Determined synthesis procedures for K intercalated SWNTs, including CNI HiPco synthesized SWNTs. 

•	 Determined purification routes for commercial Carbolex SWNTs. 

•	 Carried out initial single point isotherm measurements and Raman and x-ray diffraction measurements 

for structural characterization. 

•	 Produced K-intercalated SWNTs with room temperature sorption comparable to activated carbons. 

Future Directions 

•	 Further purification and intercalation of SWNTs. 

•	 Optimization of K intercalation into SWNTs. 

•	 Complete volumetric hydrogen adsorption measurements of SWNTs. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

The abundance of carbon and its relatively low 

molecular weight make it an attractive possibility as 

a hydrogen sorbent for fuel tank applications, where 

a high gravimetric density (mass ratio of hydrogen to 

carbon) is required. Graphite is the most commonly 

available form of carbon and consists of stacked 

graphene sheets. However, the interaction of 

graphite with hydrogen molecules is very weak, and 

the carbon layers are stacked too closely together for 

hydrogen molecules to fit between the layers, a 

necessity if a high density of hydrogen molecules is 

to be absorbed by the graphite. 

The addition of potassium as an “intercalant” 

improves the ability of graphite to absorb hydrogen. 

When processed under controlled conditions, 

potassium atoms can separate the graphite layers and 

form an open hexagonal structure. 

It has been known for over thirty years that KC24 

potassium-intercalated graphite can readily absorb 

and desorb hydrogen but that this occurs most readily 

at 77 K [1]. The overall level of absorption in KC24 

is ~1.2 wt% at this temperature. The limitation of 1.2 

wt% can be understood on the basis of a space filling 

argument. Potassium atoms form an open hexagonal 

structure on alternating graphene layers, and four 

hydrogen molecules can fit within the open hexagon, 

defining the upper absorption limit. The lattice 

separation that potassium atoms induce within the 

graphitic layers can better accommodate the size of 

molecular hydrogen. 

Adopting the approach of increasing the 

adsorption enthalpy for graphites should have a 

similar effect for SWNTs, and also have the effect of 

increasing the surface area of SWNTs. SWNTs have 

effectively high surface areas (~1600 m2

/gm outer 

surface area and ~1000 m2

/gm inner surface area) 

that are well beyond normal graphitic carbon. 

However, nanotubes typically form rope structures 

due to van der Waals interactions which promote 

rope formation, limiting the surface area to ~300 m2/ 

gm (interior and exterior surface areas for a SWNTs 

should be above 2600 m2/gm). Potassium 

intercalation of SWNTs will separate the individual 

tubes. Computational work on SWNTs shows that 

under certain conditions, increasing the van der 

Waals gap will increase the amount of hydrogen that 

can be adsorbed [2]. 

Approach 

We have been exploring 2-zone furnace 

procedures for the synthesis of KC24 and KC8 and 

nanotube materials. Following 35-year-old synthesis 

techniques, we have used Madagascar graphites 

(from Superior Graphite in Chicago), which are 

generally recognized as the best graphites for 

intercalation. We have also used Carbon 

Nanotechnologies (CNI) HiPco nanotubes in 

addition to nanotubes originally acquired from the 

group at Rice University. 

We have also obtained SWNTs from Carbolex. 

CNI no longer manufactures laser-oven synthesized 

SWNT material, which tends to have a narrower size 

distribution (typically with a 13 Å diameter) than the

HiPco material (8-13 Å diameter range) that they 

presently synthesize and sell. Part of our goal in this 

work is to synthesize a well-defined structure on the 

basis of the well-packed rope structure we have seen 

previously in laser-oven material from Rice. 

Our structural characterization tools include xray diffraction, transmission electron microscopy 

(TEM) and Raman spectroscopy. 

We are having a 2nd generation Sieverts 

apparatus constructed at the Jet Propulsion 

Laboratory (JPL) that will enable us to obtain both 

adsorption and desorption isotherms. In the 

meantime, we have been collaborating with Dr. John 

Vajo of HRL Laboratories, who has been measuring 

single point adsorption isotherms for us. 

Results 

Figure 1 shows an overlay of intercalation 

synthesis behavior for stage formation of graphite 

compared to staging behavior for SWNTs. At ∆t 

values of 0 to ~100°C, we can expect Stage 1 

compounds to appear, while ∆t values of 110 to 

150°C are required to form Stage 2 compounds. For 

SWNTs, values of ∆t up to 170°C only yield 

compounds of between KC8 and KC9 stoichiometry. 

∆t values above 170°C indicate no compound 

formation occurs. The solution to the problem of 

yielding the correct stoichiometry is to limit the 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

amount of potassium in the reactor assembly to 

match the desired final stoichiometry. 

X-ray data is shown in Figure 2. The trace in the 

upper right shows low angle data from a laser over 

synthesized nanotube from Rice and shows the 

periodic structure associated with tube packing to 

form ropes. The lower left trace shows the result of 

condensing potassium onto this material as part of 

our initial attempt to induce intercalation into 

nanotubes. The upper right trace shows that we have 

been able to disrupt the periodicity of the rope 

structure by using a ∆t of 10°C. The lower right trace 

shows our processing attempts to de-intercalate the 

sample onto which potassium had been condensed. 

Figure 1.	 Phase Diagram for Staging in Graphite 

Overlayed with Our Observed Uptake of 

Potassium in Nanotube 

Figure 2.	 X-ray Data for Unprocessed and Intercalated 

"Bucky" Paper Using Processing Conditions 

as Noted 

 FY 2003 Progress Report 

Transmission electron micrographs summarizing 

our processing procedures for purification of an 

alternative laser-oven synthesized material from 

Carbolex are shown in Figure 3. 

In Figure 4, a summary of the improvements to 

room temperature sorption behavior of potassiummodified nanotubes is plotted. We can clearly see 

Figure 3.	 TEM micrographs showing the 

microstructural evolution as a function of 

processing for as-prepared Carbolex 

nanotubes. Starting from the upper left and 

going clockwise is the as-prepared material, 

HNO3 refluxed, H2O2 refluxed and HCL 

sonicated, 2-step oxidation treated and high 

temperature oxidation treated and a high 

magnification micrograph. 

Figure 4.	 Ratio of Room Temperature to Liquid 

Nitrogen Temperature Gravimetric Densities 

for Pure and Potassium Intercalated Carbons 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

that unmodified carbons in the lower part of the plot 

have room temperature sorption that is 1/6 to 1/8 of 

the 77 K gravimetric density. Potassium 

intercalation can improve this ratio by nearly a value 

of two, indicating that the adsorption enthalpy is 

being altered. Even though the absolute values for 

gravimetric density are ~0.5 wt%, we have been able 

to effect improvements to the room temperature 

adsorption of nanotubes so that they are now 

comparable to the best activated carbons, which also 

have hydrogen gravimetric densities of ~0.5 wt%. 

We have accomplished this, even though we have not 

yet optimized the processing or structure of the 

intercalated nanotubes. 

Conclusions 

Our potassium modification to carbon nanotubes 

yields room temperature hydrogen gravimetric 

densities that are now comparable to the best 

activated carbons. This indicates that we have now 

succeeded in altering the chemical potential for 

hydrogen physisorption in nanotubes. We plan to 

continue to optimize the structure of these materials 

by expanding or swelling the structure, to improve 

the surface area in a way that preserves the packing 

or rope symmetry. We anticipate that this will further 

improve the room temperature hydrogen storage 

capacity of these materials. 

References 

1. M. Colin and A. Herold, Bull. Soc. Chim. Fr., 6, 

1982 (1971). 

2. V. V. Simonyan, J. K. Johnson, J. Alloys Comp., 

330-332, 659 (2002). 

FY 2003 Publications/Presentations 

1. Hydrogen storage in carbon nanostructures, C. 

C. Ahn, Invited Presentation, European
 

Materials Research Society Annual Mtg., 

Strasbourg (2003). 

 FY 2003 Progress Report 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Carbon-based Sorbent Systems for an Effective Containment of Hydrogen 

(New FY 2004 Project) 

Dr. Guido P. Pez 

Air Products and Chemicals, Inc. 

7201 Hamilton Boulevard 

Allentown, PA 18195-1501 

Phone: (610) 481-4271; Fax: (610) 481-7719; E-mail: pezgp@apci.com 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Objectives 

• Develop a new hydrogen storage technology using novel reversible H2-sorbent materials 

• Deliver a packaged hydrogen storage system which will hold 6.0 wt.% hydrogen 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Weight and Volume 

• M. Hydrogen Capacity and Reversibility 

Approach 

Air Products will develop a hydrogen storage 

technology using reversible H2-sorbent materials that 

will be contained in suitable robust, lightweight, lowcost containers. We propose to design and develop 

materials and processes for sorption-based hydrogen 

storage systems in support of DOE’s FreedomCAR 

program and other portable-power initiatives. 

Our goal is to devise hydrogen-containment 

systems of 6 wt.% H2-deliverable capacity at 

volumetric densities that range from 0.45 to 0.81 kg 

H2/L, that are operable with fast filling rates (<5 

min.) within a specified (-40 to 90oC) operating 

temperature range and that achieve total reversibility 

over 500 cycles. The system's cost is limited to $10/ 

kg, which corresponds to $833 for a fuel tank that 

carries 5 kg of usable hydrogen. 

Our systems are to consist of a pressure/ 

temperature H2-reversible solid sorbent material that 

is packaged in a lightweight container under a 

modest pressure of hydrogen. The critical 

performance parameters are gravimetric and 

volumetric deliverable hydrogen capacity at specific 

loading and delivery process conditions. The 

sorbent’s hydrogen capacity must actually exceed 6.5 

wt.% in order to realize the ultimate goal of a 

hydrogen storage system which contains 6 wt.% H2. 

Goals include designing reversible H2-sorbent 

materials: solid-state compositions that can take up 

hydrogen and release it by only varying the system's 

externally variable parameters of temperature and H2 

pressure, without the introduction or release of any 

other substances. Our ultimate goal of Phase I is to 

deliver to DOE a small prototype (0.1-1 kg sorbent) 

of a packaged hydrogen storage system that operates 

by temperature- or pressure-swing adsorption and 

utilizes a hydrogen sorbent material that has a 

reversible capacity, by total package weight, of 6.0% 

hydrogen in the specified temperature range (-40 to 

90o

C) and under moderate pressure of hydrogen 

(<1000 psia). 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

If successful in Phase I, we intend to submit to 

DOE a proposal for research and development 

towards an adsorbent production process (at a target 

cost of <$5/kg) and continuation of the packaged 

system prototype development, including integration 

of the packaged system with a commercial fuel cell 

stack. 

 FY 2003 Progress Report 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Process for the Regeneration of Sodium Borate to Sodium Borohydride for Use as 

a Hydrogen Storage Source (New FY 2004 Project) 

Dr. Ying Wu 

Program Director, Synthesis 

Millennium Cell, Inc. 

One Industrial Way West 

Eatontown, New Jersey 07724 

Phone: (732) 544-5718; Fax: (732) 542-2846; E-mail: wu@millenniumcell.com 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Subcontractors: Air Products and Chemicals, Inc.; Princeton University 

Objectives 

• To develop an electrolysis process for the reduction of borates to borohydrides 

• To conduct preliminary engineering studies of the electrolysis process developed 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Storage section of the Hydrogen, 

Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• Q. Regeneration Processes for Irreversible Systems 

Approach 

Under this project, Millennium Cell will 

collaborate with Air Products and Chemicals, Inc., a 

recognized industry leader in hydrogen technology, as 

well as Professor Andrew Bocarsly of Princeton 

University. This project provides a solution to the 

storage of hydrogen through cost effective use and 

production of a chemical hydride, sodium borohydride 

(NaBH4). The team proposes to develop a novel 

NaBH4 production process and pilot the process at a 

size suitable for engineering scale-up. 

Chemical hydrides, particularly NaBH4, have 

been proposed as effective hydrogen storage methods 

for a wide variety of applications in both distributed 

power generation and transportation applications. 

The hydrogen storage densities of sodium 

borohydride and its aqueous solutions meet the 

technical target of 6% hydrogen capacity set by 

DOE. The demonstrated advantages and benefits of 

NaBH4 are known; however, regeneration and 

production systems warrant further study in order to 

bring NaBH4 to widespread commercialization. 

Therefore, it is the goal of this project to determine 

the technical feasibility of a new synthetic method 

for producing NaBH4 that improves significantly 

upon the current process. It is expected that an 

improved process will lead to NaBH4-based 

hydrogen fuel systems being economically 

competitive with hydrocarbon-based fuels. 

The storage capacity of NaBH4 and the relative 

simplicity of its hydrogen delivery methodology 

make it possible to construct a hydrogen fuel system 

that allows a vehicle to achieve a 400+ mile range on 

a single fill-up without sacrificing conventional 

passenger space inside the vehicle. Sodium 

borohydride can be stored as an aqueous solution, 

adding to its advantage as a safe and convenient 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

carrier for hydrogen. Its performance characteristics 

on hydrogen delivery have been validated by 

Millennium Cell’s proprietary Hydrogen on 

DemandTM technology. Prototype testing indicated 

that the load following characteristics of hydrogen 

delivered from borohydride is essentially nondistinguishable from that of compressed hydrogen. 

An important barrier to overcome in 

commercializing this technology is the current cost 

of sodium borohydride. The key to lowering the cost 

is the technical feasibility of a more energy efficient 

NaBH4 synthetic process. The regeneration of 

NaBH4 from sodium borates requires the input of a 

substantial amount of energy. In the existing 

commercial process, this energy input is manifested 

 FY 2003 Progress Report 

as the energy input required to produce sodium 

metal, which is used in large quantities in a 

subsequent chemical process to yield NaBH4. In this 

proposal, we intend to explore the concept of 

hydrogen-assisted electrolysis for the reduction of 

sodium borates or both sodium borates and sodium 

hydroxide. Electrochemical reactions involving 

hydrogen often have the advantage of low 

overpotential and single step process operations; 

therefore, they are able to achieve higher overall 

energy efficiencies. If this project is successful, it 

will significantly advance hydrogen storage 

technology for transportation and other potential 

markets by lowering the cost while meeting the 

specific energy and density criteria set by the DOE. 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Chemical Hydride Slurry for Hydrogen Production and Storage 

(New FY 2004 Project) 

Andrew W. McClaine 

Chief Technical Officer 

Safe Hydrogen, LLC 

30 York Street 

Lexington, MA 02420-2009 

Phone: (781) 861-7016; E-mail: awmcclaine@safehydrogen.com 

DOE Technology Development Manager: Sunita Satyapal 

Phone: (202) 586-2336; Fax: (202) 586-9811; E-mail: Sunita.Satyapal@ee.doe.gov 

Objectives 

•	 Develop a MgH2 slurry system with a gravimetric density >11 wt% H2 

•	 Develop a MgH2 slurry system with a gravimetric capacity of >1.5 kWh/kg 

•	 Develop viable methods to recycle by-products and produce MgH2 from Mg and H2 to meet DOE cost 

targets 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

• A. Cost 	 

•	 B. Weight and Volume 

•	 Q. Regeneration Processes for Irreversible Systems 

Approach 

Safe Hydrogen, LLC is developing a new 

hydrogen storage medium using chemical hydride 

slurry, which is made by mixing chemical hydride 

with mineral oil and dispersants. The oil coats the 

hydride particles and protects them from inadvertent 

contact with water while also moderating the reaction 

rate of the hydride with water when desired. The 

slurry itself will store 5 kg of hydrogen in less than 

52 L of volume. The by-product of the reaction will 

be stored in the same container as the hydride slurry 

but will be separated by a baffle or barrier. 

The primary purpose for developing the slurry is 

to create energy-dense chemical hydrides that can be 

transported, pumped and metered as a liquid. 

Additionally, the slurry storage medium enhances 

safety by eliminating the need to transport hydrogen 

gas. Hydrogen gas is produced as needed by mixing 

the chemical hydride slurry with water. Unlike 

hydrogen gas, possible slurry seepage can be 

identified and contained quickly. 

A project focused on lithium hydride indicated 

that magnesium hydride slurry could provide 

additional safety and cost benefits. Magnesium 

hydride slurry reacts very slowly at room 

temperatures. As a result, if the slurry is spilled into 

a pool of water, only a few bubbles of hydrogen are 

produced each minute. The by-product of the 

reaction is quite safe (magnesium hydroxide, 

sometimes called “milk of magnesia,” is used as an 

antacid or laxative). It is also expected that 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

magnesium hydride would cost less to manufacture 

than lithium hydride. 

The proposed project focuses on: 

1. Slurry development 

2. Mixer development 

3. Recycle system development 

In the slurry development, Safe Hydrogen plans 

to develop magnesium hydride slurry as 

demonstrated with lithium hydride slurry. In the 

mixer development, Safe Hydrogen will improve the 

mixer design for slurries of magnesium hydride or 

lithium hydride. We will reduce the size, weight, and 

production cost of the mixing system while 

increasing its robustness. 

The majority of the work planned for this project 

is development of the recycle system. The 

economics of the system depend on the recycle costs. 

By using the metal several times a year, the amount 

of hydrogen carried by each unit of metal is increased 

and the cost of hydrogen is decreased. By operating 

large-scale plants, we reduce the cost of the metal 

production. We expect recycle costs to be less than 

production costs from ore because the front end and 

 FY 2003 Progress Report 

back end of the recycle process are much simpler and 

lower cost than those of the production process. 

There are two currently-used methods of 

reducing magnesium. The most common method 

electrolytically separates magnesium from 

magnesium chloride. The other is a metallothermic 

method that uses ferrosilicon as a reductant. A 

potentially lower cost carbothermic method was used 

in the 1940s and 1950s by the Permanente Metals 

Company. One of its intermediate products was 

powdered magnesium that would be particularly 

attractive for making magnesium hydride slurry. 

A new method of producing magnesium from 

magnesium oxide being developed by Boston 

University has the potential to reduce costs and 

simplify the process. We intend to evaluate and 

compare the various methods of reducing magnesium 

and lithium. The evaluations will begin with process 

design and analyses to estimate the cost of 

production by each method. Experimental activities 

are coupled with the process analyses to provide 

additional process understanding of the Boston 

University process and new carbothermic reduction 

technology. 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Novel, Light-Element Nanostructured Materials for Hydrogen Storage 

(New FY 2004 Project) 

George Gruner 

Nanomix, Inc. 

1295A 67th Street 

Emeryville, CA 94608 

Phone: (510) 428-5318; Fax: (510) 658-0425; E-mail: ggruner@nano.com 

DOE Technology Development Manager: Carole Read 

Phone: (202) 586-3152; Fax: (202) 586-9811; E-mail: Carole.Read@ee.doe.gov 

Objectives 

To demonstrate the operation of a nanostructure-based hydrogen storage tank which meets the DOE cost 

goals of $5/kW-hr 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

• A. Cost 

• B. Weight and Volume 

• M. Hydrogen Capacity and Reversibility 

Approach 

This project will develop and prototype a new 

hydrogen storage technology based on lowtemperature physisorption of hydrogen on 

nanostructured materials based on light elements. 

The Nanomix team will develop and test new 

materials and scale them up to prototype testing. The 

materials will be the heart of a simple storage system 

that takes advantage of the inherent thermodynamic 

properties of hydrogen and promises to surpass 

competing technologies in overall system 

performance. Starting with activated carbon, 

Nanomix will design and construct a pilot-scale 

prototype to define and study critical operating 

parameters such as temperature, pressure, refueling 

time, and dormancy. The research and development 

effort will identify new materials with appropriate 

heats of adsorption using computational tools, 

synthesize and test both known and new candidate 

materials, develop high surface area forms, construct 

a storage tank prototype, and test the tank with 

quantities of candidate materials that emerge 

successfully from the preceding materials 

development project. 

This three-year project includes seven separate 

tasks: 

Task 1. Planning and Management: Prepare a 

project management plan that addresses organization, 

schedule budget, procurement, health & safety, data 

quality and reporting. Participate in DOE Hydrogen, 

Fuel Cells and Infrastructure Technologies Program 

meetings, etc. 

Task 2. Computational Design and Screening: 

Identify new candidate materials for hydrogen 

adsorption; conduct screening level ab initio 

calculations of the binding energy of hydrogen; 

perform density functional calculations on promising 

candidates; and predict composition, structure and 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

stability and project cost of production and toxicity. 

Complete analysis of two groups in the first year and 

identify at least 2 new materials. 

Ta s k 3 . Experimental Verification: Procure or 

synthesize small quantities of nanostructured 

materials for screening; characterize hydrogen 

storage properties - binding energy and coverage 

over a range of temperatures; and select high 

potential materials. Complete verification of at least 

two new materials in the first year. 

Ta s k 4 . Optimize Material for Hydrogen 

Storage: Synthesize very high surface area samples 

and conduct engineering measurements of hydrogen 

 FY 2003 Progress Report 

storage properties. Complete synthesis of B2O3 and 

at least one new material in the first year. 

Ta s k 5 . Pilot Material Synthesis / Production: 

Evaluate pilot-scale and larger process feasibility and 

production costs; synthesize B2O3 or another 

material for testing in the first year. 

Ta s k 6 . Prototype Testing: Design and construct 

a prototype H2 storage tank to test material and 

operating parameters; test high surface area carbon 

structures in the first year. 

Ta s k 7 . Reporting and Deliverables: Submit 

quarterly and annual project reports. 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Standardized Testing Program For Emergent Chemical Hydride And Carbon 

Storage Technologies 

Richard A. Page (Primary Contact) and Michael A. Miller 

Southwest Research Institute 

P. O. Drawer 28510 

6220 Culebra Road 

San Antonio, TX 78228-0510 

Phone: (210) 522-3252; Fax: (210) 522-6220; E-mail: rpage@swri.org 

DOE Technology Development Manager: JoAnn Milliken
 

Phone: (202) 586-2480; Fax: (202) 586-9811; E-mail: JoAnn.Milliken@ee.doe.gov
 

ANL Technical Advisor: William Swift
 

Phone: (630) 252-5964; Fax: (630) 972-4473; E-mail: swift@cmt.anl.gov
 

Subcontractors:
 

Teledyne Energy Systems, Hunt Valley, MD
 

The National Hydrogen Association, Washington, D.C.
 

Energy Conversion Devices, Inc., Troy, MI
 

Objectives 

•	 Develop and operate a standard testing and certification program specifically aimed at assessing the 

performance, safety and life cycle of emergent complex metal hydrides and carbon adsorption/ 

desorption hydrogen storage materials and systems. 

•	 Work with industry and the U.S. government to develop an accepted set of performance and safety 

evaluation standards. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Storage section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

•	 O. Test Protocols and Evaluation Facilities 

•	 M. Hydrogen Capacity and Reversibility 

•	 F. Codes and Standards 

•	 B. Weight and Volume 

•	 D. Durability 

Approach 

•	 Task 1: Perform a comprehensive review of the current accepted practices for testing the performance 

of complex metal hydride and carbon storage media. 

•	 Task 2: Define the equipment and test protocols that will be used in the standardized testing program. 

•	 Task 3: Design and construct the test facilities for characterizing the performance of complex metal 

hydride and carbon storage media. 

•	 Task 4: Evaluate the operation of the test facility with actual sample materials to verify that all 

components operate correctly pursuant to the test protocols developed in Task 2. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Task 5: Analyze emergent complex metal hydride and carbon storage materials in accordance with the 

protocols established in Task 2. 

•	 Task 6: Work for the adoption of the test protocols developed in this program by a recognized national 

or international standards organization. 

Accomplishments 

•	 Completed literature review of current measurement state-of-the-art. 

•	 Developed preliminary facility and equipment design. 

•	 Completed visits to leading laboratories involved in hydrogen adsorption/desorption measurements. 

•	 Submitted document specifying the equipment to be used for characterization of solid-state hydrogen 

storage materials. 

Future Directions 

•	 A testing facility equipped to perform gravimetric, volumetric and thermally programmed desorption 

(TPD) measurements on small quantities of solid-state hydrogen storage materials has been defined 

(2Q, 2003). 

•	 The design of the facility to test full-scale storage systems will be finalized (3Q, 2003). 

•	 Construction of the facility for testing small quantities of solid-state hydrogen storage materials will be 

completed (2Q,2004). 

Introduction 

The choices of viable hydrogen storage systems 

at this time are limited to compressed hydrogen gas 

(CH2) storage tanks, cryogenic liquid hydrogen 

(LH2) storage tanks, chemical hydrides, and solidstate materials, including complex metal hydrides 

and carbon. While each of these enabling storage 

technologies has specific advantages and 

disadvantages, the solid-state storage systems may 

offer advantages in terms of storage capacity and, 

most importantly, safety. 

The realization that storage systems utilizing 

solid-state storage materials may most efficiently 

meet the storage capacity and safety requirements of 

a hydrogen-based infrastructure has led to significant 

interest and monetary investment to accelerate the 

development of complete hydrogen adsorption 

storage systems. However, there are no standard 

guidelines, dedicated facilities, or certification 

programs specifically aimed at testing and assessing 

the performance, safety and life cycle of these 

emergent systems. The development of a 

standardized protocol and testing system would 

allow both DOE and the R&D organizations to assess 

the potential performance of the wide array of 

materials and systems and focus their efforts on those 

that show the most promise. 

Approach 

In anticipation of the availability of many new 

materials and technologies for hydrogen storage, the 

purpose of the present effort is to develop an 

evaluation facility with established evaluation 

protocols and standards for the testing and 

assessment of these emergent solid-state storage 

materials and systems. Upon thorough validation of 

the experimental apparatuses and associated 

protocols, the testing facility and the technical staff 

that supports it will be available as the focal testing 

center to any prospective innovator of complex metal 

hydride or carbon hydrogen storage materials or 

systems. Although the final form of the test protocol 

and equipment is still being defined, it is anticipated 

that the test system will be centered around hydrogen 

sorption/desorption measurements of small quantities 

of storage materials. These measurements may be 

performed using a trio of devices, including a 

magnetically coupled thermogravimetric analyzer 

(TGA), as shown in Figure 1, a Sieverts apparatus, as 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

shown in Figure 2, and a thermally programmed 

desorption apparatus. An ability to test complete 

storage systems will also be included. 

The performance characteristics of candidate 

materials will be determined through a 

comprehensive materials characterization and 

systems testing approach. This approach will 

encompass the elements described below. 

Figure 1.	 Magnetically Coupled Thermogravimetric 

Analyzer 

Figure 2. Schematic of Sieverts Apparatus 

 FY 2003 Progress Report 

Certification of Chemical Composition and 

Crystallographic Properties. Materials selected for 

evaluation will be analyzed to determine or verify 

their elemental composition and crystallographic 

properties using appropriate analytical capabilities: 

atomic adsorption spectroscopy (AAS), X-ray 

fluorescence (XRF), Raman spectroscopy, Fourier 

transform infrared spectroscopy (FTIR), and powder 

X-ray diffraction. 

Evaluation and Certification of Performance 

Parameters. The intrinsic thermodynamic 

characteristics of candidate storage materials, where 

existing data is not available, will be evaluated by 

modulated differential scanning calorimetry 

(MDSC). Data of this sort that has already been 

generated by others will be used to the extent that it 

is relevant to the specific goals of the present study. 

The intrinsic thermodynamic characteristics that will 

be derived from the MDSC analysis include the 

following: 

•	 Determination of first and second order 

phase transitions 

•	 Heat of transition 

•	 Transition temperature 

•	 Non-reversible transitions (such as in 

decomposition) 

•	 Decomposition temperature 

•	 Decomposition exotherm 

•	 Crystalline versus amorphous compositions 

Once the intrinsic thermodynamic characteristics 

are firmly established, the storage materials will be 

subjected to the performance assessment test 

protocols. The performance parameters and 

conditions that will be derived from the testing 

regime are as follows. 

•	 Specific energy contained in storage system 

•	 Sorption/desorption cycle life 

•	 Resistance to exogenous contaminates 

•	 Average refueling time 

•	 Most favorable thermal-cycle conditions 

•	 Impact resistance (only applicable to 

complete hydrogen storage container 

technologies) 

3 
 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Vibration resistance (only applicable to 

complete hydrogen storage container 

technologies) 

•	 Fire resistance (only applicable to complete 

hydrogen storage container technologies) 

Results 

The first phase of the current project involved a 

review of the current state-of-the-art in measurement 

equipment and protocol for characterization of 

hydrogen storage behavior of small quantities of 

solid-state materials. The review involved a review 

of the pertinent literature and visits to a number of 

leading laboratories. Specifically, General Motors 

Research, Air Products, the National Renewable 

Energy Laboratory and Sandia National Laboratories 

were visited. The general findings of the review of 

the current state-of-the-art are summarized below. 

1. The wide range of materials currently under 

investigation results in a wide range of 

measurement conditions, e.g., sample quantities 

ranging from 1 mg to 1g and environments 

ranging from vacuum to 100 atm. 

2. Three prominent techniques are being used to 

measure hydrogen storage capacity: gravimetric 

(TGA), volumetric (Sieverts) and thermally 

programmed desorption (TPD). 

3. Errors in measurement results have generally been 

related to the indirect nature of the techniques 

(TGA and Sieverts) and/or operating near the 

sensitivity limits of the equipment. 

4. Single walled nanotubes (SWNTs) are currently 

the most challenging material to measure due to a 

combination of very small mass and high 

pressure. However, one laboratory depends on 

hydrogen desorption measured in a vacuum 

environment. 

Proposed Analytical Equipment. The storage 

capacities of solid-state materials are best understood 

through the use of phase diagrams, which are often 

constructed from pressure concentration temperature 

(PCT) measurements. The PCT measurements are 

isothermal measurements of the equilibrium 

hydrogen concentration as a function of the 

surrounding hydrogen pressure. Two methods are in 

use for the determination of sorption isotherms: a 

volumetric method using a Sieverts P-V-T (PressureVolume-Temperature) system and a gravimetric 

method that uses a microbalance for determination of 

weight changes. It has been proposed that both 

volumetric and gravimetric capabilities be included 

in the facility. A brief description of each is provided 

in separate sections that follow. 

In addition to the volumetric and gravimetric 

capabilities, the inclusion of a thermally programmed 

desorption (TPD) apparatus has also been proposed. 

The TPD is in use in a number of laboratories and 

has been reported by one of the leading SWNT R&D 

groups to yield the most accurate measure of SWNT 

desorption. Inclusion of the TPD will allow 

comparisons of all three primary techniques in one 

laboratory and offers the possibility to reproduce 

measurements performed at any laboratory using the 

same technique in use at that laboratory. Inclusion of 

the TPD will not involve a major investment of 

project funds since a Thermal Desorption and 

Recoiling Mass Spectrometry (TDARMS) system in 

place at SwRI can be converted to a TPD for minimal 

cost. The TDARMS/TPD is described in a 

subsequent section. 

High Pressure TGA. A high pressure TGA has been 

proposed for the gravimetric measurements. The 

proposed TGA incorporates a Rubotherm magnetic 

suspension balance and a mass spectrometer for gas 

speciation during desorption measurements. The 

accuracy of the instrument will be dependent upon 

sample mass and system pressure. Accuracy for a 

300 mg sample at 1 atm is estimated to be 3 X 10-4 

wt.%. 

Sieverts Apparatus . It has been proposed that a 

PCT Pro-2000 be employed for volumetric sorption/ 

desorption measurements. The PCT Pro-2000 is a 

fully automated, state-of-the-art Sieverts instrument 

for measuring gas sorption properties of materials. 

The instrument is designed for high precision 

measurements on small samples. Measurements can 

be made at pressures between 0.001 and 200 atm and 

at temperatures up to 400°C. This instrument has an 

estimated accuracy of 0.2 wt.% for a 300 mg sample 

measured at 100 atm. 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

TPD Apparatus . As the name implies, a TPD 

instrument is used primarily for hydrogen desorption 

measurements. It is not effective for generating PCT 

or kinetic data. Nonetheless, TPDs are in use in a 

number of laboratories and have produced the most 

accurate measures of hydrogen storage capacity for 

SWNTs. Inclusion of a TPD instrument in the 

facility would broaden capabilities and allow, along 

with the TGA and Sieverts instruments, for 

replication of any measurements made by a material 

developer. 

SwRI has a TDARMS system, which is being 

converted to a TPD instrument for minimal cost to 

the project. The SwRI instrument has a quadrupole 

mass spectrometer with axial ion source and 90° offaxis secondary electron multiplier detector. It 

utilizes a high-pressure orifice dual gate-valve 

interface between the mass spectrometer and the 

sample chamber. The sample chamber is Summa

passivated and evacuated by cryosorption roughing 

pumps and high vacuum turbo molecular pumps. 

The sample stage and heating are being modified for 

hydrogen desorption measurements. 

Conclusions 

The following conclusions have been drawn 

from the results of the review. 

1. No single measurement technique will be 

appropriate for all of the materials that are 

currently being considered for hydrogen storage. 

2. A comprehensive testing facility will need to have 

multiple techniques to cover the full range of 

materials. 

3. The presence of multiple techniques will provide 

higher confidence in results by enabling cross 

checks of storage capacity using more than one 

technique. 

4. Whenever possible, gas speciation should be 

included in the measurement of storage capacity. 

 FY 2003 Progress Report 

FY 2002 Publications/Presentations 

1. Project overview presented at FreedomCAR Tech 

Team Meeting, September 19, 2002, Detroit, MI. 

2. Project overview presented at Sandia National 

Laboratories, November 18, 2002, Livermore, 

CA. 

3. Project overview presented at IHIG H2 Storage 

Working Group Meeting, February 13, 2003, 

Chicago, IL. 

4. Project overview presented at 2003 Hydrogen and 

Fuel Cells Merit Review Meeting, May 20, 2003, 

Berkeley, CA. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Cell Systems Analysis 

Rajesh K. Ahluwalia (Primary Contact), X. Wang, and Romesh Kumar 

Argonne National Laboratory 

9700 South Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-5979; Fax: (630) 252-5287; E-mail: walia@anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Develop a validated model for automotive fuel cell systems and periodically update it to assess the 

status of technology. 

•	 Conduct studies to improve performance and packaging, to reduce cost, and to identify key R&D issues. 

•	 Compare and assess alternative configurations and systems for transportation and stationary applications. 

•	 Support DOE/FreedomCAR automotive fuel cell (FC) development efforts. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

•	 D. Fuel Cell Power System Benchmarking 

•	 F. Heat Utilization 

•	 H. Start-up Time 

•	 I. Fuel Processor Start-up/Transient Operation 

•	 M. Fuel Processor System Integration and Efficiency 

•	 R. Thermal and Water Management 

Approach 

•	 Develop, document and make available an efficient and versatile system design and analysis tool. 

•	 Validate the model against data obtained in laboratory and at Argonne's Fuel Cell Test Facility. 

•	 Apply model to issues of current interest. 

Accomplishments 

•	 Supported revision of compressor-expander module (CEM) targets by analyzing power consumed by 

the air management subsystem on standard drive cycles for direct H2 and gasoline reformed FC 

vehicles. 

•	 Supported setting of H2 storage targets by analyzing the fuel economy of FC vehicles. 

•	 Developed dynamic models of compressor, expander and motor on a single shaft; ram-air cooled 

condenser and radiator; catalytic water gas shift (WGS) and auto-thermal reactor (ATR) on microlith 

supports; and monolith-supported preferential oxidation (PrOx). 

•	 Proposed and analyzed fuel cell systems for hybrid vehicles. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Analyzed data for Nuvera system obtained at Argonne's Fuel Cell Test Facility. 

• Evaluated FC systems for combined heat and power. 

Future Directions 

• Perform drive cycle analyses of direct hydrogen and reformed FC systems. 

• Analyze FC systems for combined heat and power for stationary applications. 

• Support fuel processor engineering projects at Argonne National Laboratory. 

• Continue to support DOE/FreedomCAR development efforts. 

Introduction 

While different developers are addressing 

improvements in individual components and 

subsystems in automotive fuel cell propulsion 

systems (e.g., cells, stacks, fuel processors, balanceof-plant components), we are using modeling and 

analysis to address issues of thermal and water 

management; design-point and part-load operation; 

and component-, system-, and vehicle-level 

efficiencies and fuel economies. Such analyses are 

essential for effective system integration. 

Approach 

Two sets of models are being developed. GCtool 

is a stand-alone code with capabilities for design, offdesign, steady state, transient and constrained 

optimization analyses of FC systems. GCtool-ENG 

has an alternate set of models with a built-in 

procedure for translation to the MATLAB/ 

SIMULINK platform commonly used in vehicle 

codes such as PSAT (vehicle simulation software 

package developed at Argonne). 

Results 

One of the major activities in FY 2003 was to 

model and analyze pressurized direct hydrogen fuel 

cell systems for hybrid vehicles. The modeled 

system, shown in Figure 1, uses compressed 

hydrogen fuel and operates at 2.5 atm, 80oC, and a 

cell potential of 0.7 V at the rated power point. It is 

humidified to 90% relative humidity at the stack 

temperature using process water and heat from the 

stack coolant, as is the cathode air discharged from 

the compressor. Process water is recovered from 

spent air in an inertial separator just downstream of 

the stack, in a condenser and in a demister at the 

turbine exhaust. The waste heat transferred to the 

coolant in the stack is either used for humidifying the 

anode and cathode streams or rejected in a radiator. 

Our interest is in a load-following fuel cell 

system (FCS) coupled to an energy storage device 

operated in a charge-sustaining mode. For this type 

of hybrid system, the FCS alone must be capable of 

meeting the vehicle power demand under all 

sustained driving conditions. The minimum size of 

the FCS is then determined by the power demand at 

the top sustained speed, taken as 100 mph, or the 

power necessary to maintain the vehicle at 55 mph at 

6.5% grade for 20 min. With battery assist, the FCS 

must have the response time to allow the vehicle to 

accelerate from 0 to 60 mph (Z-60) in a specified 

time, taken as 10 seconds. To be competitive with its 

internal combustion engine counterpart, the FCS 

must have 1-s transient response time for 10% to 

90% power and be able to reach maximum power 

from cold start in 15 s at 20o

C ambient temperature 

and in 30 s at -20oC ambient temperature. We further 

require that the FCS be 50% efficient at the rated 

power and be water balanced for all rated loads at 

50% oxidant utilization and ambient temperatures up 

to 42o

C. 

Our analyses show that the air management 

system, i.e., the compressor, expander and motor, 

must be oversized to meet the cold start-up time 

targets. To meet the 1-s transient time target, over 

short time periods, the electric motor has to be 

overloaded and the maximum oxidant utilization, 

generally limited to 50%, is allowed to rise to 60%. 

FCS for Hybrid Mid-Size SUV. With the 

requirements and approach defined above, Table 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

1 lists the attributes of three FCSs for a hybrid CEM, the net derating is only 10% at 20oC and 25% 

mid-size SUV. The minimum rating of the FCS at -20oC. 

is 80 kW; it is determined by the sustained top 

speed rather than the gradeability criterion. The 

minimum power rating for the energy storage 

system (ESS) is the difference between the 

maximum power demand at Z-60 and the rating 

of the FCS. FCS-1 is a 100-kW system without 

an expander. It needs a rather large 27-kW 

motor for the air management system. FCS-2 is 

a 100-kW system with an expander and a motor 

which is one-third the size of the motor in FCS1. FCS-3 is a 160-kW system with an expander. 

It can potentially power the SUV without battery 

assist. Under all conditions, FCS-3 has the 

highest efficiency and FCS-1 the lowest 

efficiency. 

Stack Performance. Figure 1 shows the behavior of 

the stack for FCS-2, the 100-kW system with an 

expander. Under warm conditions, it produces about 

105 kWe at the rated power point. With the air 

management system oversized to satisfy the cold 

start-up time requirement, it can generate 120 kWe at 

a cell voltage of 0.65 V. At 20o

C, the power is 20% 

lower with the cell voltage decreasing to 0.55 V. At ­

20oC, the stack is derated by 35% and the cell 

voltage goes down to 0.45 V. With the oversized 

Table 1. FCS for Hybrid Mid-Size SUV (AWD = all 

wheel drive, GVW = gross vehicle weight) 

Heat Rejection System. Our analyses show that the 

size of the heat rejection system for the SUV is 

determined by the gradeability condition rather than 

the top sustained speed. Shown in Figure 3 are the 

heat duties and the heat rejection capabilities as a 

function of vehicle speed. For FCS-3, the 160-kW 

system with an expander, the heat duty is zero at 

speeds less than 60 mph, implying that the stack 

cannot be maintained at 80o

C at low speeds. A 

radiator sized for heat duty at 6.5% grade at 55 mph 

can meet the heat rejection requirements at all speeds. 

Because the maximum heat rejection is greater than 

the heat duty, a thermostatic control is required. 

The trends of heat duty and heat rejection are 

similar for FCS-2, the 100-kW system with an 

expander, but with one important difference. The 

Figure 1. Pressurized Direct H2 Fuel Cell System 

Figure 2. Stack Behavior with Oversized CEM 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

heat duty at the gradeability condition is nearly twice 

as large even though the FCS is 60% smaller. 

Water Management System. The results in Figure 

4 indicate that the criterion for sizing the water 

management system changes with FCS rating. For 

FCS-3, the 160-kW system, the maximum heat duty 

levels off after 80 mph. A condenser sized for heat 

duty at 6.5% grade at 55 mph can meet heat rejection 

requirements at all speeds. 

For FCS-2, the 100-kW system, the heat 

duty peaks at about 75 mph. Heat load at grade 

is no longer the design point, nor is the speed at 

which the heat load is highest. Instead, the 

design point is at an intermediate speed of about 

70 mph. Unlike the radiator, the condenser for a 

Figure 3. Heat Loads on the Stack Radiator 

100-kW system is smaller than one for a 160­

kW system. 

CEM Idle Speed. Our work on the air 

management system has looked at the issues of 

idle speed and maximum turndown. For 

reference, idle speed is the minimum rpm at 

which the air management system can provide 

sufficient cathode air to enable the FCS to 

generate the power needed by the CEM if it was 

overloaded to meet a sudden surge in power 

demand. Idle speed is an important parameter 

that affects the system efficiency at part load as 

well as oxygen utilization and water recovery. It 

is determined by the motor power, the motor/ 

controller algorithm and the physical design of 

the rotating turbomachinery. 

For a high speed, matched, turbo compressor/ 

expander set, we have determined that with an 

expander, the maximum turndown can be as high as 

20. Without an expander in the system, the 

maximum turndown can be as low as 5. 

FCS Efficiency. Figure 5 shows the effect of CEM 

turndown on FCS efficiency over the Federal Urban 

Driving cycle (FUDS) for FCS-2, the 100-kW 

system with an expander. Results are presented for 

CEM turndowns of 5 and 20. Differences in 

efficiency are clearly evident at low loads. Both give 

efficiencies in excess of 60% over FUDS, but with a 

turndown of 20, the peak efficiency can exceed 70% 

at low loads. However, the scatter in dynamic 

efficiency is wider at a maximum turndown of 20. 

Figure 4. Heat Loads on the Water Recovery 

Condenser 

Figure 5. Effects of CEM Turndown and Expander on 

FCS Efficiency over FUDS 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

This scatter is largely due to acceleration demand 

near idling speeds. 

Also shown in Figure 5 is the contribution of the 

expander to FCS efficiency over FUDS. Comparing 

the results for FCS-2 and FCS-1, the 100-kW 

systems with and without an expander, differences in 

efficiency at high loads are due to the additional 

power generated by the expander and at low loads 

due to the larger turndown obtainable with an 

expander in the system. Without an expander, the 

dynamic fluctuations in efficiency are minor at low 

loads but can be substantial at high loads. 

Oxygen Utilization. Figure 6 shows that in a loadfollowing FCS, oxygen utilization cannot be held 

constant over driving cycles. This is because of the 

inertia of the rotating components comprising the air 

management system and the finite turndown. In 

particular, oxygen utilization is close to zero during 

idling conditions and is low during deceleration. The 

system cannot be water-balanced at low O2 

utilization. In our dynamic simulations, we attempt 

to maintain the water tank at a constant level by 

recovering excess water at high loads to compensate 

for water being consumed at low loads. 

Conclusions 

•	 The air management system plays an important 

role in determining the transient response, cold 

start-up and part-load performance of a 

pressurized FCS. 

Figure 6. Oxygen Utilization over FUDS 

 FY 2003 Progress Report 

•	 The size of the heat rejection system for a hybrid 

mid-size SUV is determined by the gradeability 

condition rather than the top sustained speed. 

•	 The efficiency at part load and the dynamic 

fluctuations in efficiency depend on the 

maximum CEM turndown and the presence of an 

expander in the system. 

•	 In load-following FCSs, oxygen utilization 

cannot be held constant over driving cycles. 

Although it is not possible for the FCS to be 

water balanced during periods of low oxygen 

utilization, it can be water neutral over a driving 

cycle. 

FY 2003 Publications/Presentations 

1. Ahluwalia, R. K., Deville, B., Rousseau, A., Doss, 

E. D., Zhang, Q., and Kumar, R., "Performance of 

Hydrogen Fuel Cell Systems and Vehicles," Third 

IEA Annex XV Meeting, Düsseldorf, Germany, 

June 28, 2002. 

2. Ahluwalia, R. K. and Milliken, J., "Hydrogen, 

Fuel Cells and Infrastructure Technologies," 

World Renewables Energy Congress, Cologne, 

Germany, July 1-5, 2002. 

3. Ahluwalia, R. K., Wang, X., and Rousseau, A., 

"Direct Hydrogen Fuel Cell Systems for 

Transportation," Fourth IEA Annex XV Meeting, 

Palm Springs, CA, November 17-18, 2002. 

4. Ahluwalia, R. K., Wang, X., and Rousseau, A., 

"Direct Hydrogen Fuel Cell Systems for Hybrid 

Vehicles," Fifth IEA Annex XV Meeting, 

Stockholm, Sweden, June 17-18, 2003. 

5. Ahluwalia, R. K., Doss, E. D., and Kumar, R., 

"Performance of High-Temperature Polymer 

Electrolyte Fuel Cell Systems," Journal of Power 

Sources, 117, 45-60, 2003. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Cell Vehicle Systems Analysis 

Keith Wipke (Primary Contact), Tony Markel, Kristina Haraldsson, Ken Kelly, Andreas Vlahinos

 National Renewable Energy Laboratory 

1617 Cole Blvd. 

Golden, CO 80401 

Phone: (303) 275-4478; Fax: (303) 275-4415; E-mail: Tony_Markel@nrel.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Provide DOE and industry with technical solutions and modeling tools that accelerate the introduction 

of robust fuel cell technologies. 

•	 Quantify benefits and impacts of the Hydrogen, Fuel Cells & Infrastructure Technology (HFC&IT) 

Program development efforts at the vehicle level (current status evaluation). 

•	 Understand sensitivity of fuel cell technical target values and provide recommendations to DOE 

technology development managers (future goal evaluation). 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

•	 I. Fuel Processor Startup/Transient Operation 

•	 P. Durability 

•	 R. Thermal and Water Management 

Approach 

•	 Develop component and vehicle models and link to existing models to enhance systems analysis 

capabilities. 

•	 Work with industry to apply robust design techniques, optimization tools, and computer-aided 

engineering (CAE) tools to overcome technical barriers.
 

•	 Study benefits of fuel cell system and vehicle design scenarios and transfer to industry. 

•	 Assess impact of various technical team targets at component level. 

Accomplishments 

•	 Analyzed and published "Fuel Economy Impacts of Gasoline Reformer Warm-up." 

•	 Integrated two new detailed fuel cell system models into ADVISOR, expanding the range of
 

complexity of modeling capabilities.
 

•	 Published technical paper on fuel cell system water management over typical drive schedules. 

•	 Applied robust design methods to fuel cell stack design with Plug Power to understand manufacturing 

and durability sensitivities. 

•	 Developed Technical Targets Tool for tracking and analyzing the national fuel consumption impacts of 

DOE research programs. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Completed initial sensitivity analysis of vehicle fuel economy to fuel cell program technical targets 

using Technical Targets Tool. 

Future Directions 

•	 Perform fuel cell hybrid vehicle system optimization - work with FreedomCAR fuel cell, energy 

storage, and vehicle systems technical teams to develop energy storage system targets for fuel cell 

hybrid vehicles. 

•	 Assess sensitivity of fuel consumption to fuel cell technical targets applied across multiple vehicle 

platforms using Technical Targets Tool. 

•	 Continue water and thermal management analyses for fuel cell vehicles under real driving conditions. 

•	 Transfer robust design techniques to industry to address fuel cell stack cost and durability technical 

barriers. 

Introduction 

The Fuel Cell Vehicle Systems Analysis activity 

at the National Renewable Energy Laboratory is a 

continuation and expansion of previous efforts in this 

area. Previous efforts focused on the application of 

ADVISOR [1], a complete vehicle systems modeling 

tool, to understanding fuel cell hybrid vehicle design 

barriers and opportunities. The Office of Hydrogen, 

Fuel Cells & Infrastructure Technologies has used 

the simulation results from ADVISOR in the past to 

assess and revise component and system technical 

targets. Primary financial support for the 

development and maintenance of ADVISOR has 

been through the Office of FreedomCAR and Vehicle 

Technologies, and the Office of Hydrogen, Fuel Cells 

& Infrastructure Technologies has been able to 

leverage this significant investment. 

Recent efforts build upon and expand the 

capabilities of this activity. A new Technical Targets 

Tool was developed and introduced to automate the 

technical targets analysis process. It links directly to 

ADVISOR for vehicle performance estimates and 

rolls these results up to predict national fuel 

consumption impacts of DOE research efforts across 

multiple light-duty vehicle platforms. Additionally, 

we integrated and applied two new detailed fuel cell 

system models to understand the water management 

issues of fuel cell vehicle operation over typical drive 

cycles. Future studies will include analysis of 

thermal management characteristics during vehicle 

operation. Finally, we have developed collaborative 

relationships with industrial partners and have 

applied robust design methods to stack and reformer 

systems to address cost and durability technical 

barriers. 

Approach 

It has been our approach to develop component 

and vehicle models and link them to existing models 

to enhance our systems analysis capabilities. We 

work with industry to share and apply robust design 

techniques, optimization tools, and CAE tools to 

address the issues of durability, cost, and efficiency. 

Any results that we derive that are non-proprietary 

typically form the basis for a publication. 

Publication and public presentation of our study 

results have been effective means for transferring 

knowledge on simulation results and design 

sensitivities to industry. Finally, we support DOE's 

effort to set reasonable and challenging technical 

targets by assessing the impacts of various technical 

team targets at vehicle system and fleet levels. 

Results 

Using the existing models in ADVISOR, we 

estimated the fuel economy impacts on EPA drive 

cycles of gasoline reformer warm-up. Test data is 

not yet available as to how long the warm-up process 

may take or how much energy it may require; 

however, in our study, we swept the duration and 

fueling rate over reasonable ranges. We predicted 

that for long duration and high fueling rates, the fuel 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies

consumption for an urban drive cycle could increase 

by as much as 90% (Figure 1). If the DOE programs 

are successful in meeting their targets for warm-up, 

the fuel economy penalty would be 15%-30% in 

comparison to a hot start fuel cell scenario. In 

comparison, a typical internal combustion engine 

(ICE) vehicle incurs a 6%-8% fuel economy penalty 

for cold-starts. The results of this small study were 

published at the 2003 Society of Automotive 

Engineers (SAE) Future Transportation Technologies 

Conference. 

We have also integrated two new fuel cell system 

models into ADVISOR. The first, a fuel cell model 

developed by Virginia Tech, based on their 

contributions to the FutureTruck competition, allows 

us to model systems with variable pressure operating 

strategies and performs a complete thermal and water 

balance on the system. The second is a model 

developed at the Swedish Royal Institute (KTH). 

This model is based on the Springer et al. stack 

model and focuses on complete thermodynamics for 

the balance of plant system. The models were 

applied to assess the water balance of a fuel cell 

hybrid vehicle over typical drive cycles. Results of 

this study were published at the 2003 American 

Society of Mechanical Engineers (ASME) First 

International Conference on Fuel Cell Science, 

Engineering and Technology. 

The results of a study with Plug Power looking at 

the application of robust design techniques for fuel 

 FY 2003 Progress Report 

cell stack design were also published at this same 

conference. The study reviewed the sensitivity of 

pressure and pressure distribution within the 

membrane electrode assembly (MEA) due to 

variability in mounting bolt loading, MEA thickness, 

bipolar plate thickness, and material properties 

(Figure 2). Understanding how tightly these 

manufacturing variabilities must be controlled is 

critical to reducing production costs and improving 

durability. 

As a result of our efforts this year, we completed 

the first version of the Technical Targets Tool. This 

new tool provides a means for tracking and assessing 

the impacts of DOE program technical targets. The 

tool contains a database of technical targets that are 

applied across multiple vehicle platforms. The tool 

uses ADVISOR to predict the performance 

characteristics of vehicles based on the technical 

targets. A time-based penetration curve and vehicle 

class specific sales predications are used to estimate 

the potential fuel consumption savings of the DOE 

technology programs. Future results are expected to 

Figure 1.	 Estimated Fuel Consumption Impact Based 

on a Range of Startup Durations and Fueling 

Rates 

Figure 2.	 Histograms of maximum maxδztop and 

differential compressive stress ∆δztop in the 

top MEA 

3 
 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

help ensure that the existing program technical 

targets lead to applicability across multiple platforms 

and provide the greatest impact from the DOE 

efforts. 

Conclusions 

The following conclusions can be drawn from the 

Fuel Cell Vehicle Systems Analysis efforts: 

•	 Our analysis showed that the fuel economy 

impacts of gasoline reformer warm-up may be 

substantial. The DOE program targets are 

focused on minimizing this impact. 

•	 Our study on fuel cell system water management 

over typical drive schedules highlighted 

capabilities of the new fuel cell system models 

integrated into ADVISOR. Results of the water 

balance study showed that condenser and 

reservoir sizing decisions should consider both 

the drive cycle requirements and the operating 

conditions. 

•	 The application of robust design methods to fuel 

cell stack design provided our industry partner, 

Plug Power, with a process and a better 

understanding of the sensitivities that several 

design variables have on stack pressure 

distribution. This information could lead to less 

expensive, more durable fuel cell stacks. 

•	 We demonstrated that the new Technical Targets 

Tool could be used to predict impacts on national 

fuel consumption resulting from DOE research 

program efforts applied across multiple vehicle 

platforms. As expected, the initial sensitivity 

results using the Technical Targets Tool indicate 

the fuel cell system and motor efficiencies have a 

significant impact on vehicle fuel economy. 

FY 2003 Publications/Presentations 

1. Markel, Tony; Wipke, Keith; Haraldsson, 

Kristina; Kelly, Ken; Vlahinos, Andreas. "Fuel 

Cell Vehicle Systems Analysis." Presented at 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Annual Program Review. 

Berkeley, CA. May 20-23, 2003. 

 FY 2003 Progress Report 

2. Wipke, K. B.; Markel, A.; Haraldsson, K.; Davis, 

P. "Predicting the Fuel Economy Impact of 

"Cold-Start" for Reformed Gasoline Fuel Cell 

Vehicles." SAE Publication 2003-01-2253. 

Presented at SAE Future Transportation 

Technologies Conference. Costa Mesa, CA. 

June 23-25, 2003. 

3. Markel, Tony; Zolot, Matthew; Wipke, Keith B.; 

Pesaran, Ahmad A. "Energy Storage System 

Requirements for Hybrid Fuel Cell Vehicles." 

3rd International Advanced Automotive Battery 

Conference. Nice, France. June 10-13, 2003. 

4. Haraldsson, Kristina; Markel, Tony; Wipke, 

Keith. "An Analysis Of Water Management for a 

PEM Fuel Cell System in Automotive Drive 

Cycles." ASME First International Conference 

on Fuel Cell Science, Engineering and 

Technology. Rochester, New York. April 21-23, 

2003. 

5. Willis, Gordon; Weller, Rick; Wipke, Keith. "An 

Engineering System for Automated Design and 

Optimization of Fuel Cell Powered Vehicles." 

ASME First International Conference on Fuel 

Cell Science, Engineering and Technology. 

Rochester, New York. April 21-23, 2003. 

6. Vlahinos, Andreas; Kelly, Kenneth; D'Aleo, Jim; 

Stathopoulos, Jim. "Effect of Material and 

Manufacturing Variations on Membrane 

Electrode Assembly Pressure Distribution." 

ASME First International Conference on Fuel 

Cell Science, Engineering and Technology. 

Rochester, New York. April 21-23, 2003. 

7. Kelly, Kenneth; Vlahinos, Andreas; Rodriguez, 

Pablo; and Bharathan, Desikan. "Innovative 

Thermal Management of Fuel Cell Power 

Electronics." ASME First International 

Conference on Fuel Cell Science, Engineering 

and Technology. Rochester, New York. April 

21-23, 2003. 

8. Haraldsson, Kristina; Wipke, Keith. "An 

Evaluation of Select PEM Fuel Cell System 

Models." The 202nd Electrochemical Society 

Symposium. Salt Lake City, Utah. October 23, 

2002. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

9. Markel, Tony; Wipke, Keith; Nelson, Doug. 

"Vehicle System Impacts of Fuel Cell System 

Power Response Capability." SAE Publication 

2002-01-1959. Presented at FutureCar 

Congress. June, 2002. 

References 

1. Markel, T., Brooker, A., Hendricks, T., Johnson, 

V., Kelly, K., Kramer, B., O'Keefe, M., Sprik, S., 

Wipke, K., "ADVISOR: a systems analysis tool 

for advanced vehicle modeling" Journal of 

Power Sources Volume 110, Issue 2, 22 August 

2002, pp. 255-266. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Cost Analyses of Fuel Cell Stack/Systems 

Eric J. Carlson (Primary Contact) 

TIAX LLC 

Acorn Park 

Cambridge, MA 02140-2390 

Phone: (617) 498-5903; Fax: (617) 498-7295; E-mail: carlson.e@tiax.biz 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

ANL Technical Advisor: Robert D. Sutton 

Phone: (630) 252-4321; Fax: (630) 252-4176; E-mail: sutton@cmt.anl.gov 

Objectives 

To develop an independent cost model for proton exchange membrane (PEM) fuel cell systems for 

transportation applications and to assess cost reduction strategies for year 2000 to 2004 development 

projects 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 N. Cost (Fuel-Flexible Fuel Processor) 

•	 O. Stack Material and Manufacturing Cost 

Technical Targets 

System Efficiency 

Cost 

2010 2015 

Direct Hydrogen Fuel Cell Power System (including hydrogen storage) 60% $45/kWe $30/kWe 

Reformer-based Fuel Cell Power System 

- clean hydrocarbon or alcohol based fuel 

- 30 second start-up 

- satisfies emissions standards 

45% 

Approach 

•	 In the first two years, develop a baseline system configuration and cost estimate based on best 

available and projected technology and manufacturing practices, and assess the impact of potential 

technology developments on system cost reduction 

•	 In the subsequent four years, annually update the baseline cost model and system scenarios based on 

assessments of developments in PEM fuel cell system technologies and manufacturing processes. 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

• Evaluated status of bipolar plate technology for PEM fuel cells (Table 1) 

• Compared cost and performance of graphite and metallic bipolar plates 

• Examined performance impact of using graphite bipolar plates instead of metallic bipolar plates 

Table 1. Overview of Bipolar Plate Technologies Considered in this Analysis 

Substrate Material Coating Material 

Aluminum Non-Metal Metal-Based 

Stainless Steel 

Ni-Cr alloys 

Metal/polymer composite 

Graphite 

Conductive Polymer 

Noble Metals (gold, silver) 

Metal Carbides 

Metal Nitrides 

Cladding 

Future Directions 

Develop projections of future system performance and cost based on continued industry feedback, 

alternative system scenarios, and projected technology developments 

Introduction 

In 1999, a baseline cost estimate for a 50-kW 

PEM fuel cell system for passenger vehicles was 

developed based on technology available in the year 

2000, but using a high production volume scenario 

(i.e., 500,000 units per year). In 2000, we solicited 

feedback from system and component developers on 

the system configuration, design and performance 

parameters, and manufacturing process and costing 

assumptions. The impacts of alternative system 

design approaches were also assessed: specifically, 

what would be the impact of sizing the stack at the 

high power point rather than 0.8 volts, and what 

would be the impact of hybridization, i.e., reducing 

or increasing rated power, on the fuel cell system 

power cost ($/kW). In 2001, we focused on the 

development of future costs based on projected 

technology. In 2002, an electrochemical model for 

the relationship between catalyst loading, 

temperature, pressure, and power density was 

combined with the cost model to understand the 

tradeoffs between catalyst loading and cost of the 

stack. The cost model was used to develop 

projections for direct hydrogen fueled systems. In 

2003, we evaluated the impact of replacing graphite 

bipolar plates with metallic bipolar plates. 

The potential benefits of metallic bipolar plates 

that we analyzed were reduced plate thickness and 

weight and improved thermal and electrical 

conductivity. Higher electrical conductivity 

increases the efficiency of the system by decreasing 

parasitic loss, which enables the formation of smaller 

stacks. Similarly, lighter weight increases power 

density [kW/kg]. Thinner plates decrease the 

thermal management and the packaging 

requirements, which increases the applicability of 

PEM fuel cells in the automotive industry. All of 

these benefits may lead to lower cost (Figure 1). 

Finally, recyclability and consistency of metal 

forming technologies were considered as additional 

benefits of metallic bipolar plates. 

Approach 

The assessment of bipolar plate technology for 

PEM fuel cells was started with the initial hypothesis 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 2.	 Benefits and Drawbacks of Graphite, 

Composite and Metallic Bipolar Plates 

Figure 1. QUANTUM Compressed Hydrogen Storage 

Graphite (machined) Metal (SS, Al, Ti) Graphite Composite 

Benefits • Stability 

• Low specific density 

• Low contact resistance 

with electrodes 

• Corrosion resistance 

• High Thermal 

conductivity 

• Recyclable 

Consistent 

product 

•

• Lower contact 

resistance 

• Corrosion 

resistance 

Drawbacks • Expensive to machine 

• Brittle 

• Thick 

• Needs coating 

• Membrane 

poisoning 

• Formation of 

insulating 

surface oxides 

• Low bulk 

conductivity 

that metallic bipolar plates may lower stack cost by 

reduction of ohmic losses, and that increased 

volumetric power density would enhance integration 

into vehicles. The following comparative parameters 

were considered: 

•	 thickness (and its impact on volumetric 

density) 

•	 weight 

•	 thermal conductivity 

•	 electrical conductivity (bulk and interfacial 

resistance) 

•	 material and processing cost 

Metallic bipolar plates were analyzed by 

evaluating the alternatives for substrate material and 

coating technology. Thermal and electrical 

properties and feasible dimensions were studied. 

Industry representatives from the bipolar plate 

and coating industries and material suppliers were 

contacted to identify benefits and drawbacks of 

metallic and graphite bipolar plates (Table 2). 

Results 

Interfacial resistance between the bipolar plate 

and the electrode dominates bulk resistance for both 

graphite and metal bipolar plates. There was no 

Figure 2. Bulk and Interfacial Contact Resistance for 

Stainless Steel Alloy SS 904 L Bipolar Plates 

evidence indicating that the interfacial resistance for 

metallic plates was lower than graphite’s. Therefore, 

2 metal’s smaller bulk resistance (9.5 x10-3 mΩ-cm

vs. 9 mΩ-cm2) is not a clear advantage (Figure 2). 

The cost of thinner and highly corrosion resistant 

metallic plates (i.e. SS 904 L) is not lower than 

thicker graphite-based plates. As an example, the 

cost per plate (1 mm thick, 603 cm2) made of 904L 

was calculated to be $10.31, compared to $2.75 per 

graphite-based plate (3.75 mm thick, 603 cm2

), as 

shown in Table 3. Application of the conductive 

coating further increases the cost of the substrate. 

A three-fold decrease in the thickness of the 

bipolar plate (e.g. 3.75 to 1 mm) decreases the stack 

volume by at least 50% and the overall system 

volume by at least 10%. However, graphite plate 

thickness is approaching values of 1 mm, similar to 

metallic bipolar plates. Flow field requirements and 

mechanical robustness set minimum dimensions, 

regardless of manufacturing feasibility. Therefore, 

although thinner plates have a significant effect on 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 3. Metallic and Graphite Plate Costs (all costs are in U.S. dollars) 

 Plate Type 

Substrate Material Cost [$/plate] 

Substrate Material Cost [$/m2

]

Processing Cost [$/plate] 

Processing Cost [$/m2

] 

Coating Cost [$/plate] 

Coating Cost [$/m2

] 

TOTAL [$/plate] 

TOTAL [$/m2

] 

TOTAL STACK COST for BIPOLAR 

PLATES [$/kW] 

Weight [kg] 

Graphite 

Baseline
 

2.24 

37 

0.51 

8 

No 

No 

2.75 

46 

21 

179 

Metallic – SS 316 

2.22 

37 

1.07 

18 

3.79 

63 

7.08 

117 

53 

228 

Metallic - SS 904 

5.42 

90 

1.07 

18 

3.79 

63 

10.31 

171 

78 

225 

volumetric density, they can be achieved by using 

both graphite and metal. 

Thermal conductivity of metallic bipolar plates 

based on stainless steel is not superior to molded 

graphite (Figure 3). 

Conclusions 

•	 Metallic bipolar plates do not offer a clear 

performance or cost advantage over graphitebased bipolar plates. 

•	 Cost of bipolar plates could increase 23-40% 

relative to graphite plates depending on the 

stainless steel alloy used. 

•	 Metallic bipolar plates do not result in 

significantly higher volumetric density. 

•	 Thermal management requirements for metallic 

bipolar plates are not more favorable than 

requirements for graphite plates. 

•	 Development of effective coatings are critical to 

the viability of metallic bipolar technology. 

Figure 3. Thermal Conductivity of Different Materials

FY 2003 Publications/Presentations 

1. Fuel Cell Cost Issues. SAE TOPical TEChnical 

Symposium. April 8-9, 2003. Dearborn, 

Michigan. 

2. 2003 Annual Hydrogen, Fuel Cells & 

Infrastructure Technologies Program Merit 

Review and Peer Evaluation in Berkeley, 

California. 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Precious Metal Availability and Cost Analysis for PEMFC Commercialization 

Eric J. Carlson (Primary Contact) 

TIAX LLC 

Acorn Park 

Cambridge, MA 02140-2390 

Phone: (617) 498-5903; Fax: (617) 498-7295; E-mail: carlson.e@tiax.biz 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: arlene.anderson@ee.doe.gov 

ANL Technical Advisor: Bill Cleary 

Phone: (202) 586-1570; Fax: (202) 586-9811; E-mail: Bill.Cleary@ee.doe.gov 

Objectives 

The project objectives include: 

•	 Assessment of current and projected demand for platinum group metals (PGMs) exclusive of fuel cell 

applications 

•	 Estimation of the relationships between supply capacity/reserves and long-term growth in demand for 

PGMs 

•	 Development of an econometric model to simulate the impact of fuel cell market growth scenarios on 

PGM supply and pricing 

•	 Analysis of supply and pricing sensitivity to critical parameters in the model related to fuel cell 

markets and technology advances 

•	 Solicitation of critical feedback from the important participants in the PGM value chain on the model 

assumptions and projections 

•	 Development of a cost projection for the economics of recycling PGMs from fuel cells and the impact 

on PGM supply and price 

The overall goal is not only to develop projections of PGM availability and cost, but also to identify and 

quantify the industry and market drivers influencing these parameters. On the demand side, we will break 

down the demand between existing markets and the potential applications of fuel cells. We will identify 

underlying trends in the industrial/chemical and lifestyle markets with attention to growth of demand and 

potential for substitution of alternative materials. In the fuel cell markets, the impact of technology on 

PGM demands will also be considered. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• N. Cost 	 

•	 O. Stack Material and Manufacturing Cost 

The overall DOE platinum target for reformate based-systems is 0.2 g Pt/kW. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

The project has been broken into five tasks as follows: 

1.	 Collection of historical PGM supply/demand/pricing and resource data 

2.	 Development of fuel cell market commercialization scenarios 

3.	 Development of a PGM recycling scenario, including a high level PGM proton exchange membrane 

fuel cell (PEMFC) recycling cost model 

4.	 Development of an econometric model for the simulation of the impact of fuel cell introduction on 

PGM supply and price 

5.	 Solicitation of feedback from PGM industry and automotive original equipment manufacturers 

(OEMs) 

Tasks 1 and 4 were scheduled for the fiscal years 2001 and 2002. The balance of the tasks will be 

completed in year 2003. 

Accomplishments 

•	 Econometric analysis of historical platinum price, supply, and demand data completed 

•	 Platinum resource and market data compiled 

•	 Results of econometric analysis presented to Johnson-Matthey and International Platinum (IPA) for 

feedback 

•	 Market demand scenarios developed for fuel cell vehicles and platinum catalyst out to 2050; scenarios 

presented to South African mining companies, IPA, and automotive OEMs to obtain feedback on 

market projections, potential supply responses, resource projections, and technology assumptions 

Future Directions 

•	 The platinum and automotive industry feedback will be integrated to develop conclusions on the 

potential impact of PEMFC commercialization on price and availability of platinum 

•	 Final report will be issued 

Introduction 

Platinum group metals (PGMs) are critical to the 

commercialization of fuel cells because of their role 

in supporting critical levels of performance (power 

density and efficiency), but they also represent a 

significant contribution to overall system cost. 

Depending on operating design parameters, platinum 

would represent between 10 and 20% of the system 

cost of a gasoline fuel cell system produced in high 

volume. PGMs (primarily platinum and some 

ruthenium) are critical to catalyzing reforming/shift 

reactions in the fuel processor and electrochemical 

oxidation and reduction in the fuel cell, with the fuel 

cell requirements presently dominating the demand. 

Successful adoption of fuel cells in transportation 

applications in the long term could create markets on 

the order of ten million vehicles, leading to 

significant pressure on PGM suppliers to increase 

production capacity and supply. Consideration of 

stationary and portable applications for fuel cells 

further increases the demands on PGM supplies. 

Clearly, the combination of stationary, portable and 

transportation markets for fuel cells will create 

pressure on the PGM industry to increase supplies 

and might cause skyrocketing prices (thereby 

threatening fuel cell market viability) unless action is 

taken to guide the process. In addition to price, the 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies

commercialization of fuel cells will also depend on 

the amount of economically mineable PGM 

resources and the ability of the PGM value chain to 

supply the PGM materials in the needed forms and at 

reasonable markups above the London Metals 

Exchange (LME) price. 

Econometric analysis and modeling were applied 

to understand and simulate the relationships between 

supply, demand, and price for historical markets. An 

understanding of the basis for platinum resource 

projections was developed and used to compile a 

future platinum resource estimate. Inputs from the 

platinum and automotive industries are being 

obtained to project future fuel cell vehicle platinum 

demand and the ability of the mines to respond to 

these demands. The impact on price of platinum will 

be assessed using the econometric model. 

Approach 

The modeling approach starts with construction 

of an econometric model based on historic supply, 

demand, and price data. A simulation will then be 

run to study the impact of introduction of fuel cell 

vehicles on the supply and price of platinum. 

Automotive catalysts and jewelry are the two 

dominant markets for platinum (approximately 

80%); hence, they will be important elements in the 

econometric model. The investment industry 

consumes a minor amount of material but can exert 

significant influence on short-term price. However, 

over long periods of time, investment should have 

zero impact on supply and demand. 

After completion and validation of the 

econometric model, future demand scenarios will be 

input into the econometric model to project the 

impact of fuel cell commercialization on supply and 

pricing. The scenarios for stationary, portable, and 

transportation applications of fuel cells will range 

from optimistic to pessimistic and contain volume 

and time estimates. Economic growth, catalyst 

technology development, and shifts in automotive 

powertrain technology will be some of the factors 

considered in development of the demand scenarios. 

The model and the scenarios can be used to conduct 

sensitivity analyses to the various factors. Recycling 

will play a significant role as platinum consumption 

 FY 2003 Progress Report 

increases further. The high value of recycled 

platinum drives a high level of recovery today. 

Inputs from the platinum and automotive 

industries have been and are being solicited to obtain 

data, feedback on assumptions, and reactions to 

projections of fuel cell technology and 

commercialization. The two industries worked 

together to introduce platinum-based catalytic 

converters in the 1970's, and similar efforts of even 

larger scale (e.g., expansion in mining capacity and 

capital investments) will be called for in the 

commercialization of fuel cells. Consequently, input 

from the industry drivers is essential to development 

of conclusions. 

Results 

Use of the econometric model to simulate the 

impact of fuel cell vehicle commercialization 

indicates that the platinum price will increase in the 

short-run until increased production restores balance 

between supply and demand. As production catches 

up to demand, the platinum price will return to its 

long-term mean price. Table 1 contains an 

illustrative case of fuel cell vehicle (FCV) 

introduction and platinum demand. Figure 1 

illustrates the results from the simulation model for 

short-run and longer-run price. 

The total platinum demand projection was built 

up from total vehicle projections for the U.S., Japan, 

Western Europe, China, and India; fuel cell vehicle 

market penetration scenarios; and a vehicle platinum 

requirement scenario. The selected countries 

represent approximately 80% of worldwide vehicle 

Table 1. Illustrative Fuel Cell Vehicle Introduction 

Scenario and Simulated Impact on Platinum 

Price 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

sales. Vehicle projections were based on population loadings per vehicle of 20 grams in 2015 and 15 

projections for the respective countries and assumed grams by 2025. 

vehicles per capita. For the mature markets in the 

developed countries, the vehicles per capita have 

reached asymptotic values, while for the emerging 

transportation markets in developing countries, the 

vehicles per capita will show significant growth. For 

this reason, we developed vehicle per capita 

scenarios for the latter regions. We also assumed a 

time lag for fuel cell vehicle introduction into the 

emerging markets. In the developed countries, a 

moderate to declining population growth leads to a 

modest vehicle sales increase driven by the U.S. 

Large populations along with increasing vehicles per 

capita in China and India lead to significant new 

vehicle markets. In 2050, we estimated sales in the 

developed countries would be 47 million vehicles, 

while the developing countries would add an 

additional 25, 46, or 86 million vehicles depending 

on the market growth scenario (i.e., slow, moderate, 

or high). 

Preliminary fuel cell market introduction 

scenarios are shown in Figure 2. The ANL (Argonne 

National Laboratory, Ref 1) penetration curve was 

used to estimate fuel savings in the U.S. from fuel 

cell vehicle commercialization. In the ANL scenario, 

used as our bounding case, commercialization starts 

with rapid adoption in 2018 and a market penetration 

of 100% by 2037. The more moderate scenarios 

assume a slower adoption and penetrations of 80% 

and 50%. Overlaying these scenarios, we assume 

technology advances that result in reduced platinum 

Combining the vehicle projections, fuel cell 

vehicle market projections, platinum loading 

assumptions, and growth in traditional platinum 

markets leads to the primary platinum curves shown 

in Figure 3 for the moderate and slow growth fuel 

cell vehicle scenarios. Figure 4 highlights the critical 

role that recycling will play in reducing the demand 

for primary platinum. In the moderate growth 

Figure 2.	 Fuel cell vehicle market penetration scenarios 

for developed and developing countries. The 

latter countries have 10- and 15-year time lags 

for the moderate and slow scenarios. 

Figure 1.	 Simulation of platinum price response to 

increased platinum demand from fuel cell 

vehicle introduction. 

Figure 3.	 Total primary platinum demand needed to 

supply vehicle and other platinum market 

needs. The vehicle demand includes both the 

developed and developing countries. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

scenario, recycled platinum used in fuel cell vehicles 

exceeds primary platinum after 2045. Figure 5 

shows the platinum demand for the moderate 

commercialization scenario relative to historical 

platinum production data. The integration of the 

primary platinum demand out to 2050 shows the 

cumulative production represents approximately 

30% of projected resources. 

Figure 4.	 Overall annual platinum demand for the 

moderate growth scenario with the primary and 

recycled supply shown. Platinum from 

recycling exceeds primary supply after 2045. 

Figure 5.	 Moderate vehicle and fuel cell 

commercialization scenario platinum demand 

plotted relative to historical growth in platinum 

production. 

Conclusions 

The results presented in this report still require 

the final feedback from the platinum and automotive 

industries. 

•	 Short-run spikes in platinum price may occur, 

dependent on the balance between demand and 

supply. Traditionally, the platinum industry has 

tried to maintain a constant real price to sustain 

traditional markets for PGMs while promoting 

growth of new applications. The expectation is 

that the platinum industry will continue to 

increase production to keep supply and demand 

in balance. 

•	 The platinum industry will have to increase their 

rate of new production capacity to satisfy 

increased demand. 

•	 High levels of recycling will be critical to 

reducing demands on primary platinum and are 

expected to exceed primary production. 

•	 The combination of recycling and advances in 

mining technology to economically recover 

deeper sources of PGM ore will be needed to 

maintain reserves of platinum. 

References 

1. M.K. Singh, "VISION: a spreadsheet energy use 

model developed by ANL for the U.S. DOE", 

ANL, December 2002 run for DOE/OHFCIT2 

FY 2003 Presentations 

1. 2003 U.S. DOE Hydrogen, Fuel Cells & 

Infrastructure Technologies Program Merit 

Review and Peer Evaluation in Berkeley, 

California. 

2. 2002 Fuel Cell Seminar in Palm Springs, 

California. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

DFMA Cost Estimates of Fuel-Cell/Reformer Systems at Low/Medium/High 

Production Rates 

Brian D. James (Primary Contact), Gregory D. Ariff, Reed C. Kuhn, and Duane B. Myers 

Directed Technologies, Inc. 

3601 Wilson Boulevard, Suite 650 

Arlington, VA 22201 

Phone: (703) 243-3383; Fax: (703) 243-2724; E-mail: Brian_James@DirectedTechnologies.com 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

ANL Technical Advisor: Walter Podolski 

Phone: (630) 252-7558; Fax: (630) 972-4430; E-mail: podolski@cmt.anl.gov 

Objectives 

•	 Develop realistic and internally consistent detailed designs for automotive gasoline fuel processor/ 

proton exchange membrane (PEM) fuel cell systems and direct hydrogen PEM fuel cell systems by 

using current-year technology. 

•	 Apply Design for Manufacture and Assembly (DFMA) design and costing techniques to compare 

system designs at low, medium, and high annual production rates. 

•	 Develop a roadmap to lower system cost by performing a sensitivity study of the major components in 

the fuel processor and fuel cell systems. 

•	 Determine the impact on cost, volume, and mass of replacing the fuel processor unit operations with 

microchannel-type components. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Production 

•	 A. Fuel Processor Capital Costs 

Hydrogen Delivery 

•	 A. Lack of Hydrogen/Carrier and Infrastructure Options Analysis 

Fuel Cells 

•	 D. Fuel Cell Power System Benchmarking 

Approach 

•	 Conduct annual updates of design, manufacturing methods, and costs for the four 50-kWnet PEM fuel 

cell systems previously examined: 

- reformer/fuel cell system operating at 0.7 V/cell peak-power 

- reformer/fuel cell system operating at 0.6 V/cell peak-power 

- direct hydrogen fuel cell system operating at 0.7 V/cell peak-power 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- direct hydrogen fuel cell system operating at 0.6 V/cell peak-power 

•	 Perform cost sensitivity analysis for material costs and system performance parameters. 

•	 Analyze weights, volumes, and costs of microchannel device substitutes for reformer components and 

compare to baseline design. 

Accomplishments 

•	 Performed annual update to cost estimates of baseline and three alternative systems with more detailed 

estimates of peripheral components. 

•	 Conducted a sensitivity study to quantify the overall fuel cell cost reductions that could result from 

cost reductions and technological improvements in major fuel processor and fuel cell system 

components. 

•	 Compared microchannel designs for the major fuel processor components (catalytic reactors and heat 

exchangers) with the existing baseline designs, with a focus on component mass and volume. 

Future Directions 

•	 Update baseline reformer and fuel cell cost estimates to reflect advances in technology and additional 

manufacturing and design improvements. 

•	 Construct a roadmap to lower system cost based on the results of the sensitivity study. 

•	 Analyze potential cost reductions resulting from gas purification technologies. 

•	 Examine feasibility of alternate fuel cell designs and operations, such as stack construction, voltage 

and/or pressure pulsing, and air compression technologies. 

•	 Identify feasible manufacturing techniques and costs for microchannel fuel processor components. 

Introduction 

Directed Technologies Inc. (DTI) has performed 

a DFMA-style cost estimation for an onboard 

gasoline reformer and fuel cell system at several 

annual production volumes. The Design for 

Manufacture and Assembly (DFMA) technique is a 

rigorous design/redesign and cost estimation 

methodology developed by Boothroyd and Dewhurst 

(1) and adapted by DTI. DTI has previously 

analyzed the cost of a 50-kWnet baseline system and 

compared it to an alternate reformer/fuel cell system 

and two direct hydrogen fuel cell systems. 

The current report provides updates to the 

estimated costs for these four systems, a sensitivity 

analysis aimed at identification of cost reduction 

options in the baseline system, and a summary of the 

evaluation of microchannel technology for possible 

use in the fuel processor system. Microchannel 

component design takes advantage of the high 

specific heat transfer area that can be achieved 

through the use of reaction and heat exchange 

devices that have flow channels with critical 

dimensions of less than 1 millimeter. 

Approach 

System Cost Updates. Using information gained 

over the past year related to the cost of fuel cell (FC) 

materials and components as well as interactions 

with industry, the cost of the baseline 0.7 V/cell 

reformer-FC system, the 0.6 V/cell reformer-FC 

system, and both the 0.6 and 0.7 V/cell direct 

hydrogen systems have been updated. While the 

newest cost estimates are slightly different than 

previous ones, the trends and conclusions drawn in 

previous years remain unchanged. 

Cost Sensitivity Analysis. With the intent of 

developing a roadmap to lower system cost, we 

examined the sensitivity of system cost to various 

material costs and performance parameters for both 

the reforming system and the fuel cell stack. The 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

relative cost contribution of the following materials 

was examined: 

•	 Stack components: ionomer, gas diffusion 

layer (GDL), and bipolar plates 

•	 Precious metal (PM) catalysts in the fuel cell 

stack, reforming and gas-cleanup sections 

•	 Reformer shell materials 

•	 Reformer catalyst support and application 

Using a component-by-component parametric 

model, the sensitivity of system cost to the following 

parameters was evaluated: 

•	 Stack power density 

•	 Overall system efficiency 

•	 Reformer, water gas shift (WGS), and 

preferential oxidation (PrOx) bed volumes 

•	 Gasoline sulfur levels 

Microchannel Technology Assessment. We have 

considered microchannel devices as replacements for 

the following fuel processor subsystems: 

•	 Autothermal reformer/steam reformer 

(ATR/SR) 

•	 High-temperature water gas shift (HTS) 

•	 Water boiler/vaporizers (2 items) 

•	 Low-temperature water gas shift (LTS) 

•	 Preferential oxidation (PrOx) 

The subsystems listed above were screened 

through discussions with Pacific Northwest National 

Laboratory (PNNL) and by preliminary design 

calculations to determine which processing steps 

could benefit by the substitution of microchannel 

devices. 

Results 

System Cost Updates. The system cost breakdowns 

for the 0.7 V/cell reformate and direct hydrogen 

systems are shown in Figure 1. In both systems, the 

fuel cell stack contributes roughly half the cost of the 

complete system. 

Cost Sensitivity Analysis. In a fixed system design, 

material costs for various components provide an 

estimate of the relative potential for system cost 

 FY 2003 Progress Report 

reductions through material cost reductions. The 

results of the materials cost analysis are shown in 

Figure 2, where membrane ionomer, membrane 

catalyst, GDL, and bipolar plate are shown to be the 

largest cost-contributing materials. 

Figure 3 is a tornado plot for several system 

performance parameters, indicating that fuel cell 

stack power density (and, hence, active area) is the 

most significant performance parameter affecting 

system cost. The data shown correspond to the 0.7 

V/cell reformer-FC system at a manufacturing rate of 

500 units per year but are nearly identical at a 

manufacturing rate of 500,000 units per year. 

Figure 1. Cost Breakdown for 0.7 V/cell ReformerFuel Cell and Direct Hydrogen Systems 

Figure 2.	 Contribution of Material Costs to System 

Costs for Baseline Reformer-Fuel Cell 

System 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Effect of Operational Parameters on System 

Cost at Production Rate of 500 Systems/Yr 

Microchannel Technology. The autothermal 

reformer (ATR) was eliminated as a potential 

application for microchannel components due to the 

high temperatures involved (>800°C) that would 

require thick metal walls and because the adiabatic 

operation of the ATR is well-suited to using a 

ceramic monolith reactor. Additionally, design 

calculations indicate there is at most a 10% 

improvement in reactant mass transfer through the 

catalyst matrix in a microchannel with 750 mm flow 

paths compared to a monolith with 1 mm cells. 

More substantial volumetric reduction is 

potentially achievable through conversion of the 

water vaporizer to a microchannel design. Such a 

design was prepared using 480°C reformate as the 

heating fluid to vaporize the water as in the baseline 

design. The core of the microchannel design 

achieved an 82% reduction in volume compared to 

the baseline design; however, when fluid 

manifolding is included, the volume reduction 

shrinks to 32% (669 cm3

 vs. 991 cm3). This 

indicates, sensibly, that imaginative integration of 

components will be required to achieve maximum 

volumetric reduction, since manifolding can quickly 

erase much of the gains. 

The microchannel water gas shift (WGS) reactor 

design combines the high temperature shift bed, 

water vaporizer, and low temperature shift bed from 

the baseline design into a single device. The 

integration of heat exchange and reaction allows the 

WGS reaction to trace the equilibrium curve from 

400°C down to 300°C, resulting in a reduced catalyst 

volume compared to the baseline. Preliminary 

calculations show that a reduction in system volume 

of 68% is possible by using the microchannel design 

(4.2 liters vs. 13.0 liters). (The PNNL staff is in the 

process of reviewing the design for the microchannel 

WGS, and their comments will be considered before 

finalizing the design.) However, due to the addition 

of the metallic heat exchange elements, the mass of 

the microchannel core and the mass of the baseline 

system are estimated to be almost identical (12.6 kg 

vs. 12.7 kg). 

Conclusions 

The baseline design for this study was developed 

using DFMA-style techniques applied to the stack 

and fuel processing components to achieve low cost. 

In the resulting system, the fuel cell stack represents 

roughly half the system cost at all production rates. 

This fact is emphasized by both the material and 

performance parameter sensitivity analyses, in which 

fuel cell stack materials and power density are shown 

to be the most significant cost contributors. 

Substantial cost reductions in the system can only be 

achieved by addressing issues with the potential to 

reduce stack size, either directly through improved 

stack performance or indirectly through fuel 

processor improvement to deliver higher purity 

hydrogen to the stack. These approaches can be 

summarized as follows: 

• Lower stack material and fabrication costs 

- lower catalyst loading 

- less expensive stack materials 

• Increased stack power densities 

- improved membrane performance 

- improved stack operation 

- improved gas processing for pure 

hydrogen 

Microchannel devices are potentially attractive 

for fuel processor subsystems that benefit from 

combined reaction and heat exchange. The water gas 

shift and preferential oxidation steps, therefore, are 

potential applications for microchannel technology, 

while the adiabatic autothermal reforming is not. An 

integrated microchannel WGS heat exchanger/ 

reactor can potentially achieve a nearly 70% volume 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

reduction compared to the baseline non-integrated 

unit. Analysis to date suggests negligible, if any, 

mass reduction for the microchannel system 

compared to the baseline. The next step in the 

analysis is to use DFMA-style techniques to identify 

the most practical and cost efficient manufacturing 

processes and thereby determine the resulting system 

cost for the microchannel water gas shift reactor. 

References 

1. Boothroyd, G., Dewhurst, P., and Knight, W. 

Product Design for Manufacture and Assembly, 

Second Edition. Marcel Dekker, Inc. New York, 

2002. 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Brian D. James at the FreedomCAR Fuel Cell 

Tech Team on September 18, 2002. 

2. Brian D. James at the FreedomCAR Storage 

Tech Team on October 16, 2002. 

3. Brian D. James at the SAE Congress in Detroit 

on March 5, 2003. 

4. Brian D. James at the 2003 Merit Review and 

Peer Evaluation Meeting of the US DOE 

Hydrogen, Fuel Cells & Infrastructure 

Technologies Program on May 20, 2003. 

5 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Atmospheric Fuel Cell Power System for Transportation 

Michael Tosca 

UTC Fuel Cells 

195 Governor's Highway 

South Windsor, CT 06074 

Phone: (860) 727-7324; Fax: (860) 998-9589; E-mail: mike.tosca@utcfuelcells.com 

DOE Technology Development Manager: Patrick Davis 

Phone: (202) 585-8061; Fax: (202) 586-9811; E-mail: Patrick.Davis@ee.doe.gov 

Objectives 

The objectives of this project are to demonstrate, through testing, the following: 

• One fully integrated, gasoline fueled 25-50 kW proton exchange membrane (PEM) power plant. 

• Two-phase approach using catalytic partial oxidation (CPO) fuel processing system (FPS). 

- Phase one, Fuel Processor One (FP1): focus on start time, steady state and transient operation of the 

FPS and generation of quality reformate. Testing conducted in FY 2003. 

- Phase two, Power Plant One Reformate (PP1R): focus on demonstrating full integration of PEM fuel 

cell power plant. Testing to be conducted in FY 2004. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• I. Fuel Processor Start-up/Transient Operation 

• J. Durability 

• K. Emissions and Environmental Issues 

• L. H2 Purification/CO Cleanup 

• M. Fuel Processor System Integration and Efficiency 

• N. Cost 

Approach 

• Build FP1, integrated FPS assembly. 

• Test CPO based FPS, FP1. 

• Build PP1R power plant from FP1. 

• Test PP1R assembly, fully integrated PEM power plant. 

• Tear down and analyze PP1R test article. 

Accomplishments 

• Built and tested integrated fuel processing system, FP1. 

• Analyzed data and presented results at the DOE annual merit review meeting. 

• Started building fully integrated PEM power plant. 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Test PP1R assembly, fully integrated PEM power plant. 

• Analyze and present PP1R test data. 

• Tear down and analyze PP1R assembly. 

Introduction 

UTC Fuel Cells (UTCFC) is committed to the 

commercialization of PEM fuel cell power plants for 

transportation applications. UTCFC has in place a 

program addressing the technology development and 

verification of each of the necessary components, 

subsystems and fully integrated power plant. The 

focus of the program is an ambient PEM power plant 

operating on gasoline liquid fuel capable of 

delivering 25-50 kW net DC power using a CPObased fuel processor. 

Approach 

Figure 1 provides a schematic of the gasoline 

fuel cell power plant showing the distinction between 

FP1 and PP1R. The major subsystems include the 

Fuel Processing Subsystem, the Power Subsystem 

and the Balance of Plant (BOP). The BOP includes 

the Thermal Management Subsystem, the Air and 

Water Subsystems and the Controller and associated 

electrical equipment. 

A photograph of the FPS is shown in Figure 2. 

This is a fully assembled FPS that includes the CPO 

reformer, low and high temperature shift converters 

and CO cleanup. Figure 3 is a photograph of the FP1 

assembly with the FPS integrated. 

Figure 2. FPS Assembly 

Figure 3. FP1 Assembly 

Figure 1. System Schematic 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Results 

The FP1 test article was tested at UTCFC's 

facilities in South Windsor, Connecticut. The fuel 

used for this testing was California Phase II 

desulfurized reformulated gasoline (RFG) liquid 

fuel. Table 1 provides the FP1 test data summary 

compared against industry target values. 

Table 1.	 FP1 Data Summary (LHV = lower heating 

value, NMHC = non-methane hydrocarbon, 

ppmvw = parts per million by volume on a wet 

basis) 

FP1 Summary Target FP1 Test 

Data 

FPS Volume, liters 75 78 

Heat up time, s 165 171 

Number of start/stops 500 111 

Duration of operation (total hrs) 

- Longest single run, hrs 

2000 232 hrs 

10 hrs 

Range of equivalent power, kWe 10-50 10-50 

LHV efficiency, % at rated 

LHV efficiency, % below rated 

$75 

$70 

69% 

69-72% 

Emissions (ppmvw) 

- Start (NMHC, CO, NOx) 

- Run (NMHC, CO, NOx, CO4) 

- Transient (CO, NH4, 

Aromatics) 

<34, 1791, 21 

<22, 15. 1.6, 700 

<100 

5, 1.7, 9.1 

20, 14, <1, 630 

TBD 

Figure 4 provides data that show the FPS was 

able to start up in approximately 5 minutes. 

Figures 5 and 6 show the FP1 steady state and 

transient CO levels. CO levels during steady state 

and transient operation were in the 20 ppm range, 

which is the desired limit for acceptable PEM fuel 

 FY 2003 Progress Report 

cell operation. These results show that the CPObased FPS is capable of producing reformate 

acceptable for PEM fuel cell operation. 

Following FP1 testing, the test article was 

removed from the UTCFC test stand and started its 

build to the PP1R power plant, in preparation for 

phase two of testing. 

Conclusions 

The FP1 test results showed significant 

improvements over the previous generation gasoline 

reformate system (S200). Start time and CO levels 

coming out of the FPS and into the cell stack are 

critical areas for on-board reforming to be promising 

for commercial transportation applications. FP1 start 

time of approximately five minutes and CO levels in 

the 20 ppm range are very encouraging and provide a 

good baseline for the fully integrated power plant 

testing scheduled for next year. 

Figure 5. FP1 Steady State Data 

Figure 4. Start Time Demonstration Figure 6. FP1 Transient Data 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

UTCFC is committed to the commercialization 

of PEM fuel cell power plants for transportation 

applications and will test the fully integrated PEM 

power plant (PP1R) next year along with Argonne 

National Laboratory (ANL). 

FY 2003 Publications/Presentations 

1. M. Tosca, "Atmospheric Fuel Cell Power System 

for Transportation", DOE Hydrogen, Fuel Cells 

and Infrastructure Technologies Program 2003 

Annual Merit Review, Berkeley, CA (May 

2003). 

2. M. Steinbugler, "Progress and Challenges in 

PEM Automotive Fuel Cells with Gasoline 

Reformers", The 3rd International Advanced 

Automotive Battery Conference, June 10-13, 

2003, Nice, France. 

 FY 2003 Progress Report 

4 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Platinum Recycling Technology Development (New FY 2004 Project) 

Dr. Stephen Grot (Primary Contact) 

President/CEO 

Ion Power, Inc. 

Saint Andrews Industrial Park 

102-108 East Scotland Dr. 

Bear, DE 19701 

Phone: (302) 832-9550; Fax: (302) 832-9551; Toll Free: (877) 345-9198; E-mail: s.grot@ion-power.com 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov 

Objectives 

•	 Develop technology for the recycling and/or re-manufacture/reuse of catalyst-coated fuel cell
 

membranes and catalyst-coated fuel processing components that are used in fuel cell systems.
 

•	 Recover valuable platinum group metals and NAFIONTM fluorine-containing polymer. 

•	 Develop comprehensive understanding of the failure mechanisms of fuel cell catalysts and membranes. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

Approach 

The overall objective of this project is to 

develop technology for the recycling and/or remanufacture of catalyst-coated fuel cell membranes 

and catalyst-coated fuel processing components that 

are used in fuel cell systems. A novel feature of our 

approach is the recovery of the active ionomer as 

well as the precious metals. Currently, platinum is 

the most viable catalyst for proton exchange 

membrane (PEM) fuel cell systems. However, if 

the potential of this technology is to be realized, the 

long-term availability of platinum group metals 

may become a serious limitation. As platinum 

reserves are depleted, this will lead to an increase in 

the cost of fuel cells. Hence, platinum recycling is 

critical to the long-term economic sustainability of 

PEM fuel cells. In addition, the value of the 

ionomer component in catalyst-coated membranes 

currently exceeds that of the precious metals; thus, 

recovery of the ionomer is also warranted. Future 

cost estimates using projected annual fuel cell 

vehicle production volumes of 500,000 per year 

demonstrate that cost of the ionomer will continue 

to be a major cost contributor to fuel cell power 

plants relative to the platinum required. 

Furthermore, it is the presence of the NAFIONTM 

fluorine-containing polymer in the fuel cell recycle 

stream that greatly complicates conventional 

recycling methods, which are ill-suited due to the 

toxic and corrosive HF gas released during these 

processes. We will therefore develop a process that 

enables the extraction and reuse of both the 

precious metals and the ionomer in current fuel cell 

components. 

We will also demonstrate the feasibility of a 

novel vapor phase extraction process to reclaim 

precious metals from fuel processing components. 

We will recover the platinum group metals in an 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

environmentally benign manner as well as the 

valuable NAFIONTM . 

This project brings together large and small 

industrial partners with a strong group of university 

faculty researchers to develop a novel method of 

recovering all of the valuable materials of PEM fuel 

cell systems. Ion Power and DuPont have an existing 

long-term business relationship dedicated to the 

promotion of the NAFIONTM polymer in all 

applications. Ion Power, Inc. is a small business 

working on developing high performance catalyst 

coated membranes for fuel cell and electrolyzer 

applications. The faculty members from the 

Department of Chemical Engineering at the 

University of Delaware provide world-recognized 

expertise in the technical areas of vapor phase 

extraction and deposition of platinum group metals 

(PGM), characterization and evaluation of PGM 

electrocatalysts, physical characterization of 

ionomers, and separation science. 

 FY 2003 Progress Report 

In this project, we propose to develop a process 

that will allow for the re-manufacture of new catalyst 

coated membranes (CCMs) from used CCMs 

extracted from failed fuel cell stacks. This will be 

accomplished by removing the CCM from the stack, 

decontaminating the CCM to remove impurities, and 

then dissolving the CCM in an autoclave reactor to 

form a slurry of dissolved NAFIONTM together with 

the Pt/C catalyst particles. We will develop a 

technology that will then separate these two valuable 

ingredients and allow the NAFIONTM solution to be 

re-processed into a new fuel cell membrane. Ideally, 

the recovered catalyst (Pt/C) will be re-deposited on 

the re-manufactured membrane so that a completely 

re-manufactured CCM is the final deliverable. As a 

result of our multifaceted industrial and academic 

team, an important byproduct of this project will be 

fundamental research that will help determine the 

failure mechanisms that are currently hampering the 

performance of state-of-the-art catalyst coated 

membranes. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Platinum Group Metal Recycling Technology Development 

(New FY 2004 Project) 

Dr. Arthur Bruce Robertson (Primary Contact) 

Engelhard Corporation 

101 Wood Avenue 

Engelhard Corporation 

Iselin, New Jersey 

Phone: (732) 205-6015; Fax: (732) 205-6109; E-mail: Bruce.Robertson@Engelhard.com 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov 

Objectives 

•	 Develop environmentally friendly processes for recovering and recycling the platinum, palladium, 

rhodium and ruthenium present in fuel reformers and proton exchange membrane (PEM) fuel cell 

stacks. 

•	 Investigate leaching, industrial microwave, supercritical carbon dioxide, and pyrometallurgical 

processes, and select the preferred processes for recovering precious metals from the various types of 

catalysts present in PEM fuel cell systems. 

•	 Build and operate pilot equipment to demonstrate process viability. 

•	 Estimate the economics of viable processes. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Fuel Flexible Fuel Processors 

•	 N. Cost 

Component 

•	 O. Stack Material and Manufacturing Cost 

Approach 

The primary objective is to develop and 

demonstrate the viability of processes for recovering 

and recycling the platinum, palladium, rhodium, and 

ruthenium present in fuel reformers and PEM fuel 

cell stacks. For the viable processes, pilot scale 

equipment will be built and operated to gather 

information needed to estimate process economics. 

Several different types of catalysts are present in 

PEM fuel cell systems. The fuel reformers that are 

used to make hydrogen have catalyzed ceramic or 

metal substrates. Fuel cell stacks are sandwich 

structures made from membrane assemblies 

(typically composites of carbon cloth, catalysts and 

fluoropolymers) and bipolar plates. Different 

processes are required to recover and recycle the 

precious metals present in the different components 

of a PEM fuel cell system. 

An environmentally friendly process will be 

developed for recovering precious metal from 

membrane electrode assemblies (MEAs). Simple 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

combustion of MEAs produces a Pt-rich ash that is 

hard to handle. This process also gives off 

significant amounts of toxic and corrosive hydrogen 

fluoride (HF) gas. Several new processes will be 

investigated including industrial microwave 

technology, conventional leaching, microwaveassisted leaching, and supercritical carbon dioxide 

leaching. The leaching processes are unlikely to 

generate HF, thus solving the HF emissions problem, 

and, at the same time, present an opportunity for 

recovering the fluoropolymer. Following the 

leaching, pyrometallurgical reprocessing will be used 

to increase precious metal yield and sequester the 

fluoride as an insoluble slag. 

New processes will also be developed for 

recovering precious metal from the catalyzed 

ceramic and metal substrates present in a reformer. 

At present, ceramic-supported catalysts are ground 

up, and the precious metal is separated and 

 FY 2003 Progress Report 

concentrated using a pyrometallurgical process. A 

modified version of the currently used process will 

be developed to treat the slag and thereby increase 

precious metal yield. Pyrometallurgy is not well 

suited to recover the precious metal from reformer 

catalysts that are coated on metal supports such as 

metal monoliths, foams, and heat exchangers. A new 

process will be researched that delaminates the wash 

coat and treats the delaminate by conventional 

refining technology to recover precious metals. 

In the third year of the project, the most 

promising processes will be designated for scale up. 

In the final three years of the project, pilot equipment 

will be built and operated to demonstrate process 

viability and gather information to estimate process 

economics. 

The above work will take place over a 5-year 

period. 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Cost and Performance Enhancements for a PEM Fuel Cell System 

Mark K. Gee 

Honeywell Engines, Systems & Services 

2525 W. 190th Street, MS-36-2-93084 

Torrance, CA 90504 

Phone: (310) 512-3606; Fax: (310) 512-4998; E-mail: mark.gee@honeywell.com 

DOE Technology Development Manager: John Garbak 

Phone: (202) 586-1723; Fax: (202) 586-9811; E-mail: John.Garbak@ee.doe.gov 

ANL Technical Advisor: Bob Sutton 

Phone: (630) 252-4321; Fax: (630) 252-4176; E-mail: sutton@cmt.anl.gov 

Objectives 

•	 Develop an optimum turbocompressor configuration by working with fuel cell system manufacturers 

and continuing the work currently performed 

•	 Reduce turbocompressor/motor controller costs while increasing design flexibility 

•	 Develop and integrate the turbocompressor/motor controller into a fuel cell system 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

Approach 

•	 Use automotive and aerospace turbomachinery technology for low cost and low weight/volume 

•	 Build upon previous turbocompressor experience 

•	 Use VNT® (variable nozzle turbine) inlet geometry for improved performance across the desired 

flow range 

•	 Use a mixed flow type compressor for improved low flow performance 

•	 Use contamination/oil-free and zero maintenance compliant foil air bearings 

•	 Use a modular approach to improve design flexibility 

•	 Use a high efficiency, low cost two pole motor 

•	 Use a low-cost variable speed motor-controller topology design that does not require sensors 

Accomplishments 

•	 Requirements established from various developers’ inputs 

•	 Analysis and design of the reduced cost and enhanced performance turbocompressor, motor and motor 

controller are underway 

Future Directions 

•	 Complete testing of the turbocompressor VNT® variable nozzle turbine 

•	 Complete analysis, design, and fabrication of a reduced cost and enhanced performance 

turbocompressor
 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Complete analysis, design, and fabrication of a reduced cost and enhanced performance motor 

•	 Complete analysis, design, and fabrication of a reduced cost and enhanced performance motor 

controller with no sensor requirements 

Introduction 

The objective of this work is to develop an air 

management system to pressurize an automotive fuel 

cell system. The turbocompressor is a motor-driven 

compressor/expander that pressurizes the fuel cell 

system and recovers subsequent energy from the 

high-pressure exhaust streams. Under contract by 

the U.S. Department of Energy, Honeywell designed 

and developed the motor driven compressor/ 

expander and evaluated performance, weight and 

cost projection data. As compared to positive 

displacement technology, the turbocompressor 

approach offers potential for high efficiency and low 

cost in a compact and lightweight package. 

Approach 

The turbocompressor design currently 

underway for the ‘Cost and Performance 

Enhancements for a PEM Fuel Cell 

Turbocompressor’ project consists of a mixed 

flow compressor impeller, a VNT® variable 

nozzle turbine, and a motor magnet rotor 

incorporated onto a common shaft operating up 

to a speed of 110 krpm on compliant foil air 

bearings. A motor controller drives and controls 

the motor, which is capable of driving the 

turbocompressor to the maximum design speed. 

The air bearings are lubrication free in addition 

to being lightweight, compact, and selfsustaining; no pressurized air is required for 

operation. 

The turbocompressor will operate by drawing in 

ambient air, compressing it, and then delivering it to 

the fuel cell stack, fuel processor if available, and to 

the motor and bearing cavities for cooling. The 

exhaust streams will then be expanded through the 

turbine to aid in the overall turbocompressor/fuel cell 

system efficiency. The design will be modular to 

enhance system developer flexibility. The motor, 

which will be of the two pole toothed type, and the 

motor controller, which will incorporate controls that 

do not require separate sensors for operation, will be 

conducive to low cost and improved packaging. 

Both the mixed flow compressor impeller and 

the VNT® variable nozzle turbine improve system 

performance by improving the flow, pressure ratio 

and power characteristics of the turbocompressor 

over the flow range. The mixed flow compressor 

impeller design (coming from various aerospace 

applications) and the VNT® variable nozzle turbine 

(from the Garrett Engine Boosting Systems 

automotive turbocharging division) make the design 

low cost. 

Results 

The existing turbocompressor with a mixed flow 

compressor and a VNT® variable nozzle turbine, 

shown in Figures 1, 2 and 3, is scheduled to be tested 

in late 2003. The mixed flow compressor showed 

improved low flow performance with an improved 

surge line; however, the VNT® variable nozzle 

turbine, which would have further improved 

Figure 1.	 Honeywell Fuel Cell Turbocompressor with 

Mixed Flow Compressor and VNT® Variable 

Nozzle Turbine 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2.	 Cross Section of Honeywell Fuel Cell 

Turbocompressor with Mixed Flow 

Compressor and VNT® Variable Nozzle 

Turbine 

Figure 4.	 Turbocompressor Shaft Power/Compressor 

Outlet Pressure Ratio vs. Percent Flow 

(Baseline curves are based on actual data; 

mixed flow and VNT® curves are predicted.) 

Figure 3. Fuel Cell Turbocompressor Motor Controller 

performance and, consequently, lowered overall 

power consumption, was not tested due to project 

constraints. The test data noted above will be used in 

the ‘Cost and Performance Enhancements for PEM 

Fuel Cell Turbocompressor’ project. Predicted and 

tested performance of the turbocompressor and 

motor/controller with the mixed flow compressor test 

results are presented in Figure 4. 

After working with the various system 

developers and the DOE, a set of specifications was 

completed for the ‘Cost and Performance 

Enhancements for a PEM Fuel Cell 

Turbocompressor’ project. Work on the reduced cost 

and enhanced performance turbocompressor, motor 

and motor controller layout and analysis is underway 

Table 1. Fuel Cell Turbocompressor Physical Parameters 

DOE 

Parameters DOE Targets Honeywell 

Turbocompressor 

Weight 3 kg total Turbocompressor 

(w/o heat and motor: 6.0 

exchangers) kgController: 5.0 kg 

Volume 4 L total Turbocompressor 

(w/o heat and motor: 4.0 

exchangers) LController: 6.0 L 

with preliminary weight and volume shown in Table 

1. The design is scheduled to be completed in 2003. 

Conclusions 

•	 The turbocompressor concept using selfsustaining compliant foil air bearings has 

demonstrated low power consumption and good 

pressure ratio at low flow rates in a compact, 

lightweight package. 

•	 Testing and subsequent analysis has predicted 

positive effects of the mixed flow compressor to 

the fuel cell system performance, with improved 

efficiency and pressure ratio across the flow 

range. 

•	 Analysis has predicted positive effects of the 

VNT® variable turbine nozzle across the flow 

and temperature range, with efficient recovery of 

energy from the fuel cell exhaust. 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Working with the various fuel cell system 

developers and the DOE, a complete set of 

specifications has been generated. 

•	 The turbocompressor, motor and motor 

controller layout and analysis are underway. 

FY 2003 Publications/Presentations 

1. Air Management Systems, SAE TOPTEC; April 

9, 2003 

2. Fuel Cell Turbocompressor, DOE Hydrogen, Fuel 

Cells and Infrastructure Technologies Program; 

May 22, 2003 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development and Testing of a Toroidal Intersecting Vane Machine (TIVM) 

Air Management System 

Sterling Bailey (Primary Contact), Steve Chomyszak 

Mechanology, LLC 

453 South Main Street 

Attleboro, MA 02703 

Phone: (408) 472-3719; Fax: (408) 358-4012; E-mail: sterling@mechanology.com 

DOE Technology Development Manager: John Garbak 

Phone: (202) 586-1723; Fax: (202) 586-1637; E-mail: John.Garbak@ee.doe.gov 

ANL Technical Advisor: Robert Sutton 

Phone: (630) 252-4321; Fax: (630) 252-4176; E-mail: Sutton@cmt.anl.gov 

Objectives 

•	 Develop a Toroidal Intersecting Vane Machine (TIVM) air management system that satisfies DOE’s 

automotive fuel cell system requirements and is readily adaptable to alternate user requirements. 

•	 Select and demonstrate design features to assure adequate sealing, minimum porting pressure loss, and 

low friction operation. 

•	 Develop the TIVM design methodology to allow efficient application to alternate user requirements. 

•	 Develop manufacturing processes for low-cost high-volume production. 

•	 Measure the performance of the TIVM compressor/expander across the operating range. 

•	 Fabricate and deliver a compressor/expander/motor prototype for independent testing. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

Approach 

•	 Demonstrate the basic performance of the TIVM concept as a compressor/expander. 

•	 Test candidate materials for friction and wear using standard laboratory tribilogical methods. 

•	 Test candidate seal and port designs as well as low friction materials in simplified test configurations 

to select the best performing options for the TIVM compressor/expander. 

•	 Optimize the vane surface solution methodology to provide a more efficient design process. 

•	 Fabricate a TIVM compressor/expander prototype using seals, porting, and materials selected from the 

simplified feature tests and evaluations. 

•	 Conduct performance tests of the prototype covering the full operating range. 

•	 Refine the prototype features as necessary to obtain optimal performance. 

•	 Develop cost efficient manufacturing methods for high volume production. 

•	 Integrate a high efficiency motor with the TIVM prototype and test the combined unit across the 

operating range. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Deliver a TIVM compressor/expander/motor (C/E/M) prototype to Argonne National Laboratory 

(ANL) for testing. 

Accomplishments 

•	 Friction and wear tests with the primary material pair for the TIVM vanes have shown that these 

materials will meet the operating and lifetime requirements. Testing has been performed at two 

independent laboratories. 

•	 A simplified single vane test (SVT) rig has been designed, fabricated and operated to screen seal 

design concepts and low friction materials. 

•	 Computational Fluid Dynamics (CFD) calculations were performed to guide seal designs. 

•	 Several seal design concepts were developed and tested ; three of them met both leakage and friction 

requirements. 

•	 Design optimization has reduced maximum speed from 4800 rpm to 3200 rpm with no increase in 

volume. 

•	 Experimental expander vanes are being fabricated to potentially qualify a unique powder metallurgy 

process that provides net shape, finish, and hardness without secondary operations. 

•	 A theoretical mathematical analysis of the surface solution methodology has been used to provide a 

significantly improved surface definition. 

•	 Initial thermal analyses have been performed to evaluate geometric changes caused by differential 

thermal expansion. 

Future Directions 

•	 Complete seal measurements for combined leakage and friction characteristics and confirm 

satisfactory performance of at least one design. 

•	 Perform porting feature measurements to confirm satisfactory performance. 

•	 Complete investigation of the additional TIVM innovation with potential to reduce the required shaft 

power by >1kW. 

•	 Build a fully operational prototype with selected seals and ports and measure the integral performance. 

•	 Integrate a high efficiency motor and measure performance of the combined C/E/M unit; deliver to 

ANL for testing. 

Introduction 

The Toroidal Intersecting Vane Machine (TIVM) 

is an innovative mechanical concept, invented and 

patented by Mechanology, which can be configured 

as an integrated, positive displacement compressor/ 

expander or compressor/compressor. In FY 1999, 

DOE investigated the TIVM concept for potential 

application to automotive fuel cell systems and 

determined that the inherent efficiency, compactness 

and thermodynamic attributes of this concept might 

be of significant benefit. Mechanology developed a 

design specifically for the 50 kWe automotive system 

and evaluated its potential performance. Based on 

the encouraging results obtained, a first generation 

compressor/expander prototype was built and tested. 

Figure 1 illustrates this prototype partially assembled 

to show the compressor and expander. The 

compressor/expander prototype tests indicated that 

the TIVM runs smoothly with no mechanical 

problems; however, improvements are required to 

limit air leakage. Additional tests using the generic 

prototype with temporary seals demonstrated the 

capability of the TIVM to produce the necessary flow 

and pressure. Based on these observations, the 

TIVM compressor/expander development plan is 

focused on development and demonstration of seals, 

ports and low friction materials. These are necessary 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 1. Partially Assembled First Generation TIVM 

Compressor/Expander Prototype
 

to satisfy the functional performance requirements 

with low parasitic power. Although not the main 

focus of the current development project, the 

requirements for air management system packaging, 

noise, and cost are considered as critical for a 

successful TIVM based system and are carefully 

considered as development progresses. 

Approach 

The basic functions of the TIVM compressor/ 

expander (kinematics, pressure, flow) have been 

demonstrated; however, development and 

qualification of specific seals, flow ports and low 

friction materials are required to meet the 

performance requirements. 

During 2003, Mechanology has focused on the 

use of simplified feature tests to allow rapid, efficient 

characterization of a broad range of design options 

for later inclusion in a full TIVM device. The initial 

simplified tests use a single vane test (SVT) device to 

measure the leakage and friction characteristics of 

candidate vane seal designs. Computational Fluid 

Dynamics (CFD) analyses of the vane/housing/air 

interactions have been used to guide the design and 

testing of these features. Additional tests will be 

performed using the SVT device to finalize the seal 

designs to be used in the next TIVM compressor/ 

expander prototype. 

 FY 2003 Progress Report 

Definition of the vane surface configurations 

required for a specific TIVM can be accomplished 

through an iterative process developed by 

Mechanology. With sufficient iterations, a very good 

meshing surface solution can be obtained, as 

evidenced by the generic TIVM prototype vanes. 

However, this process is quite time consuming. 

Mechanology has explored alternate mathematical 

approaches to develop a more efficient surface 

design methodology. 

Low friction materials are necessary for the 

intersecting vanes to realize the predicted energy 

efficiency of the TIVM compressor/expander. 

Additionally, these materials must have sufficiently 

low wear under the TIVM operating conditions to 

perform acceptably during a 6,000 hour lifetime. 

Several candidate material pairs and potential 

coatings have been identified based on published 

data. To qualify materials for the TIVM, standard 

laboratory friction and wear tests are being 

performed. Successful materials are being tested in 

the single vane test rig, and subsequently, the best 

materials will be used in a TIVM prototype. 

In parallel with the specific technology 

development for the TIVM, Mechanology continues 

to evolve the overall design to reduce the operating 

speed and increase the efficiency. The improved 

design features will be incorporated into the 

subsequent prototypes. 

One or more full TIVM compressor/expander 

prototypes will be fabricated by Mechanology and 

tested across the full operating range. Modifications 

will be made as necessary to optimize performance. 

Subsequently, a high efficiency electric motor will be 

integrated with the TIVM to form a complete 

compressor/expander/motor component. This unit 

will be tested by Mechanology and then delivered to 

ANL for independent testing. 

Results 

ANL has constructed a tribology test rig that 

operates at the speed and interface pressure of the 

TIVM compressor/expander vanes at full power. 

During 2003, ANL resolved vibration problems with 

the test rig and performed friction and wear tests with 

stainless steel and low friction engineered polymer 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

samples provided by Mechanology under both dry 

and high humidity conditions. These measurements 

have indicated an acceptable friction coefficient at 

the TIVM operating conditions and wear rate 

consistent with the lifetime requirement. 

A simplified single vane test rig has been 

designed, fabricated and made operational for 

screening of seal designs and testing of low friction 

materials with vanes traveling at speeds in the 

planned operating range. Figure 2 illustrates the 

single vane test device design with the pressure cover 

removed. This device permits parametric variation 

of clearances and seal preloads as well as rapid 

change-out of materials and seal designs. The 

computer control and data acquisition program 

allows testing at specified speeds and pressure 

differentials with automated data logging. 

CFD calculations were performed by ANL using 

Mechanology’s single vane test configuration. These 

analyses have been used to understand the interaction 

of the vane/seal/air system as a function of operating 

conditions and to guide seal designs. Based on these 

results, non-contact seals were eliminated from the 

design concept options, and compliant contact seals 

have been selected. 

 FY 2003 Progress Report 

Mechanology has analyzed all of the potential 

leakage paths for both the compression and 

expansion cycles and has developed time histories of 

the pressure differentials across each path throughout 

the cycle. These data quantify the driving potential 

for leakage from the compression and expansion 

chambers. 

Mechanology reviewed the development of 

state-of-the-art seals relevant to the TIVM 

requirements. We found that the brush seals 

developed for jet engine and turbine applications will 

more than meet our requirements for some locations. 

Based on the seal study, new configurations were 

developed for the remaining TIVM seal locations, 

and samples were prepared for testing in the SVT rig. 

Tests were performed for leakage and friction 

individually to give accurate measurement of the 

very small values, and combined dynamic tests were 

performed for the combined behavior. Several 

design concepts were eliminated because of 

excessive leakage or friction. Figure 3 illustrates an 

example of the pressure vs. time data from a seal 

dynamic test. Pressures in excess of 7 atm have been 

generated at relatively low speeds, indicating the 

effectiveness of the seals. Three design concepts met 

both the leakage and friction requirements. 

Detailed analysis of the TIVM operation and the 

sources of inefficiency have shown the potential for a 

modified TIVM geometry that has significantly 

reduced friction. Patent disclosures are being 

prepared prior to release of the details of this 

additional innovation. 

Figure 2. Single Vane Test Equipment Figure 3. SVT Pressure vs. Time Example Data 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

Design and analysis of the first generation TIVM 

compressor/expander has shown that this concept has 

the potential to meet the DOE requirements for 

automotive fuel cell applications with significantly 

better performance than other options. Testing of the 

compressor/expander and generic TIVM prototypes 

has demonstrated correct kinematic functioning and 

the capability to produce the required pressure and 

flow. These tests have also highlighted the need for 

efficient seals and flow ports in the TIVM. 

Laboratory tribology measurements have shown 

acceptably low friction and wear for the preferred 

material pair candidate for the intersecting vanes. 

The ongoing development program is focusing on 

selection of seals, porting, and material options 

through simplified feature tests and then sequentially 

more prototypic TIVM tests. The single vane test 

results indicate that there are multiple seal design 

concepts that meet both leakage and friction 

requirements. Using the leakage and friction 

characteristics of one option tested, the expected 

power required to drive the TIVM compressor/ 

expander at full flow is approximately 6 kWe, as 

shown in Figure 4. A fully prototypic TIVM 

compressor/expander/motor will be fabricated and 

tested to measure actual performance with the 

selected options. Subsequent work will include 

development and qualification of cost efficient 

manufacturing methods for high volume production 

and development of features to assure compliance 

with noise requirements. Additional testing will 

focus on operating environment and reliability/ 

endurance issues. 

 FY 2003 Progress Report 

Figure 4. Expected TIVM Power for 50 kWe System 

FY 2002 Publications/Presentations 

1. “Toroidal Air Management System Development 

and Testing Status”, presented to the 

FreedomCAR Technical Team, April 16, 2003. 

2. “Development of a Toroidal Intersecting Vane 

Machine Air Management System for Automotive 

Fuel Cell Systems”, presented at the DOE 

Hydrogen and Fuel Cells 2003 Annual Merit 

Review, May 22, 2003. 

4. “TIVM Compressor/Expander/Motor 

Development and Demonstration, Cooperative 

Agreement DE-FC04-02AL67626, Annual 

Technical Progress Report - November 2001 to 

December 2002 and Quarterly Progress Report – 

October 2002 to December 2002”, submitted 

January 30, 2003. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Motor Blower Technologies for Fuel Cell Automotive Power Systems 

Thomas Clark (Primary Contact), Michael Arner 

UTC Fuel Cells (UTCFC) 

195 Governors Highway 

South Windsor, CT 06074 

Phone: (860) 727-2287; Fax: (860) 727-2319; E-mail: tom.clark@utcfuelcells.com 

DOE Technology Development Manager: John A. Garbak 

Phone: (202) 586-1723; Fax: (202) 586-9811; E-mail: John.Garbak@ee.doe.gov 

Subcontractors: Phoenix Analysis and Design Technologies, Phoenix, AZ; R&D Dynamics, 

Bloomfield, CT 

Objectives 

•	 Develop small, lightweight, motor driven blowers to provide cathode air and reformer air for a near 

ambient fuel cell operating on gasoline. 

•	 Identify and/or develop manufacturing methods that will allow the blowers to be produced at low cost 

in large production volumes. 

•	 Demonstrate blower performance via integration into a power plant. 

•	 Evaluate both reformer air blower approaches, regenerative vs. centrifugal, and identify superior 

technology. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

Approach 

•	 Define performance requirements, flows, pressures, temperatures as well as cost and life targets for an 

ambient pressure based fuel cell system. 

•	 Phoenix Analysis and Design Technologies (PADT) will develop and build a mixed flow type blower 

to meet requirements for cathode air and a regenerative type blower to meet reformer air requirements. 

Prototypes will be used to evaluate aerodynamic performance as well as life and durability. 

•	 R&D Dynamics will develop and build a high-speed centrifugal machine supported by air bearings as 

an alternate approach to the reformer air application. 

•	 UTC Fuel Cells will demonstrate operability and performance of both approaches by integrating the 

units into a power plant or conducting subsystem testing. 

Accomplishments 

•	 Requirements for both the cathode air blower and reformer air blower have been defined and 

documented.
 

•	 PADT has tested the mixed flow cathode air machine to 100% design speed and achieved greater than 

60% overall efficiency at rated flow and pressure rise. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 The R&D Dynamics high-speed compressor was down-selected as the preferred reformer air blower 

over the PADT proposed regenerative machine. 

•	 R&D Dynamics has tested the high-speed centrifugal machine to 85% of design speed. Demonstrated 

flow and pressure maps agree well with the predicted values, and a peak overall efficiency of 50% has 

been demonstrated. 

•	 PADT has completed a cost study which predicts production costs of $83 per blower in quantities of 

100,000 units/year. 

Future Directions 

•	 Continue testing of R&D Dynamics compressor to 100% of design speed. 

•	 Deliver both blowers to UTC Fuel Cells for evaluation in subsystems. 

•	 Continue off-design testing to evaluate robustness of designs under high ambient and process inlet 

temperature conditions. 

•	 Continue to refine designs for low cost manufacturing processes and ease of assembly. 

•	 Investigate lower cost motor and motor drive technologies. 

Introduction 

Near ambient pressure fuel cells running on 

gasoline require two sources of air, one for the fuel 

cell cathode and one for the gasoline reformer, which 

generates hydrogen. Due to the relative pressure 

differences required by the two applications, it is not 

energy efficient to fulfill the two air requirements 

with a single blower/compressor as is commonly 

utilized in pressurized type fuel cell systems. This 

project will develop two different types of machines 

to meet each air supply requirement independently. 

Blowers to meet these two applications are not 

commercially available in the size and volume 

required for packaging into a vehicle. Thus, this 

project aims to utilize high speed technology which 

will allow the blowers to develop the required flow 

and pressure rise in a small package size. Increasing 

the rotational speed presents several technical 

challenges, namely bearing life and motor heating. 

The motor heating issue is further compounded by 

the fact that we are able to reduce the size of the 

motor by running at higher speeds, yet the amount of 

shaft power required to be output by the motor 

remains the same. This results in a much higher than 

typical power density motor, and with the reduction 

in surface area, a much higher heat flux is required to 

maintain stator temperatures. This problem can be 

resolved in one of two ways: increase the efficiency 

of the motor and reduce the amount of heat generated 

by it, or increase the heat transfer capability of the 

stator and motor housing. 

Approach 

The approach for this project was to first define 

and document the blower requirements for an 

ambient pressure fuel cell system. The requirements 

issued by DOE in 2000 focused on targets for 

pressurized systems that were not directly applicable 

to the UTCFC ambient pressure system. New targets 

for blower performance, efficiency, cost, weight and 

volume were defined by UTCFC and documented in 

2001, and the air flow requirements were separated 

into two distinct applications: the cathode air blower, 

a high flow low pressure application, and the 

reformer air blower, a higher pressure low flow type 

application. 

Using these requirements for the two 

applications mentioned above, we identified three 

types of machines with possible benefits to the two 

applications, one for the cathode air blower and two 

types for the reformer air blower. The types of 

machines considered were restricted to what could be 

classified as mature air moving technology and thus 

would allow us to focus on reducing size, weight and 

cost rather than doing fundamental aerodynamic 

development. For the cathode air blower application, 

a mixed flow axial machine was selected. The 

aerodynamics for these types of machines are well 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

understood; thus, we were able to limit our scope of 

aerodynamic development to minor variations of the 

basic design to achieve optimum efficiency. 

For the reformer air blower, we considered two 

types of machines, each with its own unique set of 

advantages. The first machine was a very high 

speed, 140,000 rpm, radial centrifugal machine 

supported by air bearings. Because of the high 

speed, this type of machine is capable of delivering 

high pressure air in a very small package size with 

good overall efficiency. However, the very high 

speeds also required some technology development 

to minimize risks associated with the bearings and 

very high-speed motors and controllers. Thus, a 

regenerative type machine was evaluated as a 

potential second reformer air blower technology. 

Regenerative type machines are typically very good 

at developing higher pressures at low flow rates and 

lower speeds than typical centrifugal devices, which 

makes this technology attractive. The flow and 

pressure could be developed at speeds consistent 

with the use of grease packed ball bearings, which 

are desirable due to their low cost. However, 

regenerative type machines are typically lower 

efficiency as compared to other centrifugal 

machines; thus, a key task was to perform basic 

aerodynamic research into variations of the 

traditional regenerative wheel and housing design to 

optimize for peak efficiency. 

Results 

The cathode air blower and controller designs 

have been completed and are shown in Figures 1 and 

2. The blower and motor drive have been tested to 

100% of design speed, and performance is shown in 

Figure 3. Please note that efficiency shown in this 

figure is overall efficiency and accounts for all losses 

in the motor/motor drive and all frictional losses and is 

a true representation of the total parasitic load to the 

fuel cell system associated with providing cathode air. 

It is calculated by dividing the isentropic power by the 

direct current power input to the motor drive. 

The blower has been designed for low cost, high 

volume production, and several of the parts used in 

the prototype blowers were actually manufactured 

using injection molding techniques which will yield 

very low per piece cost in production volumes. 

Additionally, much of the effort this year focused on 

reducing effort and precision required to assemble 

the components, thereby reducing the cost associated 

with final assembly of the blower. A detailed cost 

study was conducted for each part of the blower and 

the final assembly effort, during which 

manufacturers were asked to quote production prices 

in volumes of 100,000 per year. A total cost for the 

blower and motor drive of $83 is predicted, which 

compares favorably with our initial cost target of $75 

per blower. 

The high-speed reformer air blower and 

controller, developed by R&D Dynamics, are shown 

Figure 1. PADT Cathode Air Blower 

Figure 2. PADT Cathode Air Blower Controller 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

in Figures 4 and 5, respectively. At the time of this 

writing, they have been tested to 120,000 rpm. 

Approximately 85% of design speed and 

performance, as shown in Figure 6, is inline with 

predicted values. Unfortunately, rotor heating and 

motor controller issues have prevented us from 

running to 100% of design speed thus far. This past 

year was heavily focused on reducing the severity of 

motor rotor heating effects with solutions 

concentrated in two areas: 1) increasing the amount 

of cooling air supplied to the motor cavity and 2) 

experimenting with rotor magnets and rotor materials 

to reduce heating caused by eddy current losses. A 

new motor cooling scheme that taps into process air 

from the blower exit, rejects heat through finned 

tubing and directs it through the motor cavity has 

shown good results and enabled us to achieve 

120,000 rpm. We believe this technique will allow 

 FY 2003 Progress Report 

us to reach 100% design speed. In addition to 

improving the current motor and controller designs, 

we have purchased a new motor and controller which 

have been designed from the ground up to minimize 

rotor heating due to eddy currents. We expect that 

these new motor and controller designs will allow us 

to run speeds in excess of 100% design speed, and 

combined with the improved cooling scheme, should 

give us acceptable thermal margins even with 

elevated blower inlet air temperatures. 

Figure 3. PADT Cathode Air Blower Performance (iwc 

= inches water column) 

Figure 4. R&D Dynamics Reformer Air Blower 

Figure 5. R&D Dynamics Reformer Air Blower 

Controller 

Figure 6. R&D Dynamics Reformer Air Blower 

Performance (PR = pressure ratio) 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

The regenerative technology reformer air blower 

development effort has not produced the results we 

had hoped for and the aforementioned task to achieve 

significantly improved aerodynamic efficiencies. To 

assist us in this task, a fluidic model was developed 

and calibrated with actual test data and has allowed 

us to easily and accurately predict wheel efficiencies 

for a variety of wheel configurations. Unfortunately, 

the model has shown that the traditional regenerative 

wheel design is very difficult to improve upon, as 

numerous wheel design variations were modeled and 

the best one increased pump head efficiency by only 

2 percentage points over the traditional design. As a 

result of this inherently low wheel efficiency, the 

increased shaft power required from the motor 

resulted in a severe heating problem for both the 

motor and pump head in addition to low overall 

efficiency. For this reason, we have decided to 

terminate the regenerative blower effort and redirect 

our efforts to more meaningful technical challenges 

in other areas within the program. 

Conclusions 

•	 The cathode air blower is a very efficient way to 

move air at low pressure ratios. Work in the 

coming year will focus primarily on increasing 

blower reliability and durability in high 

temperature and high vibration applications. 

 FY 2003 Progress Report 

•	 The high-speed, centrifugal reformer air blower 

design has produced predicted aerodynamic 

performance in a very compact package. Future 

work will focus on the achievement of 100% 

design speed, redesigning the unit for low cost, 

high volume production and achieving motor 

controller durability. 

•	 When working with compact, high-speed motors, 

the number one issue is motor rotor heating. The 

motor controller and motor rotor must be designed 

as a package to minimize this effect. 

•	 Regenerative type machines are inherently 

inefficient and are best suited for applications 

requiring a pressure ratio less than 1.3. 

FY 2003 Publications/Presentations 

1. Freedom Car Annual Review, April 16, 2003, 

Detroit, MI 

2. DOE Merit Review, May 22, 2003, Berkeley, CA 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hybrid Compressor/Expander Module 

George E. Selecman (Primary Contact) and Paul E. McTaggart 

TIAX LLC 

Acorn Park 

Cambridge, MA 02140-2390 

Phone: (617) 498-6083; Fax: (617) 498-7250; E-mail: selecman.g@tiax.biz 

DOE Technology Development Manager: John Garbak 

Phone: (202) 586-1723; Fax: (202) 586-9811; E-mail: John.Garbak@ee.doe.gov 

ANL Technical Advisor: Robert D. Sutton 

Phone: (630) 252-4321; Fax: (630) 252-4176; E-mail: sutton@cmt.anl.gov 

Subcontractors: Concepts NREC, White River Junction, VT; Scroll Corporation, Carlisle, MA 

Objectives 

•	 Based on the experience of two previous generations of scroll-based Compressor/Expander Modules 

developed with DOE, design and build a hybrid compressor/expander combining turbomachinery and 

positive displacement scroll compression. 

•	 Deliver a system with equivalent thermodynamic performance, at significantly lower weight and 

volume, when compared to previous generations of scroll Compressor/Expander Modules. 

•	 Develop the algorithms and hardware to ensure stable and effective control of the hybrid system. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

Approach 

•	 In the first phase, develop system architecture and subsystem designs consistent with the overall goals 

of maintaining thermodynamic performance while reducing weight and volume relative to previous 

generations. 

•	 In the second phase, complete detailed engineering and initiate fabrication of brassboard and final 

subsystem components, and develop the control system hardware and algorithms. 

•	 In the third and final phase, complete fabrication of components and conduct subsystem assembly and 

test, followed by system integration and performance verification. 

Accomplishments 

•	 Completed detailed system design tradeoff study, resulting in specific definition of requirements for 

both the turbocompressor and scroll compressor subsystems. 

•	 Completed detailed subsystem design tradeoff studies for turbocompressor and scroll compressor 

subsystems, resulting in selection of design configurations for both subsystems. 

•	 Completed preliminary detailed design of both major subsystems, including component identification 

and sizing, cost estimation and performance estimates. 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Identified specific opportunities for performance enhancement through the use of limited exhaust gas 

recirculation. 

•	 Initiated preliminary brassboard system testing of scroll compressor drive configuration to evaluate 

bearing performance and lubricant management. 

Introduction	 scroll Compressor/Expander Modules, in 

Most current automotive fuel cell systems are 

designed for pressurized operation in order to reduce 

system size, boost stack efficiency, and improve 

water management. Because of the aggressive 

efficiency goals driving fuel cell development, the 

compressor must operate efficiently over a wide flow 

range, and efficient waste energy recovery in an 

expander is required to offset the compression load. 

Traditionally, high-speed turbomachine technology, 

such as that used in automotive turbochargers, has 

resulted in a compact package that delivers high 

efficiency at the design point, but with performance 

that falls off dramatically under off-design 

conditions. Scroll technology, a type of positive 

displacement machinery, provides high compressor 

and expander efficiencies across a broad range of 

operating conditions, but results in a package that is 

significantly larger and heavier than that of highspeed centrifugal technology. 

The objective of this project is to develop a 

hybrid compressor/expander module, based on both 

scroll and high-speed turbomachine technologies, 

which will combine the strengths of each technology 

to create a concept with superior performance at 

minimal size and cost. The resulting system will 

have efficiency and pressure delivery capability 

comparable to that of a scroll-only machine, at 

significantly reduced system size and weight when 

compared to scroll-only designs. In addition, this 

configuration offers the advantage of applying the 

required external power to the scroll compressor, a 

relatively low-speed device, eliminating the need for 

a high-speed motor to supply mechanical power to a 

turbomachine. 

Approach 

The design approach for the Hybrid TurboScroll 

Compressor/Expander Module (CEM) exploits the 

experience of developing the first two generations of 

combination with the substantial experience of our 

turbomachine subcontractor, Concepts NREC. 

(Figure 1 shows the Second Generation Scroll CEM 

on its test stand). By combining the performance 

attributes of a positive displacement scroll 

compressor (electrically driven) with those of a 

turbocharger (driven by fuel cell exhaust gases), we 

expect to be able to very closely match the pressure/ 

flow requirements of the DOE guidelines in a 

package that is smaller and lighter than previous 

generations. Figure 2 tabulates several key design 

goals for the project; they show dramatic 

improvement over the Second Generation 

performance noted. 

A novel approach to the development of an 

appropriate system architecture resulted in the block 

diagram shown in Figure 3.In this configuration, the 

turbocompressor draws in atmospheric air and 

compresses it to an intermediate pressure. In order to 

reduce both the size and operating temperature of the 

scroll compressor, an intercooler is provided to reject 

part of the heat of compression to atmosphere. The 

partially compressed gas, now cooler and denser, is 

then fed into the scroll compressor, which uses 

electrical power to achieve the final compression of 

the gas. Finally, the compressed air is fed into the 

Figure 1. Second Generation Scroll Compressor/ 

Expander Module 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

fuel cell, which increases its temperature and reduces • Managing any possible stack toxins in the disits pressure slightly. The exhaust gas from the fuel charge stream. 

cell drives the turbine and, the bulk of its energy 

extracted, is exhausted to atmosphere. The turbine 

provides the shaft power to drive the 

turbocompressor by direct coupling. This operating 

mode is used up to a selectable fraction of maximum 

flow, currently set to approximately 80-90%, at 

which point a relief valve opens, permitting a small 

fraction of the discharge gas mass flow to bypass the 

turbine and be fed directly into the intercooler inlet. 

With this system feature, the turbomachine is 

dramatically simplified by eliminating the 

controllable inlet guide vanes, and its operating range 

is substantially reduced, thereby improving its 

overall efficiency profile. 

This architecture offers some important 

advantages: 

•	 The turbocompressor provides stack operating 

pressure control by purely passive means, eliminating the need for an active control element and 

its associated parts, actuator and control logic; 

•	 The bypass valve permits recapture of a significant fraction of the discharge enthalpy without 

passing through the turbomachine; 

•	 A fraction of the waste water in the discharge 

stream is recirculated into the inflow stream; and 

•	 The scroll compressor provides pressure/flow 

characteristics that enable efficient operation 

across a broad range of flow rates. 

Capturing these advantages entails, of necessity, 

overcoming certain risks: 

•	 Overcoming a small oxygen deficit in the inflowing process gas that results from recirculating a small amount of discharge gas, and 

Starting with the turbocharger, pictured in Figure 

4, the design approach involved balancing competing 

elements.; Over a dozen different turbomachine 

configurations were considered, exploring the 

potential for multiple stage and controllable 

geometry designs to address the performance 

requirements. Although ultimate performance can 

only be achieved with controllable guide vanes for 

the expander and/or compressor, these features add 

substantially to the cost and complexity of the 

turbomachine. By exploiting the opportunity to 

recirculate a small fraction of the discharge gas, a 

fixed geometry turbomachine can be made to cover 

the full required performance range. For the scroll, 

the design approach has involved the detailed 

evaluation of three competing configuration options 

and the selection of a single conventional design 

approach, as shown in Figure 5. This design 

represents a low-risk approach, incorporating new 

and stringent lubricant management features into 

well-proven design configurations. A brassboard 

working model of the drive mechanism currently 

under construction will prove the utility and 

functionality of the preliminary design. 

Results 

A novel system architecture has been developed 

that exploits a simple pressure-operated relief valve 

to permit a fixed-geometry turbine to provide stack 

Figure 2. Key Hybrid TurboScroll Performance Figure 3. Hybrid TurboScroll System Architecture 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

pressure control tailorable to a wide variety of compression and positive displacement scroll 

possible pressure-flow profiles. The system feeds compression in this system. Manufacturing costs 

both the turbocompressor output and any bypass gas based on these preliminary designs have also 

into an intercooler for rejection of heat and improved. 

densification of the process gas prior to compression 

to final operating pressure through the scroll 

compressor. Based on detailed preliminary designs, 

substantial improvements in system weight and 

volume, relative to previous generation machines, 

have been achieved by the hybridization of turboFigure 4. TurboCompressor Preliminary Design 

Figure 5. Scroll Compressor Preliminary Design 

Preliminary design of the turbocompressor has 

been completed. In the turbocompressor, 

conventional grease-lubricated ball bearings have 

been identified and selected. Lubricant management 

is simplified by the relatively low vapor pressure of 

the selected grease, as well as the physical and 

pressure-gradient isolation provided in the design of 

the turbocompressor. Aluminum wheels and 

housings have been designed, and the rotordynamics 

configured to provide "stiff," or below-resonance, 

operation over the whole operating range. Estimated 

maximum turbine efficiencies of 86%, and 

compressor efficiencies up to 75%, closely approach 

the targets defined in the DOE guidelines. The 

intercooler has conventional performance 

requirements, and, indeed, the selected approach is to 

use an available automotive intercooler of the 

appropriate size and integrate it into the system. 

Preliminary design of the scroll compressor has 

been completed. The selected scroll compressor 

design uses a conventional crank-driven orbiting 

scroll, supported on a roller-Oldham thrust bearing 

system, grease lubricated. This configuration has the 

substantial advantage of conventionality, enabling 

the direct utilization of knowledge gained in dozens 

of scroll compressor design programs. The most 

highly stressed machine element, the crank bearing, 

has been selected and will be tested in a full-scale 

brassboard drive mechanism demonstration device. 

This roller bearing will be of conventional design and 

grease lubricated. The lubricant for both the crank 

and thrust bearings will be isolated from the process 

gas by three means: (1) the high viscosity and low 

volatility of the grease itself, (2) mechanical sealing 

of the process gas space from the lubricant space, and 

(3) pressure gradient isolation of any tramp lubricant 

from entering the process stream. Estimated 

compressor peak efficiencies of 70% are comparable 

with the efficiencies demonstrated in previous 

generations of scroll compressors and indicate that 

the overall net shaft power consumption of the 

system will be approximately 5-6 kW. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

Based on detailed preliminary designs of the 

critical system elements, the Hybrid TurboScroll 

Compressor/Expander Module concept will deliver 

significant improvements in weight, volume and 

manufacturing cost relative to previous generation 

systems. Further, based on analysis of the 

preliminary designs, the parasitic power 

requirements of the system are also expected to 

improve. A novel system architecture substantially 

simplifies the overall system, permits flexible 

pressure/flow tailoring of the system behavior, and 

provides important improvements in 

manufacturability with minimal performance penalty 

provided that the small decrease in oxygen 

 FY 2003 Progress Report 

concentration in the feed gas is well tolerated by the 

fuel cell. 

FY 2003 Publications/Presentations 

1. DOE Compressor/Expander Module 

Development Program, Tech Team Meeting, April 

16, 2003. 

2. DOE Compressor/Expander Module 

Development Program, Merit Review Meeting, 

May 22, 2003. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Carbon Foam for Fuel Cell Humidification 

Ronald D. Ott (Primary Contact), P. Kadolkar, J. W. Klett 

Oak Ridge National Laboratory 

P. O. Box 2008 

Oak Ridge, TN 37831-6083 

Phone: (865) 574-5172; Fax: (865) 574-4357; E-mail: ottr@ornl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 To fabricate a compact, efficient humidification system to recover water and heat from the exhaust of a 

polymer electrolyte membrane (PEM) fuel cell to humidify the inlet air. 

•	 Utilize carbon foam as heat and mass transport medium. 

•	 Optimize carbon foam density, window and pore size to maximize efficiency in heat and water 

transport. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 R. Thermal and Water Management 

Approach 

•	 Design test rig to evaluate the carbon foam's ability to absorb water, provide humidification, and 

provide heat rejection. 

•	 Determine the ability to pass water through the carbon foam. 

•	 Evaluate the structure of the carbon foam and how it pertains to its ability to function as a water and 

heat transfer medium. 

•	 Analyze data to determine how the carbon foam could be used to develop an improved humidification 

system in order to reduce energy requirements, size and cost of a recovery unit. 

Accomplishments 

•	 Demonstrated the carbon foam's ability to absorb water and reject heat while humidifying air. 

•	 Demonstrated the ability to pass water through the foam, proving that once water condenses on the 

foam, it will pass through. 

•	 Demonstrated that the structure and window/pore size of the carbon foam are directly related to its 

ability to transfer heat and water. 

Future Directions 

•	 Tailor the window/pore opening size so that the wicking capability of the carbon foam is optimized to 

deliver saturated air at 80°C, at required flow rates, to the inlet air stream of a PEM fuel cell. 

•	 Determine the effects of tailoring the window/pore opening size to the heat transfer capability of the 

carbon foam. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Interface with a manufacturer of recovery units for fuel cell technology so that all aspects of a recovery 

unit are considered. 

•	 Design a full-scale recovery unit to evaluate the carbon foam's ability to recover water from the 

exhaust side of the fuel cell. 

•	 Demonstrate reduced need for ancillary equipment (no need for water pumps, heaters, etc...). 

• Work alongside a fuel cell manufacturer to field test a carbon foam recovery unit on PEM fuel cells. 

Introduction 

The efficiency of the automotive polymer 

electrolyte membrane (PEM) fuel cell depends on 

many factors, one of which is the humidification of 

the inlet air. If the inlet air is not sufficiently humid 

(saturated), then the stack can develop dry spots in 

the membrane, and efficiency and voltage will drop. 

Therefore, it is necessary to ensure that humid inlet 

air at the proper elevated temperature is supplied to 

the stack. Current methods involve using a spray 

nozzle to atomize water droplets onto a cloth or wire 

mesh substrate. As the inlet air passes over the cloth, 

it gains moisture and becomes more humid; however, 

since the air is not preheated, the actual level of 

humidification (percent humidity) drops as the air is 

heated in the fuel cell. If heat could be supplied to 

the water efficiently, the system would become 

independent of the ambient conditions, the inlet air 

could become more humid at the proper 

temperatures, and the overall stack could maintain a 

high level of efficiency. Carbon foam has been 

demonstrated to be very efficient in heat transfer in 

previous work with power electronic heat sinks and 

automotive radiators. Using the carbon foam in the 

PEM fuel cell may solve the inlet air humidification 

problems. 

This unique carbon foam (Figure 1) has a density 

between 0.2 and 0.6 g/cm3

 and a bulk thermal 

conductivity between 40 and 187 W/m·K. The 

ligaments of the foam exhibit a thermal conductivity 

higher than that of artificial diamond. Additionally, 

in combination with a very accessible surface area 

(>4 m2

/g), the overall heat transfer coefficients of 

foam-based heat exchangers can be up to two orders 

of magnitude greater than those of conventional heat 

exchangers (in some designs). 

The high thermal conductivity, combined with a 

very high specific surface area, permits the carbon 

Figure 1. Oak Ridge National Laboratory's Carbon 

Foam Showing the Pore and Window Sizes 

foam to use waste heat from power electronics, 

cooling fluids, and exhaust gases to vaporize water 

on the pore surfaces more efficiently than other 

media, thus enhancing humidification. The high 

conductivity of the foam will also permit heating of 

the inlet air, thereby supplying hot, humid inlet air to 

the fuel cell stack, regardless of the ambient 

conditions. 

Approach/Results 

To characterize the behavior of the foam as a 

humidifier, a test chamber (Figure 2) was modified to 

quantify its ability to saturate air with water. The 

system is designed with no gap around the foam 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Schematic of the Humidification System 

thereby forcing the fluid to pass through the windows 

and pores of the foam. A tube was inserted into the 

chamber to supply water directly to the foam, so it 

saturates the foam completely. As the air is forced 

through the foam, it forces the water over the 

surfaces of the foam, leading to efficient evaporation. 

As the water evaporates, it removes significant 

amounts of heat while simultaneously saturating the 

air. A simulated power inverter (cartridge heaters in 

a 5x5x2 cm aluminum block) is mounted to the 

aluminum plate and is capable of generating up to 

800 W (32 W/cm2). Refer to Table 1 and Figure 3 

for the complete data set. 

Table 1. Results of Humidification Tests at a Power 

Density of 19 W/cm2 

Water flow rate (cm3/min) 0 10 20 

Air flow rate (kg/min) 0.17 0.17 0.17 

Electronics temperature (EC) 162 151 136 

Outlet air temperature (EC) 103 73 58 

RH% outlet air <0.5 24 87 

RH% @ 60EC 1.17 43.5 79 

RH% @ 80EC 0.5 18.3 33 

As seen in Table 1, the carbon foam reduced the 

electronics temperature with dry air alone. However, 

when the water was added to the foam for 

evaporation, the electronic temperature dropped. 

Because the latent heat of vaporization of water is 

several orders of magnitude greater than the sensible 

heat capacity of water and air, only small amounts of 

water are needed to effect a large absorption of 

energy. The relative humidity of the outlet air (inlet 

Figure 3.	 Heater Temperature as a Function of Power 

Density for Various Water Flow Rates for 

Humidification 

to the fuel cell) can be modified easily by changing 

the amount of water added to the foam. The problem 

will be to balance the heat rejection from the power 

electronics of the coolant with the volume of inlet air 

and water needed to humidify the inlet air. 

Water flow experiments through the foam were 

conducted by passing a specified amount of water 

through a funnel with a piece of carbon foam placed 

at the base of the funnel. The carbon foam piece 

measured 10 mm in diameter and 10 mm in length. 

There were three different densities utilized, thus 

with varying pore and window sizes. Refer to Table 

2 to review the data for the experiments. As can be 

seen, the low-density foam had lower thermal 

conductivity, larger window size (more open 

structure), thus higher water flow rates than the 

higher density foams. 

A heat flow resistance model designed for 

carbon foam radiators has been helpful in further 

development of heat exchangers utilizing the carbon 

foam. It has shown that the highest resistance to heat 

flow is convective heat transfer at the foam/air 

surface. Therefore, there is a need to allow more air 

to pass through the foam in order to take advantage 

of the tremendous amount of surface area available. 

This leads to examining more open structured carbon 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 2. Results of Water Flow Experiments Utilizing 

a 10 mm Diameter by 10 mm Long Piece of 

Carbon Foam with Three Different Densities 

Density (g/cm3) 0.403 0.492 0.556 

Thermal conductivity 

(W/m@K) 

26.56 71.62 90.72 

Window size (mm) 0.195 0.148 0.147 

Pore size (mm) 0.381 0.382 0.501 

Water flow rate (cm3/sec) 0.259 0.072 0.049 

foams which lead to higher water flow rates and high 

heat transfer. 

Conclusions 

Carbon foam is an ideal medium for a recovery 

unit to humidify and heat the inlet air of a fuel cell. 

While it has been demonstrated to be able to 

humidify inlet air to near-saturation levels, several 

problems exist. First, the volume of water needed is 

enormous, and it is anticipated that the water will 

have to be captured in the exit stream of the fuel cell. 

By cooling the exit stream while humidifying the 

inlet air, the dew point of the exit gas can easily be 

reached, and water will condense, allowing the water 

to be recycled. 

Second, while the fuel cell inlet air will be 

required to operate at several atmospheres above 

ambient for proper fuel cell application, this pressure 

will be sufficient to force the air through the foam. 

With less dense carbon foams, the pressure drop 

across the foam will be significantly less. Other 

future work of this project will be to collaborate with 

a fuel cell manufacturer to develop a prototype 

humidifier and test it in a real system. Because the 

water balance on the system will be the most difficult 

task to overcome, several different designs will be 

desired to optimally achieve the humidification while 

recovering excess water from the fuel cell. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Proton Exchange Membrane Fuel Cell Power System on Ethanol 

Ahmed Amrani (Primary Contact), Thomas Richards 

Caterpillar Inc. 

Technical Center, P.O. Box 1875 

Peoria, Illinois 61656 - 1875 

Phone: (309) 578-3913; Fax: (309) 578-8934; E-mail: Amrani_Ahmed@cat.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

ANL Technical Advisor: William M. Swift 

Phone: (630) 252-5964; Fax: (630) 972-4473; E-mail: swift@cmt.anl.gov 

Subcontractors: 

Nuvera Fuel Cells, Cambridge, Massachusetts 

Aventine Renewable Energy, Inc. (formerly Williams Bio-Energy), Pekin, Illinois 

Objectives 

Caterpillar, Nuvera Fuel Cells, and Aventine Renewable Energy have teamed up to develop and 

demonstrate a 10-15 kWe ethanol-fueled proton exchange membrane (PEM) fuel cell system. The primary 

objectives of this project are to: 

•	 Demonstrate performance, durability & reliability via field demonstration 

•	 Remove technical uncertainties 

•	 Understand correlation and reduce gaps between stationary and transportation applications 

•	 Collect data to evaluate economic feasibility 

•	 Assess commercial viability of the total system 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Durability 

•	 G. Power Electronics 

•	 K. Emissions and Environmental Issues 

Approach 

•	 Nuvera will assess and modify advanced fuel cell power module (processor and fuel cell stack) designs 

that are now under development in separate projects to develop the power module for this project. 

•	 Caterpillar will design the power converter module and will integrate the system. 

•	 Aventine will supply the ethanol and the host site to test the unit and conduct endurance testing. 

Accomplishments 

•	 The fuel cell power module accumulated 200 hours at various fuel cell power levels, while the fuel 

processor had been operating in idle mode for more than 600 hours. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 The power converter (laboratory direct current [DC] power supply to alternating current [AC] into 

utility grid) has operated in the range 8 to 16 kW for over 300 hours. 

•	 The Aventine site in Pekin, Illinois has been prepared for system installation. 

•	 The data acquisition system has been run with real-time field data. 

•	 The web site for external reporting of field operation is 90% complete. 

•	 The safety review of operations is complete, and all permits have been approved. 

•	 The response plan for field operations and supportability is close to completion. 

Future Directions 

•	 Operate the power module at rated power (>5 kWe) for 250 hours with full automation (Nuvera in 3Q, 

2003). 

•	 Following above, operate integrated power module and power converter with full automation and 

complete acceptance testing (Nuvera and Caterpillar in 3Q, 2003). 

•	 Ship the functional unit to the test site and start the endurance-testing phase (Nuvera, Caterpillar, and 

Aventine starting in 4Q, 2003). 

Introduction 

Nuvera will design, build, test, and deliver a 10-

15 kWe DC fuel cell power module that will be 

specifically designed for stationary power operation 

using ethanol as a primary fuel. Two PEM fuel cell 

stacks in parallel will produce 250 A and 60 volts at 

rated power. The power module will consist of a fuel 

processor and CO clean-up, fuel cell, air, fuel, water, 

and anode exhaust gas management subsystems. A 

state-of-the-art control system will interface with the 

power system controller and will control the fuel cell 

power module under start-up, steady state, transient, 

and shutdown operation. Temperature, pressure, and 

flow sensors will be incorporated in the power 

module to monitor and control the key system 

variables under these various operating modes. The 

power module subsystem will be integrated with the 

power converter, tested at Nuvera and subsequently 

delivered to the Aventine site in Pekin, Illinois. 

Approach 

Nuvera plans to modify advanced fuel cell power 

module designs that are now under development in 

separate projects for use in this project. They will 

start with a power module that is a multi-fuel design 

for transportation (light-duty vehicle) applications. 

The purpose of using this design baseline is twofold. 

•	 By using an existing design, Nuvera will 

avoid much of the design effort and technical 

risk associated with a completely new power 

module design. 

•	 By using a transportation-based design, this 

demonstration will simultaneously illustrate 

that renewable ethanol can be used in fuel 

cell power systems applied to stationary 

power generation as well as transportation. 

Caterpillar will design, build, test and deliver a 

power converter module that converts the DC output 

of the power module into AC power. Caterpillar will 

also provide system level control to ensure all major 

subsystems work in harmony and provide constant 

power to the industrial load on site. The fuel cell 

system will deliver power to the grid at the Aventine 

ethanol production site in Pekin, Illinois. 

The power converter design will rely on 

Caterpillar's experience with state-of-the-art solidstate power converters that employ switches, 

inverters and pulse width modulation to shape a 

sinusoidal voltage and current in time with the 

existing power source on site. 

Caterpillar also aims to demonstrate technology 

to the greatest extent possible that can meet the dual 

requirements of the transportation industry and the 

stationary electric power generation industry. In 

addition to low levels of emissions, we intend to 

demonstrate high efficiency, durability, and 

reliability. These technical objectives will enable us 

to calculate the cost of electricity ($/kW-hr) for 

transportation and stationary power applications. 

Aventine will host the industrial site for this 

demonstration. Aventine provided site electrical load 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1. Power Converter at Caterpillar Technical 

Center 

and ethanol fuel requirements. They have prepared 

the site to ensure the fuel cell system links to their 

power network, supply of ethanol fuel and other 

utilities. During the demonstration, Aventine's 

personnel will monitor and service (general 

maintenance and where feasible, troubleshoot and 

repair) equipment and permit visitors to witness the 

demonstration in comfort and safety. 

Results 

The cooperative team has achieved several 

milestones to date since project inception and 

commencement. The results are highlighted below 

for the two major subsystems. 

Power Converter. The power converter has been 

built and tested. Figure 1 shows the unit at 

Caterpillar's Technical Center, and Table I 

summarizes the test data to date. 

Power Module. The power module has been built 

and continues to be tested. Figure 2 shows the unit 

at Nuvera Technical Center, and Table II 

summarizes the test data to date. 

Industrial Demonstration Site. Aventine has 

completed the site preparation at their plant in 

Pekin, Illinois, where the integrated power system 

will be tested for endurance. Figure 3 shows the 

fully prepared site ready for system installation. 

Table I. Summary of the Power Converter Laboratory 

Test Results 

Description Physical 

Units 

Numerical 

Value Comments 

Maximum DC 

input power (230 

A, 70 V) 

kW 16 

Maximum AC 

output power 

kW 13.5 Into local utility 

grid 

Energy efficiency 

at rated power 

(15 kW) 

% 90 

Total Harmonic 

Distortion at rated 

power (15 kW) 

% 2 Meets UL 1741 & 

IEEE 519 

Total laboratory 

time operating 

above 4 kW 

hours 85 Design & 

Packaging are 

complete, 2nd unit 

under construction 

as spare 

Table II. Summary of the Power Module Laboratory 

Test Data 

Criterion Specification Status 

Power Idle to 15 kWe Idle to 11 kWe 

Start-up time 60 min Less than 60 min 

Efficiency >25% 29% 

Laboratory 

Hours 

500 hours for 

Factory Acceptance 

Testing 

145 hours at various power 

levels 

Start-up Afterburner free Afterburner free 

Controls 

Automation 

Unattended 

operation 

Combination of manual and 

automated operation 

In addition, Nuvera, Aventine, and Caterpillar 

have worked together to generate data collection and 

retrieval. Table III summarizes accomplishments 

related to data collection, data display, and field 

operation with remote control. 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Power Module at Nuvera Test Laboratory 

Figure 3. Aventine Industrial Site for 4000-hour 

Demonstration 

Table III. Summary of Data Collection, Data Display, 

and Remote Control 

Utility grid interactive connections are installed at test site. 

Ethanol storage and handling is installed at test site. 

Data acquisition system running on laboratory data is 90% 

complete. 

Remote monitoring, data backup and Internet viewing is 90% 

complete. 

Visitor parking and observation amenities are installed. 

Hazardous operations procedures are complete. 

Conclusions/Future Work 

A Final Design Review was hosted by and held 

at Nuvera in Cambridge on June 10, 2003, with DOE 

and Caterpillar focusing on critical issues and plans 

for resolution while refining the project plan with 

milestones, targeting critical test and review dates. 

The plan identified critical paths and methodologies 

to follow them in order to stay on track within budget 

and time. Also reviewed were the power converter 

and module integration plans and acceptance criteria 

to allow shipment. A facility tour to witness the ongoing factory acceptance testing of the power module 

was provided by Nuvera. 

Nuvera will continue the automation of the 

controls and factory acceptance testing and prepare 

for the shakedown integrated testing (power module 

and power converter). Caterpillar has completed the 

second (spare) power converter and will test it, while 

fine-tuning the first one and also preparing it for 

integration. Aventine will finalize and fine-tune all 

installed equipment to date on site in preparation for 

the endurance testing. 

The team expects to commence field 

demonstration of possibly the nation's first ethanolpowered PEM fuel cell unit in 4Q, 2003. 

FY 2003 Publications/Presentations 

1. Midwest Regional Hydrogen Infrastructure 

Forum, 10 October 2002, Chicago, Illinois 

2. Renewable Fuels Association Booth, Fuel Cell 

Seminar, 18 to 21 November 2002, Palm 

Springs, California 

3. Illinois Coalition Meeting, 17 April 2003, Des 

Plaines, Illinois 

4. DOE Merit Review, 21 May 2003, Berkeley, 

California 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

New Proton Conducting Solid Sulfide Membranes for Intermediate Temperature 

Fuel Cells 

Steve W. Martin (Primary Contact), Steven A. Poling, Jacob T. Sutherland, Carly R. Nelson 

Iowa State University of Science and Technology, Materials Science and Engineering Department 

3053 Gilman Hall 

Ames, Iowa, 50011 

Phone: (515) 294-0745; Fax: (515) 294-5444; E-mail: swmartin@iastate.edu 

DOE Technology Development Manager: Roxanne Danz 

Phone: (202) 586-7260; Fax: (202) 586-9811; E-mail: Roxanne.Danz@ee.doe.gov 

Objectives 

•	 Investigate a new class of inorganic sulfide-based proton conducting membranes for hydrogen fuel cell 

applications. 

•	 Produce anhydrous solid membranes having minimal fuel crossover capability and address many of 

the problems associated with current hydrogen fuel cell technologies. 

•	 Optimize membrane materials to yield high proton conductivities (10-3 to 10-1 S/cm) in the
 

intermediate temperature range of 125oC to 300oC.
 

•	 Demonstrate performance, thermally stability, and chemical stablility to H2O and O2 in a typical fuel 

cell setup at operating temperatures. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 F. Heat Utilization 

•	 O. Stack Material and Manufacturing Cost 

•	 R. Thermal and Water Management 

Approach 

•	 Synthesize new protonated sulfides (thio-acids). 

•	 Synthesize membrane materials from thio-acids; final product may be a glass, glass/ceramic, or 

ceramic material with stable sulfur-hydrogen bonds. 

•	 Measure the proton conductivity between –70o

C and 500oC. 

•	 Determine the thermal stability. 

•	 Determine the chemical stability with respect to H2O and O2. 

•	 Determine electrochemical properties, including reduction and oxidation potentials, and cyclic 

voltammetry. 

•	 Cooperatively fabricate and test membrane electrode assemblies (MEAs) using the most promising 

membranes. This is to be done in partnership with an external company specializing in fuel cells. 

Accomplishments 

•	 The hydrosulfides of potassium, rubidium, cesium, and barium have been synthesized. Proton 

conductivity of 10-9 to 10-6 S/cm has been acheived in the temperature range of 25o

C to 200oC. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Mixed hydrogen alkali thiogermanates have been synthesized with the adamanatane-like Ge4S10 

4­

anion. Proton conductivity of 10-10 to 10-5 S/cm has been acheived in the temperature range of 50oC 

to 225o

C. 

•	 A new class of anhydrous proton conducting materials has been recently synthesized (patent protection 

pending). These materials acheive fast proton conductivity (10-3 to 10-2 S/cm) from 65oC to 270oC. 

Future Directions 

•	 Test the recently developed fast proton conducting anhydrous membrane materials (patent protection 

pending) under relative humidity (RH) conditions as subject by a fuel cell environment. Build MEAs 

using these membrane materials in cooperation with UTC Fuel Cells. Continue to sythesize and 

characterize structurally similar membrane materials. 

•	 Synthesize pervoskite and distorted pervoskite type ABS3 (A = Ca, Sr, Ba, etc.; B = Zr, Ce, etc.) 

precursor materials. These materials may then be doped with trivalent anions (Y, La, etc.) and reacted 

with liquid H2S to produce proton conducting membranes. 

•	 Synthesize adamantane-like AxGe4S10 (1.5 ≤ x < 2) and MyGe4S10 (M = K, Rb, Cs; 3 ≤ y < 4) 

precursor materials. These materials may then be reacted with liquid H2S to produce proton 

conducting membranes. 

Introduction 

Hydrogen-based fuel cells are becoming 

increasingly popular as an alternative energy source 

for automobiles. This is evident by the recent 

presidential Hydrogen Fuel Initiative to reverse 

America's growing dependence on foreign oil by 

developing the technology needed for commercially 

viable hydrogen-powered fuel cells. At the heart of 

the fuel cell is the proton exchange membrane 

(PEM), which transports protons from the anode to 

the cathode while providing electronic insulation 

between them. Currently, there are many types of 

electrolyte materials for application as PEMs. 

However, each material has specific limitations 

restricting its usefulness for application to fuel cells. 

With these current fuel cell membrane materials, 

there remains a temperature region between 125oC 

and 300o

C in which currently no one membrane can 

provide optimum performance. In this regime, we 

propose the use of sulfide-based proton conducting 

membranes. In general, these membranes are being 

developed to be anhydrous in nature, thermally stable 

up to 300o

C, and chemically stable with respect to 

H2O and O2. Being solid in nature, these membranes 

are not expected to exhibit fuel cross-over problems. 

Additionally, proton conductivities of these 

membranes are expected to be orders of magnitude 

higher than their oxide counterparts, assuming they 

follow the trend exhibited by monovalent cations 

such as Li and Ag in chalcogenide verses oxide host 

materials (Angell 1992). Well-ordered crystalline 

structures exhibiting fast proton conductivity may 

also be developed for sulfide materials analogous to 

those previously reported for various oxide materials 

(e.g. Huang 1995, Haile 2001). 

Approach 

Various precursor materials, including oxides, 

hydroxides, sulfides, fluorides, chlorides, bromides, 

and iodides, that are capable of forming thio-acids in 

liquid H2S solutions have been identified. As an 

example, the reaction of GeO2 or GeS2 with liquid 

H2S at room temperature produces the thio-acid 

H4Ge4S10. Membranes may be produced by 

tailoring precursor materials to obtain structural 

ordered reaction products with high proton 

conductivities. Taking various alkali or alkaline 

earth modified glassy or crystalline materials and 

reacting them in a liquid H2S solution is one way to 

accomplish this. 

Proton conductivity in the protonated reaction 

products, i.e. membrane materials, is being 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

determined through impedance measurements as a 

function of temperature and frequency. Direct 

current polarization experiments have been used to 

determine the electronic verses ionic conductivity of 

these materials. Physical properties of the protonated 

materials have been determined, including 

decomposition, sublimation, and crystallization. 

Structural comparisons have been used to examine 

stability with exposure to H2O and O2. 

Conductivity measurements under RH 

environments are underway. Additionally, a 

cooperative effort to fabricate and test MEAs using 

our most promising membranes is being carried out 

in partnership with UTC Fuel Cells. 

Results 

Many protonated sulfide materials have been 

produced from liquid H2S reactions with various 

precursor materials. The conductivities of these 

protonated materials have been measured with 

reference to alkali and/or electronic base 

conductivity. Figure 1 illustrates proton conductivity 

for alkali hydrosulfides of K, Rb, and Cs. These 

materials have low conductivities (< 10-6 S/cm) and 

average thermal stability (< 200oC). Additionally, 

the alkali hydrosulfides readily react with H2O and 

CO2 under atmospheric conditions, precluding them 

from being successful candidates for MEAs. 

 FY 2003 Progress Report 

Another class of protonated materials is based on 

the crystalline Ge4S10 

4- anion. Figure 2 shows the 

infrared (IR) vibrational spectra illustrating mixed 

hydrogen and alkali terminal units. Peaks observed 

below 550 cm-1 represent vibrational modes of the 

Ge4S10 

4- structural unit cage, whereas the peaks 

around 2500 cm-1 represent the S-H stretching mode. 

The broad mode ~2250 cm-1 for the hydrogen cesium 

systems indicates the presence of intercalated H2S; 

this is analogous to intercalated H2O as required for 

many fast proton conducting materials (e.g. 

Nafion®). Figure 3 shows typical conductivity 

spectra of these hydrogen alkali thiogermanate 

phases. For the phases with higher alkali content (x 

≥ 2), a discontinuity from Arrhenius behavior is 

typically observed with higher proton conductivity 

(~10-5 S/cm), suggesting a well-ordered structure 

capable of effective proton transport. At higher 

temperatures (> 175oC), these phases start 

decomposing by losing mobile proton species, and as 

a result, the conductivity decreases. Further work is 

underway to optimize these materials for proton 

conductivity and thermal stability. 

Figure 4 shows examples of proton conductivity 

for some of the recently designed anhydrous 

membrane materials (patent protection pending). 

Figure 1. Proton Conductivity of Alkali Hydrosulfides 

of KSH, RbSH, and CsSH 

Figure 2. IR Spectra of Hydrogen Alkali 

Thiogermanates 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Typical Proton Conductivity for Hydrogen 

Alkali Thiogermanates 

Figure 4. Fast Proton Conductivity for Recently 

Developed Anhydrous Membrane Materials 

Fast proton conductivity is observed (10-3 to 10-2 S/ 

cm) from 65o

C to 270oC. These new protonated 

materials illustrate the viability and promise of 

alternative proton conducting membrane materials 

for the intermediate temperature range of 125o

C to 

300oC. RH testing and MEA fabrication and testing 

are currently underway with these new anhydrous 

proton conductors. 

Conclusions 

•	 A new synthesis route for producing thio-acids, 

hydrosulfides, and sulfides has been identified 

and patented. 

•	 The structure, conductivity, thermal and 

chemical stability of many protonated materials 

have been investigated; many more are being 

pursued. 

•	 Structurally ordered membrane materials have 

been identified as potential fast proton 

conductors, and effort is underway to produce 

these new protonated materials. 

•	 Recently, one of these new classes of fast proton 

conducting materials have been identified and 

synthesised for the first time (patent protection 

pending). 

•	 Preliminary ionic conductivity values as high as 

10-3 to 10-2 S/cm have been realized from 65o

C 

to 270oC; these materials are thus classified as 

fast proton conductors. 

References 

1. Martin, S.W., Poling, S.A., Sutherland, J.T., 

Design and Development of New Glass-Ceramic 

Proton Conducting Membranes. DOE Hydrogen 

Program Annual Review, Proceedings (2002): 

NREL/CP-610-32405. 

2. Angell, C.A. 1992. Mobile Ions in Amorphous 

Solids. Annual Review of Physical Chemistry, 

43:693-717. 

3. Huang, P. and Petric, A. 1995. Electrical 

Conduction of Yttrium-doped Strontium 

Zirconate. J. Mater. Chem., 5:53-56. 

•	 4.Haile, S.M., Boysen, D.A., Chisholm, C.R.I., 

and Merle, R.B. 2001. Solid acids as fuel cell 

electrolytes. Nature, 410:910-913. 

FY 2003 Publications/Presentations 

1. S.A. Poling, C.R. Nelson, and S.W. Martin, 

“Anhydrous proton conductivity in hydrogen 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

alkali thiogermanates,” submitted to Solid State 

Ionics (2003), talk presented at the 14th 

International Conference on Solid State Ionics 

(2003) 

2. J.T. Sutherland, S.A. Poling, C.R. Nelson, and 

S.W. Martin, “Formation reaction routes for the 

thiogermanic acids with GeO2 and GeS2 

precursors,” to be submitted to Solid State Ionics, 

poster presented at the 14th International 

Conference on Solid State Ionics (2003) 

3. C.R. Nelson, S.A. Poling, and S.W. Martin, 

“Synthesis and characterization of potassium, 

rubidium, and cesium thiogermanate glasses,” to 

be submitted to the Journal of Non-Crystalline 

Solids 

4. J.T. Sutherland, S.A. Poling, R.C. Belin, and S.W. 

Martin, “Exploration of the H2S-GeS2 system,” to 

be submitted 

5. J.T. Sutherland, S.A. Poling, C.R. Nelson, and 

S.W. Martin, “H2S synthesis route for high purity 

L.T. 3-D a-GeS2,” in press, Material Science 

Letters (2003) 

6. S.A. Poling, C.R. Nelson, J.T. Sutherland, and 

S.W. Martin, “Crystal structure of thiogermanic 

acid H4Ge4S10,” in press, Inorganic Chemistry 

(2003) 

 FY 2003 Progress Report 

7. S.A. Poling, C.R. Nelson, J.T. Sutherland, and 

S.W. Martin, "Proton conductivity in anhydrous 

and hydrous thiogermanic acids," submitted to 

Solid State Ionics (2003) 

8. S.A. Poling, C.R. Nelson, J.T. Sutherland, and 

S.W. Martin, "Synthesis and characterization of 

the thiogermanic acids H4Ge4S10 and H2Ge4S9," 

Journal of Physical Chemistry B 107 (2003) 5413­

5418 

Special Recognitions & Awards/Patents 

Issued 

1. Synthesis and uses of Thio Acids, Steve W. 

Martin, Steven A. Poling, Jacob T. Sutherland, 

Iowa State University, ROI ISURF 2894, 

February 8, 2002. Provisional filing date of July 

26, 2002. 

2. Record of invention for fast proton conductors, 

Iowa State University, ROI ISURF, July, 2003. 

3. Invited talk, 14th University Conference on Glass, 

“Preparation and Characterization of New Proton 

Conducting Glasses and Ceramics,” Rensselaer 

Polytechnic Institute, Troy, NY, August 13-15, 

2003. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Cell Distributed Power Package Unit: Fuel Processing Based on 

Autothermal Cyclic Reforming 

Ravi Kumar, Parag Kulkarni, Court Moorefield, Shawn Barge, and Vladimir Zamansky 

(Primary Contact) 

General Electric Company 

18 Mason 

Irvine, CA 92618 

Phone: (949) 859-8851 ext. 166; Fax: (949) 859-3194; E-mail: Vladimir.Zamansky@ps.ge.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-1637; E-mail: Kathi.Epping@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: Benjamin@cmt.anl.gov 

Objectives 

•	 Design, fabricate and operate an integrated pre-commercial fuel processor to produce a continuous 

proton exchange membrane (PEM) fuel cell grade hydrogen-rich stream. 

•	 Assess the reliability, potential cost and performance of the fuel processor. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Cost 

•	 B. Operation and Maintenance (O&M) 

•	 C. Feedstock and Water Issues 

•	 D. Carbon Dioxide Emissions 

•	 E. Control and Safety 

Approach 

•	 Design a pre-commercial 50-kWe fuel processor to produce PEM fuel cell grade hydrogen-rich gas 

from natural gas based on GE's Autothermal Cyclic Reforming (ACR) technology. 

•	 Analyze several process configurations that include ACR reactors, shift reactors, preferential oxidation 

reactors (PrOx) and heat exchangers, and select the best configuration with high efficiency, high 

reliability and low capital cost. 

•	 Design, fabricate and operate the ACR-based fuel processor. 

•	 Develop a control system for safe operation of the fuel processor with low O&M cost. 

•	 Develop tools to quantify the efficiency, cost and reliability of the fuel processor. 

Accomplishments 

•	 Designed, fabricated and operated a pre-commercial 50-kWe fuel processor that includes the ACR, 

shift and PrOx reactors and heat exchangers to produce a continuous hydrogen-rich stream with less 

than 50 ppm CO. 

•	 Developed a control system for safe operation of the fuel processor. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Developed a cost analysis model to estimate the delivered electricity cost from the ACR and PEM fuel 

cell based power system as a function of capacity and mass production rate. 

•	 Developed tools (Failure Reporting, Analysis and Corrective Action System {FRACAS} and 

Reliasoft) to track and quantify the reliability of the fuel processor. 

Future Directions 

•	 Optimize the ACR-based fuel processor to get <10 ppm CO in the product stream. 

•	 Integrate the fuel processor with a PEM fuel cell. 

•	 Develop an ACR catalyst that is active and durable for over 5,000 hours to reduce the O&M costs 

further. 

Introduction 

GE is developing a proton exchange membrane 

(PEM) fuel cell based distributed power generation 

unit that uses a proprietary fuel processor to convert 

fossil fuels to a hydrogen-rich gas for use in the PEM 

fuel cell. The target application is commercial and 

residential buildings with electric demand in the 20-

200 kWe range and with cogeneration needs. The 

goal of this project is to design, develop, and 

demonstrate an integrated unit for generating electric 

power in buildings. Phase II is a demonstration of 

the integrated fuel processor to continuously generate 

PEM fuel cell grade hydrogen. This integrated unit 

will be used to generate data needed in the design of 

a prototype power generation package. The unit 

promises high efficiency, low emissions and low cost 

by utilizing a novel process called autothermal cyclic 

reforming (ACR). 

ACR is an autothermal cyclic catalytic steam 

reforming technology for converting hydrocarbons to 

a hydrogen-rich stream. The ACR process operates 

in a three-step cycle that includes steam reforming of 

the fuel in a Ni catalyst bed (Step 1 - Reforming), 

heating the reactor through oxidation of the Ni 

catalyst (Step 2 - Air Regeneration), and finally 

reducing the catalyst to the metallic state (Step 3 - 

Fuel Regeneration). The heat required for the 

endothermic reforming step is provided during the 

exothermic air regeneration step. The ACR process 

consists of two low pressure reactors cycling 

between the reforming and regeneration (air and fuel) 

steps to produce a continuous stream of hydrogenrich gas. The fuel processor produces a 70-80% 

hydrogen stream that can be purified downstream for 

PEM fuel cell quality using a shift and a PrOx 

reactor. The ACR process is a unique technology 

that can be applied for the production of hydrogen 

from different fuels, including natural gas, diesel 

fuel, and renewable feedstock, such as bio-fuels. The 

ACR process represents a significant technological 

advancement in comparison with autothermal 

reforming (ATR) and partial oxidation (POX), as the 

ACR-produced syngas is not diluted with nitrogen, 

and the overall efficiency of the ACR process is 

higher than ATR and POX. When compared to 

conventional steam methane reforming (SMR), the 

ACR process has significantly lower capital costs 

and lower emissions. In addition, the ACR process is 

fuel flexible and has been successfully demonstrated 

using high-sulfur fuels. 

Approach 

A major goal in the Hydrogen, Fuel Cells & 

Infrastructure Technologies Program Multi-Year 

Research, Development and Demonstration Plan is to 

reduce the cost of H2 or electricity produced from 

natural gas or other fossil fuels. The ACR 

technology promises to reduce the capital cost and 

improve the efficiency and reliability of the fuel 

processor as compared to other reforming 

technologies (SMR, ATR and POX). The final 

process configuration for the ACR-based fuel 

processor was selected after detailed process analysis 

of several configurations to achieve the desired 

performance targets including capital cost and 

efficiency. 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1. ACR-based 50-kWe Fuel Processor 

A 50-kWe fuel processor was designed and 

fabricated. The integrated fuel processor consists of 

ACR reactor, shift reactor, PrOx reactor and heat 

exchangers. Figure 1 shows the picture of the fuel 

processor. A control system was developed for 

automatic and safe operation of the fuel processor. 

A detailed safety review, including preliminary 

hazard analysis (PHA), hazardous operations 

review (HAZOP) and accident scenario review 

(ASR) of the fuel processor, was carried out before 

operating the fuel processor. The integrated fuel 

processor was operated to produce a continuous 

hydrogen-rich stream. 

Process analysis tools were developed to 

quantify the efficiency, cost and reliability of the fuel 

processor. The efficiencies of several ACR-based 

process configurations were calculated and compared 

with efficiencies of existing reforming technologies. 

An economic model was developed to calculate the 

capital and O&M costs for the fuel processor under 

different scenarios of capacity and mass production. 

The reliability of the fuel processor is being tracked 

and quantified by using GE's tools, such as FRACAS 

and Reliasoft. 

Results 

The ACR unit produces a continuous hydrogenrich stream (70-80% hydrogen on a dry basis) 

through cyclic operation of two reactors. Methane 

slip from the ACR reactors is less than 5%. Figure 2 

shows the typical dry gas composition of the product 

gas from the ACR reactors. The reformate stream 

contains 8-10% carbon monoxide. 

The shift reactor reduces the concentration of CO 

in the product gas to less than 0.5% via water gas 

shift reaction (CO + H2O Y H2 + CO2). The PrOx 

reactor further reduces the CO concentration below 

50 ppm via selective oxidation of CO to CO2. 

Further optimization of PrOx reactor operating 

conditions will result in reducing the CO 

concentration in the product below 10 ppm. Figure 3 

summarizes the typical product dry composition after 

ACR, shift and PrOx reactors. 

The cost analysis model was developed to 

estimate the cost of electricity produced by the ACR 

fuel processor integrated with a fuel cell. The model 

takes into account the capital cost, O&M costs, fuel 

cost and consumable cost. Figure 4 shows the 

relationship between the cost of electricity and the 

Figure 2. Composition of the Product Gas (Dry Basis) 

from the ACR Reactors 

Figure 3. Composition at the Outlets of ACR, Shift and 

PrOx Reactors (Dry Basis) 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

fuel processor/fuel cell capacity at different mass 

production rates based on the cost analysis model. 

The plot shows that the fuel processors will be cost 

effective at higher capacities (> 300 kWe) and when 

mass-produced (> 5,000 units/year). 

Figure 5 shows the cost of electricity as a 

function of catalyst life for a 200-kWe fuel processor. 

If the catalyst life is over 2,000 hours, the fuel 

processor becomes cost effective. Nearly 30 

different reforming catalysts were studied in a related 

project funded by the California Energy 

Commission. A catalyst that is active and durable for 

2,000 h has been identified. 

The reliability of the fuel processor is currently 

being tracked in the failure reporting, analysis and 

corrective action system (FRACAS). Once the 

Figure 4.	 Relationship Between the Cost of Electricity 

and the Fuel Processor Capacity at Different 

Mass Production Rates 

Figure 5. Cost of Electricity as a Function of Catalyst 

Life 

 FY 2003 Progress Report 

FRACAS system is populated with statistical failure 

data, the reliability of the entire fuel processor will be 

calculated using a software tool called Reliasoft. 

Reliasoft links the reliability of individual 

components through a block diagram to calculate the 

reliability of the integrated fuel processor. 

Conclusions 

•	 The ACR-based fuel processor produces a continuous hydrogen-rich stream (70-80% hydrogen on a dry basis) through cyclic operation of 

two ACR reactors. The heat required for the 

endothermic reforming process is generated by 

exothermic oxidation reaction of the nickel catalyst followed by its regeneration. 

•	 The shift and PrOx reactors reduce the CO concentration in the product stream below 50 ppm, 

thus generating a PEM fuel cell grade hydrogenrich stream (further optimization of the PrOx 

reactor will reduce the CO concentrations below 

10 ppm). 

•	 Optimization of the ACR-based fuel processor 

will improve the efficiency and reliability of the 

system and will result in cost reduction. 

FY 2002 Publications/Presentations 

1. Hydrogen Refueling System Based on 

Autothermal Cyclic Reforming, Kumar, R., 

International Energy Agency Annexe XV 

Meeting, Palm Springs, CA, Nov 17-18 2002. 

2. Hydrogen Refueling Station Based on 

Autothermal Cyclic Reforming, Kumar, R., 

Barge, S., Kulkarni, P., Moorefield, C., Zamansky, 

V., Fuel Cell Seminar, Palm Springs, CA, Nov 18-

22 2002. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Advanced Buildings PEM Fuel Cell System (New FY 2004 Project) 

Arne LaVen 

Buildings Fuel Cell Program Manager 

IdaTech, LLC 

63160 Britta Street 

Bend, OR 97701 

Phone: (541) 322-1038; Fax: (541) 322-1159; E-mail: alaven@idatech.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

Objectives 

•	 Validate and deploy an advanced, integrated 50-kilowatt (kW) proton exchange membrane (PEM) fuel 

cell system for hotel systems and follow-on applications. 

•	 Develop the fuel cell stack and associated balance of plant by scaling up an existing 25-kW stack 

design and employing advanced membrane electrode assemblies (MEA). 

•	 Develop the fuel processor and associated balance of plant by scaling up an existing 10-kW equivalent 

steam reformer and integrating a pressure swing adsorption (PSA) hydrogen purification module for 

generating hydrogen fuel with purity consistent with a targeted 40,000-hour life system. 

•	 Develop approach for seamless and affordable grid interconnectivity. 

•	 Characterize hotel systems and follow-on market requirements for distributed cogeneration fuel cell 

systems, and establish a commercialization strategic plan. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Distributed Generation 

•	 E. Durability 

•	 F. Heat Utilization 

•	 H. Startup Time 

Fuel Flexible Fuel Processor 

•	 J. Durability 

• N. Cost 	 

Components 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

Approach 

The overall objective of this project is to develop 

an advanced 50-kW PEM fuel cell system. The CM50 power plant will deliver both electricity and 

thermal energy. It will serve hotel systems initially, 

and follow-on segments including multi-family 

dwellings, prison systems, hospital/medical care 

facilities, office buildings, and similar defense market 

applications. An Integrated Product Team comprised 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

of IdaTech, LLC; Hydrogenics Corporation; Southern 

California Gas; San Diego Gas & Electric; Puget 

Sound Energy; Marriott International; and the 

California Hotel & Lodging Association, as supported 

by W. L. Gore & Associates and R4 Energy, Inc., will 

perform this work. 

An assessment of building systems by the utility 

partners has revealed that the targeted market 

segments will effectively use 50 kW of electricity 

and 65 kW of thermal energy, saving energy costs 

while reducing environmental emissions. These onsite baseload generators will employ developed and 

scaled-up fuel cell stack and fuel processing 

technology, leveraging existing U.S. and Canadian 

federal investments. The PEM system will reduce 

baseload electricity and thermal energy expense for 

mid-sized and large hotel systems through single unit 

and ganged fuel cell configurations. 

The key to the CM-50 fuel cell system solution is 

a blend of advanced fuel cell technology developed 

by Hydrogenics, and proven fuel processing 

technology consisting of steam reforming of natural 

gas and pressure swing adsorption purification 

integrated by IdaTech. Hydrogenics will use the 

latest membrane electronic assembly componentry 

developed by W. L. Gore & Associates in its lowpressure fuel cell stack. Low pressure is a key to 

achieving long lifetimes and higher system 

efficiencies. 

Sempra Energy (with members Southern 

California Gas and San Diego Gas & Electric) and 

Puget Sound Energy will each site one field trial 

power plant in their service territories in the 2005 

timeframe. Marriott International will select a third 

field trial site at one of its West Coast properties. 

The utility and hotel systems will supply grid 

interconnection solutions as well as manage the 

overall siting and field trial projects. The California 

Hotel & Lodging Association will provide guidance 

regarding hotel systems energy requirements, 

including buildings integration and expected 

 FY 2003 Progress Report 

performance parameters. R4 Energy will provide 

building and follow-on markets consultation services 

and recommendations for compliance with federal, 

state and local buildings codes and standards. 

The fuel cell system gross electrical efficiency is 

projected to be 38% using the DOE definition for 

efficiency: direct current power at the fuel cell 

electrodes divided by the total energy of the fuel 

metered into the fuel cell system based on the lower 

heating value of natural gas. Overall system 

efficiency is projected at 71% for installations 

recovering useful heat down to 50°C. The power and 

thermal ratings are directly driven by the targeted 

hotel requirement. 

The proposed fuel cell system incorporates the 

ability to operate in stand-alone uninterrupted power 

supply mode, displacing for example more than 

1,000 emergency diesel gensets deployed in San 

Diego alone. A diesel genset emits approximately 3 

lbs NOx per megawatt hour (MWh), while the 

proposed system will emit a virtually undetectable 

level of NOx, CO and CO2. Since sulfur is trapped 

during fuel processing, fuel cell SOx emissions will 

be in the low parts per billion range. 

Forty percent of over 13,000 domestic hotel 

properties could use the forthcoming CM-50 power 

plant as their source of primary power. The Team 

will develop the CM-50 fuel cell system, conduct 

three comprehensive demonstration field trials along 

West Coast markets from California to Washington 

state, and proceed to commercial deployments 

throughout North America. 

The Team is committed to deploying the CM-50 

commercially at the conclusion of the proposed 

project. Given the high potential for achieving 

performance, cost, reliability and durability 

objectives, early market deployment is achievable. 

Additionally, applications for a 50-kW system are 

evolving, indicating a broader market appreciation 

for their utility. 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

150-kW PEM Fuel Cell Power Plant Verification and Regional Demonstration 

of 150-kW PEM Fuel Cell Power Plant (New FY 2004 Project) 

Douglas Wheeler (Primary Contact) 

UTC Fuel Cells, LLC 

195 Governor's Highway 

South Windsor, CT 06084 

Phone: (860) 727-2513; Fax: (860) 998-9231; E-mail: douglas.wheeler@utcfuelcells.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

Objectives 

•	 Verify the specification, durability, and reliability of a 150-kW natural gas fueled proton exchange 

membrane (PEM) power plant 

•	 Verify multiple power plants can be connected to a distribution feeder with no adverse interconnection 

effects 

•	 Confirm that integration of power plant heat with a liquid desiccant dehumidification system increases 

warm weather heat utilization 

•	 Demonstrate market viability and expedite commercial application of large PEM fuel cell power plants 

in the distributed generator (DG) market 

•	 Validate grid interconnectivity compliance with UL1471 and IEEE1547 at utility sites throughout 

the U.S. 

•	 Demonstrate high power plant availability in utility generation service 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year RD&D Plan: 

Distributed Generation Systems 

•	 E. Durability 

•	 F. Heat Utilization 

•	 G. Power Electronics 

Fuel-Flexible Fuel Processors 

•	 J. Durability 

Components 

•	 P. Durability 

•	 R. Thermal and Water Management 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Approach 

UTC Fuel Cells (UTCFC) is in the process of 

developing a 150-kW PEM power plant whose 

planned specifications will meet the DOE targets for 

fuel cells. 

As part of this project, the prototype power plant 

operated in Task 1 is dedicated to verifying the 

specification and capability to operate in climate 

extremes. In Task 2, the plan is to field three 

evaluation power plants that demonstrate power plant 

reliability. Cell stack and fuel processor catalyst 

durability testing and accelerated stress testing of 

mechanical components in Task 2 will complement 

the power plant data. Field evaluation power plants 

will provide an experience base in order to 

demonstrate high reliability. Task 3 addresses 

concern with heat utilization in commercial 

buildings. Integration between the power plant and 

liquid desiccant dehumidification will be evaluated 

by the United Technologies Research Center. Liquid 

desiccant dehumidification appears to be a good use 

of power plant heat to address 30 to 50 percent of the 

air conditioning load. Task 4 seeks to verify that a 

power plant certified for interconnection to UL1741 

can be installed with minimum cost or delay and 

provides data measured by a distribution utility 

(Connecticut Light and Power) on interconnection 

effects of multiple power plants on a single 

distribution feeder. The Electric Power Research 

Institute will conduct analysis to extend these results 

to the U.S. as a whole. 

The team assembled to verify the 150-kW PEM 

fuel cell power plant includes UTCFC, Hydrogen 

Source (HYS), United Technologies Research Center 

(UTRC), Connecticut Light and Power (CL&P) and 

the Electric Power Research Institute (EPRI). 

As part of the regional demonstration portion of 

this project, UTCFC will use four 150-kW PEM 

natural gas fueled power plants to demonstrate grid 

connectivity, high power plant availability, low 

emissions and high efficiency to utilities, owners/ 

operators and the investment community. 

 FY 2003 Progress Report 

A Team of UTCFC, New York Power Authority, 

Austin Energy, San Francisco Public Utilities 

Commission/Hetch Hetchy Water and Light, and 

EPRI has been formed to provide expertise in the 

area of grid interconnectivity. 

Use of the 150-kW PEM power plant will assess 

the readiness of the technology for these initial field 

demonstrations. The team has defined the work of 

the project to broadly address grid interconnectivity 

issues. The issues include 1) participation in 

developing and reviewing interconnectivity 

standards, e.g., UL1471 and IEEE1547 and 

individual State standards and regulations for grid 

interconnection; 2) selecting utility test sites in load 

intensive areas with a diversity of grid 

characteristics, e.g., generating mix, load 

composition, equipment and generator age, and 

geographical, regional and climatic variation; 3) 

confirming applicability of standards to all sites and 

situations and establishing appropriate field test 

protocols for confirmation; and 4) resolving specific 

technical issues, e.g., islanding, fault clearing 

capability, personnel safety considerations, reactive 

power support, and power quality including flicker, 

voltage sag and harmonics. 

The regional demonstration project technical work 

is conducted in three tasks. In Task 1, the Team will 

select a diversity of sites throughout the U.S. for 

installation and testing of power plants. UTCFC will 

fabricate, acceptance test and deliver power plants to 

the sites for installation. The host utility will install 

the power plant. In Task 2, host utilities will perform 

tests to determine power plant availability, emissions, 

efficiency and grid connectivity characteristics. 

UTCFC will provide field support to demonstrate a 

power plant availability of more than 95%. UTCFC 

also will evaluate two alternative strategies for cost 

effectively achieving availabilities of more than 95% 

in commercial service. In Task 3, EPRI and UTCFC 

will establish protocols for grid connectivity testing. 

EPRI and UTCFC will analyze the grid connectivity 

data collected by host utilities and the remote data 

center to validate the use of standards UL1471 and 

IEEE1547 for grid connectivity certification and grid 

connection. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Backup/Peak Shaving Fuel Cell Systems - Design and Development of the 

GenCoreTM II (New FY 2004 Project) 

John Vogel 

Plug Power Inc 

968 Albany-Shaker Road 

Latham, NY 12110 

Phone: (518) 782-7700 ext. 1937; Fax: (518) 786-1494; E-mail: john_vogel@plugpower.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

Objectives 

•	 Develop a cost-reduced, polymer electrolyte membrane (PEM) fuel cell stack tailored to hydrogen fuel 

use 

•	 Develop an advanced electrical energy storage system 

•	 Develop a modular, scalable power conditioning system tailored to market requirements 

•	 Design a scaled-down, cost-reduced balance of plant (BOP) 

•	 Certify design to Network Equipment Building Standards (NEBS), Underwriters Laboratories (UL) 

and European Conformity (CE) requirements 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Durability 

•	 G. Power Electronics 

• H. Start Up Time 	 

Approach 

Plug Power Inc. is conducting a 30-month 

project to advance the state-of-the-art of fuel cell 

technology with the development of a new 

generation of commercially viable, stationary, backup/peak-shaving fuel cell systems. 

The GenCoreTM II (GCII) backup fuel cell 

system, to be designed, developed and tested by Plug 

Power in this project, will be the first massmanufacturable implementation of Plug Power’s 

GenCore (GC) platform targeted for battery and 

small generator replacement applications in the 

telecommunications, broadband and uninterruptible 

power supply markets. The GCII will be a 

standalone, H2-in-DC-out battery and small 

generator replacement system. 

In designing the GCII specifically for the 

telecommunications market, Plug Power’s efforts 

will be greatly enhanced by our teaming arrangement 

with BellSouth Telecommunications, Inc., a leading 

industry end user. 

The final GCII system, to be fielded in 2005, will 

represent a market-entry, mass-manufacturable and 

economically viable design. Phase I of the project 

employs Plug Power’s Technology Delivery Process 

to develop the technology initiatives of the design. 

This structured process uses rigorous testing and 

evaluation methods in order to minimize the risks 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

inherent in bringing new technologies into 

commercial designs. The technology development 

effort for the GCII has two major tasks that 

essentially run in parallel: system technology 

development and module technology initiatives. As 

module technology innovations are completed, they 

will be integrated and verified in the system. Phase 

II uses Plug Power’s New Product Delivery process 

to introduce the technology initiatives as hardware 

modules for integration. Phase III also employs the 

New Product Delivery Process to bring the hardware 

from a set of technology modules to an integrated 

system through field-testing and certification. Phase 

III culminates in the system demonstration at DOE. 

The project will follow the schedule below: 

 FY 2003 Progress Report 

•	 Q3, 2003 – Q4, 2004: Collect field data for 

GenCore II development on certification testing 

and field deployment of prototypes 

•	 Q2, 2004 – Q1, 2005: Design and develop 

GenCore II 

•	 Q4, 2004: Build confirmation and life test 

systems 

•	 Q2, 2005 – Q1, 2006: Conduct field testing with 

BellSouth and NEBS, UL and CE testing 

•	 Q4, 2005 – Q1, 2006: Demonstrate GenCore II at 

DOE’s Argonne National Laboratory 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Economic Analysis of PEMFC Systems (New FY 2004 Project) 

Harry J. Stone 

Battelle 

655 Eden Park Dr., Suite 540 

Cincinnati, OH 45202 

Phone: (513) 362-2602; Fax: (513) 362-2610; E-mail: stoneh@battelle.org 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

Objectives 

•	 Task 1: Perform a study focusing on fuel cell technology, market, economic, and environmental 

analyses. The objective will be to develop a complete understanding of fuel cell technology, potential 

fuel cell capacity, the energy market, market size and potential in a wide range of possible stationary 

building applications, supply curves for promising fuel cell markets, and government policies and 

impacts. This knowledge will enable analyses of the economics and national impacts of the 

technology. 

•	 Task 2: Employ the Interactive Future Simulations (IFSTM) software to generate alternative scenarios 

to determine the commercial viability of fuel cells by the year 2020. (IFSTM software is commercial 

computer software owned by Battelle.) The future economic viability and impacts of fuel cells in the 

U.S. are highly uncertain and based on widely diverging market conditions. Anticipating these 

diverging market conditions is indispensable for understanding and influencing the actions required to 

encourage the successful commercialization of fuel cells. 

•	 Task 3: Develop a stakeholder’s forum for: 

- Focused investigations of critical issues and identification of foremost industry, government, and 

other consumer needs; 

- Identification of critical success factors and principal barriers; 

- Development of strategies and partnerships for addressing barriers; 

- Development of training modules and communications tools. 

•	 Task 4: Establish the PEM Fuel Cell Center (One-Stop Information Center for PEM Fuel Cells 

website). There is a considerable amount of research being conducted by federal laboratories and the 

private sector, as well as a number of university research centers. Presently, there is no single 

repository for proton exchange membrane (PEM) fuel cell information. The information center will 

inventory or link to information and educational resources that presently exist, while augmenting the 

information with the results from other work completed as part of this project. The Center’s website 

will have several access areas that will be tailored to meet the information demands of distinct 

stakeholder groups. Public policy will impact both time-to-market and the speed of market penetration 

of PEM fuel cells. Battelle will provide expertise to support policy development and analysis. This 

will include, as demanded by policy-makers, forums and seminars on targeted aspects of the PEM fuel 

cell policy environment. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

 Fuel Cells 

•	 D. Fuel Cell Power System Benchmarking 

Education 

•	 B. Lack of Demonstrations or Examples of Real World Use 

•	 C. Institutional Barriers and Access to Audiences 

•	 D. Regional Differences 

Approach 

Battelle will complete a comprehensive four-task 

action plan/process that includes technologyeconomic, contingent valuation, and forecasting 

assessments to identify critical success factors in the 

commercialization of fuel cells. Battelle will also 

initiate a formal stakeholder involvement process to 

govern our assessments and to share information 

critical to promoting user acceptance of this 

technology. 

In Task 1, Battelle will evaluate the economic 

variability of stationary PEM fuel cells of different 

sizes (1, 5, 25, 100, and 250 kW), operated as standalone, distributed generators (DGs) and as combined 

heat and power (CHP) systems. Battelle will solicit 

extensive stakeholder involvement, specifically from 

industry, academia, and research institutes, to gather 

accurate information on systems, technology 

performance, developmental status, applications, and 

economics. 

In Task 2, since the future of PEM fuel cells is 

highly uncertain, Battelle will use a proven, 

computer-based method to generate alternative 

futures or scenarios. In each scenario, we will 

identify defined alternative outcomes, such as rapid 

market penetration of PEM fuel cells in the 

application of stationary power. Each scenario will 

be different, which will allow us to see the total sets 

of conditions associated with the rapid market 

penetration. Battelle will identify the most important 

trends, issues, and factors to be included in the 

scenarios. 

In Task 3, a stakeholder group will be formed 

that represents a balance among interests in the fuel 

cell industry, academia, government, non-profit 

organizations, consumers, and, as they are identified, 

target markets such as electric power generators. 

Battelle will solicit and carefully manage the 

involvement of technology developers or vendors to 

provide an unbiased opinion of technology 

commercialization options. Developers and vendors 

may act as members of the stakeholder group to the 

extent that they represent the general technology 

area, or an association of developers or users. The 

collaboration among stakeholder group members 

also will enrich the development of effective 

communications tools for educating the broader 

stakeholder community. 

In Task 4, Battelle will focus on three key 

objectives in facilitating the commercialization of 

PEM fuel cells: 

•	 Improving understanding of the technology in 

target markets. Providing information and tools 

to target markets will enable informed decisions 

about the uses and applications of PEM fuel 

cells. 

•	 Enhancing the technology’s competitiveness. 

PEM fuel cells will compete with other energy 

technologies on a mix of attributes that will 

include the pure economics of cents/kW. 

Battelle will provide information to the PEM fuel 

cell industry to enhance understanding of other 

factors important to develop for and convey to 

promising target markets. 

•	 Collecting data on emerging technologies. 

Battelle will actively search for technologies that 

could reduce the cost of fuel cells, thereby 

improving their competitiveness in the 

marketplace. These innovations will be 

communicated to the PEM fuel cell industry. 

2
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Water-Gas Shift Catalysis 

Sara Yu Choung (Primary Contact), John Krebs, Magali Ferrandon, Razima Souleimanova, Deborah 

Myers, Theodore Krause 

Argonne National Laboratory 

9700 South Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-3420; Fax: (630) 972-4454; E-mail: choung@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-1637; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop water-gas shift (WGS) catalysts for on-board fuel processing that meet the DOE targets for 

performance [gas-hourly space velocity (GHSV) $30,000 h-1, CO conversion $90%, CO selectivity 

$99%], durability [lifetime >5000 h], and cost [<$1/kWe]. Eliminate the drawbacks of commercial WGS 

catalysts, CuZn and FeCr oxides, for on-board fuel processing, including the need for well-controlled in 

situ activation, the loss of activity due to temperature excursions, and the need to sequester the catalysts 

during shutdown to prevent deactivation. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 J. Durability 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

• N. Cost 	 

Approach 

•	 Explore metal/metal oxide combinations that exhibit the bifunctional mechanism where the metal 

adsorbs CO, CO is oxidized by the metal oxide, and the metal oxide is then reoxidized by water. 

•	 Metals (e.g. Pt, Ru, Co, Cu) that have CO adsorption energies of 20-50 kcal/mol 

•	 Metal oxides that exhibit redox activity under WGS reaction conditions 

Accomplishments 

Pt Catalysts 

•	 Improved the activity and stability of Pt/doped ceria catalyst with a bimetallic formulation. 

•	 Identified Zr and Gd as dopants for ceria that can improve WGS activity at temperatures >300°C 

compared to undoped Pt/ceria. 

•	 Demonstrated that 5 ppm H2S does not enhance deactivation of Pt/doped ceria catalyst at 300°C but 

does promote deactivation at 400°C. 

Cu Catalysts 

•	 Investigated Re, Ni-Re, and Mn as promoters to enhance the activity of Cu catalysts. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

Pt Catalysts 

•	 Optimize bimetallic formulation to increase activity while decreasing Pt loading to achieve DOE cost 

target. 

•	 Retard Pt sintering. 

• Address H 	 2S poisoning at 400°C. 

•	 Evaluate catalyst performance on monolith. 

Cu Catalysts 

•	 Increase low temperature (230-300°C) activity. 

•	 Reduce Cu sintering through the addition of promoters to improve stability. 

•	 Improve sulfur tolerance. 

•	 Conduct characterization studies (SEM/TEM 

and EXAFS/XANES) to improve activity 

and reduce deactivation. 

Introduction 

On-board reforming of hydrocarbon fuels for H2 

generation for fuel cell-powered vehicles produces 

reformate containing #10% CO. The CO content in 

reformate must be reduced to <100 ppm because it 

poisons the polymer electrolyte fuel cell (PEFC). The 

water-gas shift (WGS) reaction (CO + H2O = CO2 + 

H2) converts CO to CO2. Commercial WGS catalysts, 

CuZn and FeCr oxides, have a number of drawbacks, 

including the need for a well-controlled in situ 

activation process, the loss of activity due to 

temperature excursions, and the need to sequester the 

catalysts during shutdown to prevent reoxidation. All 

of these factors make the commercial WGS catalysts 

undesirable for use in on-board fuel processing. The 

goal of this project is to develop new WGS catalysts 

that overcome these drawbacks and meet the DOE 

performance, durability, and cost targets. 

Approach 

Metal/metal oxide combinations that exhibit 

bifunctional mechanisms are being explored where 

the metal active sites adsorb CO and the oxide 

support provides the oxygen for CO oxidation and is 

reoxidized by water. Pt and Cu are being studied 

because their CO adsorption energies are 20–50 kcal/ 

mol, which is considered to be optimal for WGS 

catalysts [1]. Gadolinia and zirconia doped ceria are 

being investigated as supports because they exhibit 

redox chemistry under WGS reaction conditions. 

Kinetic studies on Pt/ceria catalysts have shown that 

the rate is zero order in CO and one-half order in 

H2O (i.e., the CO conversion rate is proportional to 

PCO 

0 PH2O 0.5) [2,3], suggesting that the Pt surface is 

saturated with CO and the reaction is controlled by 

the reoxidation rate of ceria by water, the oxygen 

transfer rate from the ceria to the metal interface, or 

the metal dispersion and surface area. Our approach 

is to improve ceria redox/oxygen transfer rates by 

cation doping, improve water dissociation on the Pt 

surface by addition of a second metal, and stabilize 

Pt against sintering. 

WGS rates were measured in a microreactor 

using synthetic reformate (6.9% CO, 10.4% CO2, 

31.1% H2, 31.0% H2O, and 20.7% N2) on powder 

samples at a catalyst temperature of 250–400°C. 

High space velocities were used (GHSV=200,000– 

1,500,000 h-1) to maintain differential reactor 

conditions (i.e., conversion #15%) at the lower 

temperatures (250–300°C). 

Results 

The effect of Pt loading on WGS activity was 

investigated. The WGS activity (per gram catalyst) 

increased with Pt loading (0.87–2.86%) while the CO 

conversion rates (per mole Pt) were nearly identical 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 Effect of Pt Weight Loading on WGS 

Activity (per mole of Pt) of Pt Supported on 

Doped Ceria 

Figure 2. Water-Gas Shift Activity of Pt and Pt+M 

Supported on Doped Ceria 

(Figure 1), indicating that WGS rates (per mole Pt) 

are independent of Pt loading. Therefore, the CO 

conversion per unit volume of reactor can be 

increased by increasing the Pt loading to achieve the 

volume/weight targets. 

Pt bimetallic formulations were investigated in 

an attempt to reduce the amount of Pt while 

enhancing its activity. Bimetallic formulations were 

selected on the basis of theoretical studies of the 

energetics of H2O dissociation and reactions between 

COads + OHads on Pt-mixed metal clusters [4]. The 

WGS activities (per mole Pt) of different Pt 

bimetallic formulations (Pt+M) are compared to Pt in 

Figure 2. Pt+A and Pt+B showed higher rates than 

Pt, indicating that the addition of A and B is 

favorable for promoting the WGS reaction. On the 

other hand, the addition of C and D seemed to have 

inhibiting effects on WGS because lower rates were 

observed on Pt+C and Pt+D than with Pt. The 

activities of Pt+A and Pt+B are compared to Pt at 

300°C with time on stream in Figure 3. Pt lost half of 

its activity after ~40 hours and Pt+B deactivated 

more rapidly than Pt and lost half of its activity after 

~2 hours. Pt+A was more stable than Pt and had a 

half life of ~217 hours. Wang et al. reported that 

deactivation observed during WGS on Pt/ceria and 

Pd/ceria catalysts is caused by metal surface area loss 

[5]. The Pt+A bimetallic formulation may inhibit the 

sintering of Pt, resulting in enhanced stability. 

Co, Sn, Ni, Re, and Mn promoters were added to 

Cu-based WGS catalysts to try to improve the air 

stability. The activity decreased when Co and Sn 

were added, and these were subsequently dismissed 

as potential promoters. Rhenium was selected 

because it improved the air stability of Co-based 

WGS catalysts. Rhenium and copper do not form a 

solid solution or alloy of definitive stoichiometry. 

Nickel forms a solid solution with both Cu and Re 

and was used to increase their interaction. The CuRe catalyst is significantly more active than the CuNi-Re catalyst (Figure 4). The selectivity to H2 is 

considerably reduced with the presence of Ni 

because nickel is a very efficient methanation 

catalyst, particularly under WGS conditions. As 

shown in Figure 4, the Cu-Mn catalyst showed 

higher activity than the Cu catalyst at temperatures 

>275°C. However, the air stability of the Cu-Mn 

catalyst was poor; 10–20% of the initial activity was 

lost after a single exposure to dry air at 400°C. The 

promoted samples were more active than Cu at the 

higher temperatures (>375°C) after exposure to air. 

Preliminary powder x-ray diffraction studies were 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Water-Gas Shift Activity of Pt and Pt+M 

Supported on Doped Ceria 

Figure 4. Effect of Promoters on WGS Activity of Cu/ 

γ-Al2O3 

inconclusive regarding the extent of interaction of the 

promoters (Re, Mn) with Cu in these catalysts. 

Manganese is expected to form a spinel phase with 

Cu, based on available CuO-Mn2O3 phase diagrams. 

Conclusions 

•	 WGS activity (per gram catalyst) increased with 

Pt loading while CO conversion rates (per mole 

Pt) were similar, indicating that rates (per mole 

Pt) are independent of Pt loading (0.87–2.86 

wt%). 

•	 Activity and stability of Pt/doped ceria catalysts 

increased with bimetallic formulations. 

•	 Ni, Re, and Mn promoters enhanced WGS activity of Cu/γ-Al2O3, but promoted samples were 

less stable after air exposure. 

References 

1. D. C. Grenoble, M. M. Estadt, D. F. Ollis, J. 

Catal. 1981, 67, 90. 

2. T. Bunluesin, R. J. Gorte, G. W. Graham, Appl. 

Catal. 1998, 15, 107. 

3. S. Hilaire, X. Wang, T. Luo, R. J. Gorte, J. 

Wagner, Appl. Catal. A 2001, 215, 271. 

4. Y. Ishikawa, M.-S. Liao, C. R. Cabrera, Surf. Sci. 

2002, 513, 98. 

5. X. Wang, R. J. Gorte, J. P. Wagner,	 J. Catal. 

2002, 212, 225. 

FY 2002 Publications/Presentations 

1. S. Y. Choung, M. Ferrandon, and T. Krause, 

“Water-Gas Shift Catalysis on Pt Bimetallic 

Catalysts,” To be presented at the 226th American 

Chemical Society National Meeting, New York, 

NY, September 7-11, 2003. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Catalysts for Autothermal Reforming 

Jennifer Mawdsley (Primary Contact), Magali Ferrandon, Cécile Rossignol, James Ralph, Laura 

Miller, John Kopasz, and Theodore Krause 

Argonne National Laboratory 

9700 South Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-4608; Fax: (630) 972-4452; E-mail: mawdsley@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Develop advanced autothermal reforming (ATR) catalysts that meet DOE targets for fuel-flexible fuel 

processors, i.e., fuel efficiency $99.9%, H2 selectivity $80%, gas-hourly space velocity (GHSV) 

$200,000 h-1, durability $5000 h, and cost #$5/kWe. 

•	 Develop a better understanding of reaction mechanisms to increase catalytic activity, reduce
 

deactivation, and improve sulfur tolerance.
 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cell section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-up/Transient Operation 

•	 J. Durability 

•	 K. Emissions and Environmental Issues 

• N. Cost 	 

Approach 

•	 Building on past experience, we are investigating two classes of materials, transition metals supported 

on mixed-oxide substrates and perovskites containing no precious metals. 

•	 Determine catalyst performance (i.e., yields of H2, CO, CO2, and CH4) as a function of catalyst 

formulation, fuel composition (including sulfur content), and operating parameters (e.g., O2:C and 

H2O:C ratios, temperature, and GHSV). 

•	 Conduct catalyst characterization and mechanistic studies to gain insight into reaction pathways. 

•	 Work with catalyst manufacturers to optimize catalyst structure and performance. 

Accomplishments 

For transition metals on mixed oxide supports 

•	 Optimized catalyst formulation to improve performance of monoliths. 

•	 Demonstrated 54.6 vol% H2 (dry, N2-free) from sulfur-free (<450 ppb S) gasoline at GHSV of 110,000 

h-1 with Rh catalyst on a monolith. 

•	 Identified Pt sintering as a major cause for catalyst deactivation. 

•	 Identified oxide formulation that does not lose surface area during reforming. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

For the Ni-based perovskites 

•	 Identified La0.8Sr0.2Cr0.9Ni0.1O3 as a composition with improved structural stability compared to 

LaNiO3 under ATR conditions. 

•	 Demonstrated <50% loss in activity with benchmark fuel with 50 ppm S. 

Future Directions 

•	 Evaluate catalyst performance on a larger scale using 1-5 kWe adiabatic reactors to confirm 

microreactor results, better evaluate long-term and startup performance, and determine optimal 

geometry for structured support. 

•	 Work to decrease precious metal loading while improving catalyst stability and sulfur tolerance. 

•	 Work to improve catalyst activity and sulfur tolerance of perovskite catalysts. 

•	 Address the effect of rapid startup on catalyst stability. 

•	 Increase our fundamental understanding of reaction processes and mechanisms for deactivation and 

sulfur poisoning. 

Introduction 

Catalytic autothermal reforming (ATR) of 

hydrocarbon fuels to generate H2 has been widely 

accepted as the most promising route to meet the 

efficiency, weight and volume, durability, and cost 

goals for on-board fuel processors for automotive 

fuel cell systems. Argonne National Laboratory is 

developing new reforming catalysts tailored to meet 

the unique operating requirements for reforming 

complex fuel mixtures, such as gasoline. Two 

different classes of materials are being examined: 

Group VIII transition metals (e.g., platinum, 

rhodium, or nickel) supported on an oxide ionconducting substrate (e.g., gadolinium-doped ceria 

(CGO)), and mixed non-noble metal oxides with the 

ABO3 stoichiometry and the perovskite structure. 

The transition metal-based catalysts have 

demonstrated near-equilibrium yields of H2 from a 

number of fuels, including gasoline, diesel, and 

natural gas, exhibiting high catalytic activity and 

resistance to coking. Süd-Chemie, Inc., of 

Louisville, Kentucky, currently produces this catalyst 

under a licensing agreement. 

Approach 

Catalyst samples as powders and coated on 

monoliths are evaluated for H2 yield, fuel 

conversion, and resistance to coking and sulfur 

poisoning as a function of operating parameters (such 

as the type of fuel, its sulfur content, O2:C and 

H2O:C ratios, and reaction temperature) in a 

microreactor system. Fuels tested include sulfur free 

(<450 ppb S) and low sulfur (~30 ppm S) gasolines, 

isooctane (2,2,4-trimethylpentane), and a benchmark 

fuel mixture1 . Catalyst characterization techniques 

such as extended X-ray absorption fine structure 

spectroscopy (EXAFS) are used to understand 

changes in catalyst morphology during ATR and to 

help improve catalyst performance and stability. 

Results 

Transition Metals Supported on an Oxide-Ion 

Conducting Substrate. Monoliths coated with Rhcontaining catalysts, Rh-CGO or Rh-Pt-CGO, 

produced reformates from sulfur-free gasoline with a 

higher H2 yield, 8.7 and 9.3 moles of H2 per mole of 

gasoline, respectively, than the monolith coated with a 

catalyst containing only Pt (2.5 moles of H2 per mole 

of gasoline) as shown in Figure 1. The methane yield 

was 0.4 moles of CH4 per mole of gasoline for both 

Rh-CGO and Rh-Pt-CGO. Non-methane 

hydrocarbons included C2-C6 paraffins and the 

aromatics benzene, toluene, and xylenes. For RhCGO, the H2 yield increased to 9.3 moles of H2 per 

mole of fuel when the reaction temperature was 

increased from 700 to 750o

C. For Pt-CGO, the H2 

yield increased from 2.5 to 8.4 moles of H2 per mole 

of gasoline as the reaction temperature was increased 

from 700 to 800oC. For ATR, the steam reforming 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

component of the reaction produces the H2, and the 

higher H2 yields observed with the Rh-containing 

catalysts are consistent with various studies which 

have shown that Rh is the most active Group VIII 

transition metal for steam reforming.2 As the GHSV 

was increased from 27,500 to 110,000 h-1, the H2 

yield decreased slightly from 8.7 to 8.4 moles of H2 

per mole of gasoline for Rh-CGO as shown in Figure 

2. On a concentration basis, the H2 concentration 

decreased from 55.4 to 54.6 vol% (dry, N2-free) as the 

GHSV was increased from 27,500 to 110,000 h-1 . 

Tests are in progress to determine if modifying the 

structured support can reduce hydrocarbon 

breakthrough. 

Figure 1.	 Comparison of the H2, CO, CO2, and CH4 

Yields Produced from <450 ppb S Gasoline 

Catalyzed by Rh-, Rh-Pt, or Pt-CGO at 

700o

C 

 FY 2003 Progress Report 

Previous studies have shown that Pt-CGO is 

more sulfur tolerant than Rh-CGO.1 The sulfur 

tolerance of Rh-Pt-CGO was evaluated by reforming 

two gasolines, one which contained <450 ppb S and 

the other which contained 30 ppm S. As shown in 

Figure 3, the H2 concentration decreased from 58.2 

to 54.8 vol%, representing a 6% decrease, during the 

first 48 h with sulfur-free gasoline. The fuel was 

then switched to the 30 ppm S gasoline. The H2 

concentration decreased further to 49.8 vol%, which 

represents a 10% decrease, over the next 48 h, 

indicating that sulfur in the fuel was poisoning the 

catalyst. EXAFS analyses showed that Pt is highly 

dispersed on Pt-CGO before ATR but undergoes 

sintering during ATR. Sulfur in the fuel appears to 

enhance the sintering of Pt. Similar studies are in 

progress for the Rh and Rh-Pt. 

Mixed Metal Oxides with the Perovskite Structure. We have previously reported that for the 

lanthana-based pervoskites containing first-row 

transition metals (i.e., LaCrO3, LaMnO3, LaFeO3, 

LaCoO3, and LaNiO3), the highest H2 yields are 

observed with the least stable complexes, LaCoO3 

and LaNiO3, which decompose into La2O3 and 

metallic Co and Ni, respectively, under ATR 

conditions.3 The stability of LaNiO3 under ATR was 

increased by replacing some of the Ni with Cr, 

termed “B-site” doping. This resulted in a slight 

decrease in the H2 yield, which could be recovered 

Figure 2.	 Effect of GHSV on H2, CO, CO2, and CH4 

Yields Produced from <450 ppb S Gasoline 

Catalyzed by Rh-CGO at 700oC 

Figure 3.	 Comparison of vol% of H2, CO, CO2, CH4, 

and Total Hydrocarbons (HCs) in Reformate 

Produced from <450 ppb S and 30 ppm S 

Gasolines Catalyzed by Rh-Pt-CGO/ 

Monolith 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

by replacing some of the La with Sr, termed “A-site” 

doping. La0.8Sr0.2Cr0.9Ni0.1O3 was identified as the 

optimal composition. 

The sulfur tolerance of La0.8Sr0.2Cr0.9Ni0.1O3 

was evaluated by comparing the H2 yield from 

reforming benchmark fuel containing two different S 

contents, 5 and 50 ppm, added as benzothiophene. 

La0.8Sr0.2Cr0.9Ni0.1O3 is susceptible to sulfur 

poisoning with the decrease in the H2 yield being 

greater and more rapid at the higher sulfur content. 

Attempts to improve the sulfur tolerance by replacing 

Cr with metals such as Mn or Fe were not successful, 

as shown in Figure 4. 

Conclusions 

Transition Metal(s) Supported on an Oxide-Ion 

Conducting Substrate 

•	 Showed that formulations containing Rh are the 

best-performing ATR catalysts. 

•	 Demonstratedthat Rh-CGO on a monolith can 

produce a reformate containing 54.6 vol% H2 

(dry, N2-free) from a <450 ppb S gasoline at a 

GHSV of 110,000 h-1 . 

•	 Using EXAFS, showed that Pt sinters under ATR 

conditions and that S may enhance sintering. 

Figure 4.	 Comparison of the Effect of 5 and 50 ppm S 

on H2 Yield Produced from Benchmark Fuel 

Catalyzed by La0.8Sr0.2Cr0.9Ni0.1O3, La0.8Sr0.2Mn0.9Ni0.1O3, and 

La0.8Sr0.2Fe0.9Ni0.1O3 

 FY 2003 Progress Report 

Mixed Metal Oxides with the Perovskite Structure 

•	 Identified La0.8Sr0.2Cr0.9Ni0.1O3 as a composition with improved structural stability compared 

to LaNiO3 under ATR conditions. 

•	 Determined that deactivation due to sulfur poisoning depends on the sulfur content in the fuel; 

however, complete loss of activity was not 

observed. 

References 

1. J. P. Kopasz, D. Applegate, X. Wang, L. Miller, S. 

Ahmed and M. Krumpelt, "Effects of Fuels and 

Contaminants on Performance of Reforming 

Catalysts," 2001 Annual Progress Report, Fuels 

for Advanced CIDI Engines and Fuel Cells, U.S. 

Department of Energy, Office of Transportation 

Technologies, Washington, D.C. 

2. D. L. Trimm, Z. I. Onsan, Catal. Rev. Sci. Eng. 

2001, 43(1-2), 31. 

3. T. Krause, J. Mawdsley, C. Rossignol, J. Kopasz, 

D. Applegate, M. Ferrandon, J. D. Carter, and M. 

Krumpelt, "Catalytic Autothermal Reforming," 

FY2002 Progress Report for Hydrogen, Fuel 

Cells, and Infrastructure Technologies Program, 

U.S. Department of Energy, Office of Hydrogen, 

Fuel Cells, and Infrastructure Technologies, 

Washington, D.C. 

FY 2003 Publications/Presentations 

Publications 

1. M. Krumpelt, T. R. Krause, J. D. Carter, J. P. 

Kopasz, and S. Ahmed, "Fuel Processing for Fuel 

Cell Systems in Transportation and Portable 

Power Applications," Catalysis Today, 77, (1-2), 

3-16 (2002). 

2. M. G. Sobacchi, A. V. Saveliev, A. A. Fridman, L. 

A. Kennedy, S. Ahmed, and T. Krause, 

"Experimental Assessment Of A Combined 

Plasma/Catalytic System For Hydrogen Production 

Via Partial Oxidation Of Hydrocarbon Fuels," Int. 

J. Hydrogen Energy, 27, 635-642 (2002). 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Presentations 

1. Theodore Krause, Magali Ferrandon, Cécile 

Rossignol, "Reforming Catalysts For On-Board 

Fuel Processing," To be presented at the 226th 

American Chemical Society National Meeting, 

New York, NY, September 7-11, 2003. 

2. Theodore Krause, Cécile Rossignol, Magali 

Ferrandon, John Kopasz, Jennifer Mawdsley, 

Joong-Myeon Bae, "Transition Metals on Oxide 

Ion Conducting Supports as Reforming Catalysts 

for Fuel Cell Systems," Presented at the 18th 

Annual Meeting of the North American Catalysis 

Society, Cancun, Mexico, June 1-6, 2003. 

 FY 2003 Progress Report 

3. J. R. Mawdsley, T. R. Krause and J. P. Kopasz, 

"Perovskite Catalysts for Producing Hydrogen 

Using Gasoline Fuel," Presented at the 2003 

American Ceramic Society Annual Meeting, 

Nashville, TN, April 28-30, 2003. 

4. Theodore Krause, Cécile Rossignol, Magali 

Ferrandon, John Kopasz, and Joong-Mayeon 

Bae, "Pt And Rh Supported On Oxide-Ion 

Conducting Substrates As Catalysts For 

Generating H2 For Fuel Cells," Presented at the 

2003 Spring National Meeting of the American 

Institute of Chemical Engineers, New Orleans, 

LA, March 30-April 3, 2003. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of Novel Water-Gas-Shift Membrane Reactor 

W.S. Winston Ho 

Department of Chemical Engineering 

The Ohio State University 

140 West 19th Avenue 

Columbus, OH 43210-1180 

Phone: (614) 292-9970; Fax: (614) 292-3769; E-mail: ho@che.eng.ohio-state.edu 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

ANL Technical Advisor: Thomas G. Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: benjamin@cmt.anl.gov 

Objectives 

•	 Synthesize and characterize CO2-selective membranes for the novel water-gas-shift (WGS) membrane 

reactor. 

•	 Use the membrane data obtained in the mathematical model developed to show the feasibility of 

achieving H2 enhancement via CO2 removal and CO reduction to 10 ppm or lower and to elucidate the 

effects of system parameters on the reactor from the modeling study. 

•	 Develop the membrane reactor for achieving H2 enhancement and <10 ppm CO. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

Approach 

•	 Synthesize and characterize CO2-selective membranes containing amino groups. 

•	 Use the membrane data obtained in the modeling work to study membrane reactor performance and to 

guide/minimize experimental work. 

•	 Incorporate the membrane synthesized in the reactor to demonstrate H2 enhancement via CO2 removal 

and CO reduction to 10 ppm or lower. 

Accomplishments 

•	 Synthesized membranes with high CO2 permeabilities and high CO2/H2 and CO2/CO selectivities. 

•	 Elucidated the effects of system parameters including CO2/H2 selectivity on the membrane reactor for 

synthesis gases from autothermal reforming. 

•	 Showed the feasibility of achieving H2 enhancement via CO2 removal, CO reduction to #10 ppm, and 

high H2 recovery based on the modeling study using the membrane data obtained. 

•	 Obtained <10 ppm CO in the H2 product in initial WGS membrane reactor experiments using the 

synthesis gas feed with 1% CO. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Continue to synthesize and characterize improved membranes for the reactor. 

• Complete the proof-of-concept demonstration using the lab membrane reactor. 

• Conduct the prototype membrane reactor demonstration for a fuel cell. 

Introduction 

A water-gas-shift (WGS) reactor for the 

conversion of carbon monoxide (CO) and water to 

hydrogen (H2) and carbon dioxide (CO2) is widely 

used in chemical and petroleum industries. The 

reactor is also critically needed for the conversion of 

fuels, including gasoline, diesel, methanol, ethanol, 

natural gas, and coal, to H2 for fuel cells. Since the 

WGS reaction is reversible, it is not efficient, 

resulting in a high concentration of unconverted CO 

(~ 1%) in the H2 product and a bulky, heavy reactor. 

This reaction can be enhanced significantly through a 

CO2-selective membrane, which removes the 

reaction product, CO2, to beat the reaction 

equilibrium and shift the reaction towards the 

product side. The CO2-selective WGS membrane 

reactor has advantages including (1) a high-purity H2 

product is recovered at the high pressure (feed gas 

pressure) and (2) air can be used as the sweep gas to 

remove the permeate, CO2, on the low-pressure side 

of the membrane to have a high driving force for the 

separation. These advantages are especially 

important for fuel cell vehicles. The first advantage 

eliminates the need for an unwanted compressor. 

With the second advantage, the high driving force 

created by the air sweep can result in low CO 

concentration and high H2 purity and recovery. 

Approach 

We have synthesized novel CO2-selective 

membranes by incorporating amino groups in 

polymer networks. The membranes synthesized 

were characterized in a gas permeation unit to 

determine their CO2 permeabilities and CO2/H2 and 

CO2/CO selectivities. We have used the selectivity 

and flux data obtained as the input to the 

mathematical model developed [1] to show the 

feasibility of achieving H2 enhancement, CO 

reduction to #10 ppm, and high H2 recovery; to study 

the effects of system parameters on the reactor; and 

to guide/minimize experimental work. In the model, 

the low-temperature WGS reaction kinetics for the 

commercial catalyst (Cu/ZnO/Al2O3) reported by 

Moe [2] and others [3] was used. In addition, we 

have incorporated the membrane synthesized in the 

laboratory WGS membrane reactor to show CO 

reduction to 10 ppm or lower in the H2 product in 

initial reactor experiments using the synthesis gas 

feed with 1% CO. 

Results 

Synthesis and Characterization of Novel CO2-

Selective Membranes. Figure 1 shows the CO2 

permeability and CO2/H2 selectivity results as a 

function of temperature from 100o

C to 180oC for the 

feed gas pressure of 2.1 atm and the sweep gas (air or 

nitrogen) of atmospheric pressure. As shown in this 

figure, the CO2 permeability was about 4000 Barrers 

[1 Barrer = 10–10 cm3(STP)-cm/cm2-s-cmHg] or 

higher for the temperatures ranging from 100o

C to 

150oC. However, the permeability decreased to 

about 2000 Barrers as the temperature increased to 

180oC. This was due to the reduction of water 

retention in the membrane as the temperature 

Figure 1. CO2 Permeability and CO2/H2 Selectivity 

Results as a Function of Temperature 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

increased. Also shown in this figure, the CO2/H2 

selectivity was about 100 or higher for the 

temperatures ranging from 100o

C to 150oC. 

However, the selectivity decreased slightly as the 

temperature increased to 170oC. This was a result of 

the CO2 permeability decrease due to the reduction 

of water retention in the membrane as described 

above. At 180oC, the selectivity decreased 

significantly to slightly greater than 10 due to the 

significant swelling of this membrane at this high 

temperature. Nonetheless, the selectivity of 10 is still 

good enough to give a high H2 recovery of about 

90%, which will be described in the following 

modeling work. 

Figure 2 gives the CO2 permeability results as a 

function of feed pressure from about 2 atm to about 4 

atm at 150o

C. As shown in this figure, the 

permeability did not change significantly with the 

feed pressure. 

Figure 3 shows the CO2/CO selectivity results as 

a function of temperature from 100oC to 160oC for 

the feed gas pressure of 2.1 atm. The CO2/CO 

selectivity results were greater than 215, which is 

very good. However, the selectivity decreased as the 

temperature increased. This was a result of the CO2 

permeability decrease due to the reduction of water 

retention in the membrane as described above. 

Modeling of Membrane Reactor Using Membrane 

Data Obtained. The CO2/H2 selectivity of 40 and 

the CO2 permeability of 4000 Barrers were used in 

the modeling work. We have investigated the 

performance of the countercurrent membrane reactor 

for the synthesis gases from the autothermal 

reforming of gasoline with air. The three synthesis 

gases investigated at 3 atm contained CO at 

concentrations of 10%, 5%, and 1%. Figure 4 

illustrates the profiles of the CO concentration in the 

H2 product for a total reactor length of 61 cm for 

these three feed CO concentrations. As shown in this 

figure, a H2 product with less than 10 ppm CO was 

obtained from each of these synthesis gases. In the 

membrane reactor, for each of these synthesis gases, 

the syngas flow with an inlet temperature of 140oC 

was countercurrent to the flow of hot air sweep with 

an inlet temperature of 140oC, the molar flow rate 

ratio of the air sweep to the syngas (γ) was 1.5, and 

Figure 3. CO2/CO Selectivity Results as a Function of 

Temperature 

Figure 2. CO2 Permeability Results as a Function of 

Feed Pressure at 150o

C 

Figure 4.	 Profiles of Carbon Monoxide Mole Fractions 

in the Hydrogen Products along the 

Membrane Reactors for 10%, 5%, and 1% 

CO Feed Gases 

3 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

the catalyst was the commercial Cu/ZnO supported 

on alumina. 

For each of these synthesis gases, significant H2 

enhancement was achieved via CO2 removal. For 

example, the H2 concentration was increased from 

41% in the inlet 1% CO feed gas to 48.5% in the 

outlet H2 product on the wet basis (from 45.3% to 

53.6% on the dry basis). Similar significant H2 

enhancement was also achieved for the 5% and 10% 

CO feed gases. In addition, a high H2 recovery of 

greater than 97.4% was obtained for these synthesis 

gases, as indicated in Figure 4. 

We have also investigated the effects of CO2/H2 

selectivity on exit CO concentration and H2 recovery 

for these synthesis gases through the modeling. For 

the CO2/H2 selectivity ranging from 10 to 80, the exit 

CO concentration of less than 10 ppm was 

achievable. A lower selectivity actually resulted in a 

slightly lower exit CO concentration as a lower 

selectivity (higher H2 loss) enhanced the WGS 

reaction. However, the selectivity had a significant 

effect on H2 recovery as depicted in Figure 5 for the 

1% CO feed gas. A selectivity of 10 gave a H2 

recovery of about 90%, which is still quite good. As 

the selectivity increased, the H2 recovery increased 

significantly. At the selectivity of 40, the H2 

recovery was greater than 97.4%, as mentioned 

earlier. For the selectivity of 60 or greater, the H2 

recovery was greater than 98.3%. 

Figure 5. Effect of CO2/H2 Selectivity on H2 Recovery 

for 1% CO Feed Gas 

 FY 2003 Progress Report 

Initial Membrane Reactor Experiments. We 

began to incorporate the membrane synthesized in 

the laboratory WGS membrane reactor to conduct the 

proof-of-concept demonstration. In initial membrane 

reactor experiments, the commercial Cu/ZnO 

catalyst supported on alumina was placed on the top 

of the membrane, the operating temperature was 

150oC, and the synthesis gas (from autothermal 

reforming) containing 1% CO was used. The 

rationale for using this synthesis gas was that it could 

be readily made from the commercial WGS reactor. 

In the initial membrane reactor experiments, a CO 

concentration of 10 ppm or lower in the H2 product 

was obtained. This membrane reactor work is in 

progress. 

Conclusions 

We have synthesized membranes with high CO2 

permeabilities and high CO2/H2 and CO2/CO 

selectivities. The membranes showed a high CO2 

permeability of about 4000 Barrers, a high CO2/H2 

selectivity of greater than 40, and a high CO2/CO 

selectivity of greater than 215 at 100 – 150o

C. These 

membranes could be operated to about 180o

C. Based 

on the modeling study using the membrane data 

obtained, we showed the feasibility of achieving H2 

enhancement via CO2 removal, CO reduction to #10 

ppm, and high H2 recovery. In addition, we obtained 

<10 ppm CO in the H2 product in initial WGS 

membrane reactor experiments using the synthesis 

gas feed with 1% CO. 

References 

1. W. S. W. Ho, "Development of Novel Water-GasShift Membrane Reactor", Final Technical Report 

for the DOE Project Conducted at the University 

of Kentucky (September 2002). 

2. J. M. Moe, "Design of Water-Gas-Shift Reactors", 

Chem. Eng. Progr., 58, 33 (1962). 

3. R. L. Keiski, O. Desponds, Y. F. Chang, and G. A. 

Somorjai, "Kinetics of the Water-Gas-Shift 

Reaction over Several Alkane Activation and 

Water-Gas-Shift Catalysts", Applied Catalysis A: 

General, 101, 317-338 (1993). 

4 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Publications/Presentations 

1. W. S. W. Ho, "Engineering Membranes for 

Environmental and Energy Applications", 

Invited Talk at the University of Illinois, Urbana, 

IL, September 24, 2002. 

2. W. S. W. Ho, "Engineering Membranes for 

Environmental and Energy Applications", 

Invited Talk at Case Western Reserve University, 

Cleveland, OH, October 17, 2002. 

3. L. El-Azzami and W. S. W. Ho, "Modeling of 

CO2-Selective WGS Membrane Reactor for Fuel 

Cells", AIChE Annual Meeting, Indianapolis, 

IN, November 3 - 8, 2002. 

4. W. S. W. Ho and Y. H. Tee, "CO2-Selective 

Membranes Containing Mobile and Fixed 

Carriers", AIChE Annual Meeting, Indianapolis, 

IN, November 3 - 8, 2002. 

 FY 2003 Progress Report 

5. W. S. W. Ho, "Engineering Membranes for 

Environmental and Energy Applications", 

Invited Talk at University of California, 

Riverside, CA, December 6, 2002. 

6. W. S. W. Ho, "Development of Novel WaterGas-Shift Membrane Reactor", Presentation to 

FreedomCAR Fuel Cell Tech Team, USCAR, 

Detroit, MI, 3/19/03. 

Patent Pending 

1. W.S. Winston Ho, "CO2-Selective Membranes 

Containing Amino Groups", U. S. Patent 

Application Serial No. 10/145,297, filed on May 

14, 2002. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

On-Board Vehicle, Cost Effective Hydrogen Enhancement Technology for 

Transportation PEM Fuel Cells 

Zissis Dardas (Primary Contact), Thomas Vanderspurt, Ying She, Mallika Gummalla 

United Technologies Research Center (UTRC) 

East Hartford, CT, 06108 

Phone: (860) 610-7371; Fax: (860) 610-2453; E-mail: dardasz@utrc.utc.com 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: Donna.Ho@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: Benjamin@cmt.anl.gov 

Subcontractors: 

UTC Fuel Cells, South Windsor, Connecticut 

HydrogenSource, South Windsor, Connecticut 

Objectives 

Develop technology based on an integrated water gas shift (WGS) reactor/Pd membrane H2 separator for a 

fuel processor that is capable of producing on-board high purity hydrogen for 50 kWe gasoline-based 

proton exchange membrane (PEM) fuel cell transportation power plants. This fuel processor design 

should satisfy DOE’s 2005 technical targets for system efficiency, volume, weight, cost, life, start-up time, 

transient response time and emissions. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Startup/Transient Operation 

• N. Cost 	 

Approach 

•	 Develop a WGS/H2 separator reactor design integrated into a 50 KWe gasoline-based fuel processing 

system (FPS) and assess FPS and overall PEM fuel cell (FC) system performance using proprietary, 

physics-based, validated reactor mathematical models and system level mathematical models. 

•	 Perform trade studies between differential operating pressure, inlet temperature, number of tubes, tube 

diameter, length and Pd effective layer thickness for the Pd membrane modules to identify optimum 

reactor design and operating conditions for maximum H2 recovery efficiency and minimum reactor 

size/cost. 

•	 Use the models to analyze different reactor and system designs and integration schemes to identify 

best system efficiency and minimum size/cost. 

•	 Synthesize and assess performance (H2 permeance, selectivity) of advanced, thin, low cost, long-life, 

Pd-based, supported (on porous metal supports) membranes. 

•	 Test best Pd membranes under WGS conditions and assess their performance as a function of
 

operating time and number of start up/shut down events (future task).
 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Identified, through reactor models, optimum WGS reactor configuration and operating conditions. H2 

recovery efficiencies up to 96% demonstrated for a membrane reactor operating pressure not higher 

than 6 atm. Identified best FPS design and Pd membrane reactor integration scheme. 

•	 Demonstrated, through system level models, that a PEM FC power plant with a Pd membrane-based 

FPS could achieve ~6 points higher efficiency than the conventional system that does not employ a Pd 

membrane WGS reactor. 

•	 Demonstrated, through system level models, that the FC power plant is in water balance with a ~20% 

smaller size Energy Recovery Device (ERD) and ~10% smaller radiator and accumulator sizes relative 

to the baseline power plant. 

•	 Estimated an FPS volume of 1140 W/L, weight of 1100 W/kg, start-up time of <1 minute for 50% of 

full rated power, transient response time of ~5 seconds and cost of $16/kWe+0.4x (Cost of Baseline 

FPS). 

•	 Synthesized, by electroless plating and appropriate surface treatment conditions, a ~15 micron, 

“defect-free” Pd membrane over a porous metal support with H2 permeance of ~15 m3

/m2-hr-atm0.5 

and H2/N2 selectivity of 1,100 at 350oC. No membrane performance deterioration was observed in 

250 hours of testing and under 10 thermal cycles. Identified the critical characteristics of the porous 

metal supports for robust and thinner (< 5 microns) Pd membranes. 

Future Directions 

•	 Assess capability for Pd deposition on the internal tube surface by electroless plating. 

•	 Obtain porous metal supports with narrower pore size distribution and lower surface roughness on the 

surface where the Pd phase will be deposited. 

•	 Down select Pd membrane manufacturing process from the critical evaluation of two candidates 

(electroless plating and UTRC proprietary process). 

•	 Synthesize and characterize low thickness (<5 microns), “defect-free”, Pd-Ag alloy membranes with 

H2 permeance and selectivity targets of 30-45 m3

/m2-hr-atm0.5 and 2,000 at 350oC, respectively by 

optimizing porous metal supports. 

•	 Evaluate membrane performance (H2 permeance and selectivity) and percent H2 recovery under first 

stage WGS reformate test conditions. 

•	 Evaluate best membrane performance under an aggressive number of thermal cycling tests (~100 

cycles). 

•	 Develop mathematical models from lab-scale tests that predict performance of the reactor under 

specified life (4,000 hrs for automotive) and start up/shut down events (1,000 for automotive) targets. 

•	 Design, build and test an integrated WGS Pd membrane reactor hardware prototype. 

Results 

Figure 1 highlights the significant fuel 

processing system (FPS) simplification that can be 

achieved with an integrated WGS Pd membrane 

reactor by comparing this system (Figure 1b) to the 

conventional one (Figure 1a). Figure 2 (plots (A) 

through (C)) illustrates some of the trade studies 

performed to access the optimum WGS Pd 

membrane reactor operating conditions. H2 

concentration profiles were generated as a function 

of the reactor length in the high pressure tube side 

(where the WGS catalyst is located) and in the 

ambient pressure shell side (where the separated H2 

product and the steam sweep gas flows) to access the 

changes of the differential H2 partial pressure 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1A. Schematic of a Conventional Fuel Processing 

System 

(process driving force). It was determined that the 

amount of WGS catalyst does not account for more 

than one third of the required reactor volume, while 

the reactor volume and H2 separation efficiency 

depend on the differential operating pressure, 

membrane thickness, and number and length of 

membrane tubes. A multi-criteria type of 

optimization approach was applied to identify the 

Table 1. FPS System Characteristics 

Figure 1B. Schematic of a Pd Membrane-Based Fuel 

Processing System 

optimum FC system efficiency for a specified 

operating inlet pressure in the membrane reactor (6 

atm). For this system that employs a compressor/ 

expander in order to improve system mechanical 

efficiency and reduce parasitic power, it was found 

that with a 7 liter membrane reactor, ~31% FC 

system efficiency is possible with a ~67% FPS 

efficiency. The membrane reactor was operated at 

85% H2 recovery efficiency. The results of this 

simulation are summarized in Figure 3 and imply that 

a maximum FC power plant efficiency does not 

necessarily imply a maximum FPS efficiency. 

However, we recommend this design, since the 

overall FC system efficiency rather than the FPS 

efficiency should be maximized. The effective Pd 

thickness for the Pd membrane reactor that was used 

in this simulation was ~4 microns, resulting in a H2 

permeance of ~45 m3/m2-hr-atm0.5 at 350oC. 

Metric DOE Target Conventional 

System 

Pd Membrane 

System 

FPS Efficiency 78% 67% 67%* 

FPS Power Density (W/L) > 700 570 1140 

FPS Power Density (W/kg) > 700 550 1100 

FPS Cost ($/kWe) 25 C 0.4xC+16 

FPS Start Up Time (min) < 1 min for 33% Full 

Power (FP) 

~3 min for < 50% FP 

(non optimized) 

< 1 min for 50% FP 

FPS 10%-90% Transient Response Time > 5 sec N/A ~5 sec 

PEM FC System Efficiency N/A ~25% 30.80% 

* 77.7% FPS Efficiency can be achieved, but with lower overall PEM FC efficiency 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2.	 Impact of Operating and Physical Parameters 

on Performance of the WGS Pd Membrane 

Reactor 

The simulation results for system start-up, shown 

in Figure 4, illustrate a less than one minute start up 

time for the FPS for 50% of the full rated power and 

<5 sec transient response time. This achievement is 

significant and is due to the elimination of a large 

number of components from the FPS. In addition, 

the FPS provides the cells stack with ~100% purity 

H2 right from the start. The estimated FPS 

performance characteristics in comparison to DOE 

targets are shown in Table 1. As this table illustrates, 

Figure 3. Subsystem and Overall PEM FC System 

Efficiencies 

Figure 4.	 Model Simulation Shows that the Pd 

Membrane-Based FPS Achieves 50% Power 

within ~30 Seconds (CPOX = catalytic partial 

oxidation) 

the proposed system design promises excellent 

progress towards the desirable system targets. 

Conclusions 

•	 The FPS design incorporating an integrated 

WGS Pd membrane reactor satisfies DOE's 

efficiency, size, start up and transient response 

targets. Furthermore, the predicted FC power 

plant efficiency is ~6 points higher than the 

current system design. 

•	 This design will reduce balance-of-plant volume 

and cost (ERD, radiator, accumulator), while the 

significantly simplified system will be easier to 

control under transients. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Surface treatment approaches and required 

support characteristics have been identified that 

will yield high performance membranes. 

FY 2003 Publications/Presentations 

1. Mallika Gummalla, Benoît Olsommer, Nikunj 

Gupta, and Zissis Dardas. "Physics-Based 

Simulations of Water Gas Shift Membrane 

Reactor for Prediction Reactor Volume and 

Performance", Presentation, Abstract, and 

Presentation Record, American Institute of 

Chemical Engineers, 2003 Spring Meeting, Fuel 

Processing Session II, New Orleans, LA, March 

2003 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Plate-Based Fuel Processing System 

R. A. Dalla Betta (Primary Contact), J. Barnes, C. Faz, T. Ho, H. Liu, J. Nicole, V. Sokolovskii, D. Yee 

Catalytica Energy Systems 

430 Ferguson Drive 

Mountain View, CA 94043 

Phone: (650) 940-6310; Fax: (650) 965-4345; E-mail: rdallabetta@CatalyticaEnergy.com 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: Donna.Ho@ee.doe.gov 

Technical Advisor: Walt Podolski 

Phone: (630) 252-7558; Fax: (630) 972-4430; E-mail: podolski@cmt.anl.gov 

Objectives 

•	 Develop reactor designs and catalyst systems for the direct steam reforming of gasoline to a hydrogencontaining stream adequate for a proton exchange membrane (PEM) fuel cell. 

•	 Develop computer simulation models of these systems to predict and optimize performance. 

•	 Develop and test prototype reactors in a 1 to 10 kW(e) size range and demonstrate DOE target
 

performance, especially fast startup and load change.
 

•	 Demonstrate integrated fuel processor system operation. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Startup/Transient Operation 

•	 J. Durability 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 M. Fuel Processor System Integration 

• N. Cost 	 

Approach 

•	 Develop conceptual plate reactor designs for steam reforming, water gas shift and preferential CO 

oxidation. Assemble detailed computer simulation models for these designs. 

•	 Develop catalyst washcoat compositions with the required activity, selectivity and initial durability 

consistent with the catalyst performance requirements specified by the simulations. As required, 

measure detailed reaction kinetics for these catalyst compositions. 

•	 Design and fabricate prototype plate reactor mechanical designs in the 1 to 10 kW(e) size range. 

•	 Demonstrate plate reactor performance including startup, transient operation, efficiency and other 

performance factors. 

Accomplishments 

•	 Completed structural analysis of plate reactor system and established design criteria for required cyclic 

durability (startup and transient) and developed prototyping strategy for an initial laboratory 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

demonstration directed at transient and efficiency criteria. Proceeding with multiple parallel paths 

with future down-select to one or two final prototype units for demonstration. 

•	 Developed and demonstrated a steam reforming catalyst with the required performance using the 

Argonne National Laboratory (ANL) Benchmark Fuel I with 10 ppm sulfur. Global kinetics have been 

measured for use in the plate reactor simulation model. 

•	 Developed a base metal, non-pyrophoric water gas shift catalyst that is air stable and does not require 

pre-reduction. Demonstrated stability to 500 hours and activity meeting the DOE target performance. 

•	 Developed a preferential CO oxidation catalyst that can achieve the required reactor performance for a 

plate configuration operating at 150°C. Demonstrated stability to 800 hours. 

Future Directions 

•	 Using measured kinetics for the best catalysts, complete simulation modeling for the target steam 

reforming plate reactor system. Complete prototype plate reactor designs for this reactor and fabricate 

at least one and possibly two prototype designs at the 1 to 10 kW(e) size for demonstration testing. 

Modify test rig facilities to accommodate the prototype units to accomplish testing including startup 

and transient operation over the required load range. Demonstrate startup to full load in less then 60 

seconds and, if possible, less then 30 seconds, and demonstrate rapid transient load variation. 

•	 Develop computer simulation models of the water gas shift reactor and preferential CO oxidation 

reactor designs using measured kinetics and design results from reformer prototype tests. Develop 

prototype plate reactor designs for these processes and fabricate prototype hardware for demonstration 

testing. 

•	 Develop a transient simulation to demonstrate full fuel processor startup and transient operation 

consistent with DOE targets. 

Introduction 

The major obstacles to on-board reforming of 

liquid fuels to provide hydrogen for fuel cell 

applications are 1) time required for startup from a 

cold start; 2) ability to handle fast output transients; 

and 3) general complexity, size, weight and cost. 

These obstacles are being addressed in a number of 

DOE projects through development, integration and 

optimization of existing fuel processing system 

designs. This project is directed at investigating and 

developing plate reactor concepts where the catalytic 

function is integrated into a primary surface heat 

exchanger. The catalyst is coated onto the surface of 

a thin walled plate heat exchanger. For example, in 

the case of the steam reforming reactor, a reforming 

catalyst driving the endothermic reaction is coated on 

one side of the thin plate and a catalytic oxidation 

catalyst is coated onto the other side to drive the 

exothermic reaction, with the heat transferred 

efficiently between these catalysts by the thin metal 

plate. These structures can provide fast transient 

operation, compact reactors, very good temperature 

control and optimized operation. This project is 

directed at developing and demonstrating these 

reactor systems for processing gasoline to PEMquality hydrogen. 

Approach 

The development of plate reactor designs for 

conversion of gasoline to hydrogen requires the 

integration of the detailed reactor design with details 

of the catalyst performance. To integrate all of these 

aspects and optimize the design, this project makes 

extensive use of reactor modeling that includes all 

important aspects of the system, e.g. convective gas 

flow, diffusion, catalyst layer structure, heat transfer 

throughout the structure and detailed kinetics of the 

catalytic reaction. Since in many cases reaction 

kinetics are not available, initial work was directed at 

developing catalyst materials with activity in the 

desired range that could be applied as a thin washcoat 

layer onto the plate surface. The kinetics of the 

catalytic reaction were then measured in sufficient 

detail to allow adequate modeling of the plate reactor 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

design using in-house developed computer codes for 

each reactor design. In many cases, improved 

catalysts were required and were developed. 

The resulting target reactor design and catalyst 

system were then used to develop mechanical 

designs for a plate reactor to be used in laboratory 

demonstration at the 1 to 10 kW(e) size. Some early 

work was directed at understanding the effect of 

rapid temperature transients (startup, shutdown and 

loading) on the plate reactor design, and design 

aspects were identified that would lead to good cyclic 

life, particularly for the steam reformer reactor where 

the temperature transients are most severe. 

Results 

Steam Reforming: The defined approach is to 

directly steam reform gasoline in a plate reactor 

configuration using combustion on the opposite side 

of the plate to provide the endothermic heat of 

reaction. A catalyst has been developed that shows 

good activity and stability. Some test results are 

shown in Figure 1. Test conditions were: 

•	 Temperature: 825°C, Pressure: 3.0 atm 

•	 Space velocity (SV): 21.0 g fuel per g catalysthour 

•	 Steam to carbon ratio: 3.8 

•	 Fuel: ANL Benchmark Fuel I with 10 ppm sulfur 

•	 Tube wall coated test reactor that simulates the 

required flow conditions, catalyst washcoat layer 

and catalyst temperature 

While pressure variation causes some 

fluctuations in the H2 yield, the catalyst performance 

is relatively stable. The amount of catalyst required 

for a 50-kW(e) reactor is 0.42 kg, assuming the 

catalyst activity is stable at this performance level. 

Measurements are in progress to obtain a global 

kinetic expression for use in developing a detailed 

simulation of the plate reformer system. This 

catalyst will be incorporated into the demonstration 

prototype plate reformer described later. 

Water Gas Shift Reactor: Catalytica Energy 

Systems Inc. (CESI) has developed an improved 

water gas shift catalyst (WGS) formulation with 

highly desirable characteristics such as 1) no preconditioning requirement, 2) no air sensitivity, 3) 

non-precious metal based, and 4) low sensitivity to 

condensed water. This catalyst has shown good 

durability (Figure 2) in reactor runs up to 500 hours. 

For this level of activity, 5 kg of catalyst would be 

required for a 50-kW(e) fuel processor, which meets 

the DOE WGS catalyst performance targets. 

Durability data for WGS catalysts is very 

important due to the high sensitivity of this system to 

thermal degradation and past experience that 

durability is highly dependent on composition and 

operating conditions. For this reason, a static aging 

system is being developed to age the catalyst 

materials for long times, e.g. up to the target 

durability of 5000 hours, with minimum effort and 

cost. The strategy is to age a large batch of the target 

material at conditions that simulate water gas shift 

Figure 1.	 Steam Reforming of ANL Benchmark Fuel I 

with 10 ppm Sulfur on 4 Different Catalyst 

Materials under Plate Reactor Conditions 

Figure 2. Water Gas Shift Reaction Durability Run with 

Base Metal Catalyst 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

reactor operation and periodically remove samples 

for characterization and activity testing. CESI has 

shown this to be a cost effective strategy for 

obtaining catalyst durability data. Work is currently 

in progress to validate this system by comparison of 

static aged catalyst materials with materials aged in 

the laboratory bench-scale test reactor as presented in 

Figure 1. New catalyst compositions will be 

similarly aged to determine long-term durability. 

Detailed kinetics have been measured for these 

stable base metal water gas shift catalysts, and these 

data are being used to model plate reactor designs for 

optimum operation. As an example, the plate reactor 

configuration using countercurrent air as the 

temperature control media with the catalyst materials 

developed in this program provides greater then 90% 

CO conversion with a typical steam reformer outlet 

composition and a catalyst loading of 3 kg, as shown 

in Figure 3. While this shows the potential 

performance of such a system, catalysts with 

durability at higher temperatures (340 to 380°C) 

must be developed. 

Preferential Oxidation: The plate reactor approach 

allows the close control of catalyst temperature during 

reaction. This is especially important for the 

preferential oxidation of CO, where the selectivity of 

the reaction is highly temperature dependent. Testing 

with a packed bed reactor was unsuccessful due to this 

temperature dependence, and work was shifted to a 

wall coated test reactor design where the catalyst 

temperature could be controlled. Preliminary catalyst 

development is complete, and kinetics have been 

obtained over a wide range of operating conditions. 

Durability test results are shown in Figure 4, where a 

fresh catalyst and an aged catalyst are compared. The 

catalyst was aged by operation in preferential 

oxidation reaction, including kinetic measurements 

and long-term runs at conditions simulating low load 

to high load and low conversion to high conversion. 

Test conditions are: 

•	 Inlet gas composition: 1% CO, 1% O2, 64% H2, 

18% H2O, 16% CO2 

•	 Gas space velocity: 118 liters/gcat-hr 

The performance of the aged catalyst is 

essentially identical to the fresh material. One 

unusual aspect of this catalyst is the observation that 

the selectivity for oxidation of CO compared to 

oxidation of H2 was observed to vary from 50 to 60% 

over most conditions. The amount of catalyst 

required for a 50-kW(e) preferential oxidation 

reactor in the plate configuration is about 600 g when 

operated at 150°C and achieving 20 ppm CO in the 

outlet gas stream. 

Demonstration Prototype Plate Reformer: One of 

the major issues in the design of a plate reactor 

Figure 3.	 Model simulation of water gas shift plate 

reactor design with countercurrent cooling gas 

flow. CO conversion of 90% achieved with 3 

kg of catalyst if activity can be maintained over 

these conditions. 

Figure 4.	 Catalyst durability demonstration for the 

preferential oxidation of CO. CO conversion as 

temperature was varied from 80 to 200°C for a 

fresh and 800 hour aged catalyst. No catalyst 

deactivation was observed. 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

system is the high stress level arising from the startup 

and transient cycles that produce large temperature 

transients and large thermal gradients. Previously 

reported work described extensive finite element 

structural analysis of the plate reactor concept and 

examined numerous reactor design approaches. A 

design approach was developed that resulted in a 

calculated maximum strain of 0.28%, close to the 

target value that would provide the required cyclic 

fatigue life for the rapid thermal transients occurring 

during startup and load following. This design 

approach was used to develop three approaches to a 

prototype reactor mechanical design for fabrication 

and demonstration testing. Typical design aspects of 

the prototype will be: 

•	 Primary surface plate thickness: 0.15 mm 

•	 Catalyst washcoat layer thickness: 20 to 50 

microns 

•	 Gas flow channel dimensions: 0.6 to 1.5 mm 

diameter by 100 mm 

The manifolds supplying the feed (fuel and air to 

the combustion side, fuel and steam to the reformer 

side) are sized to ensure uniform distribution (within 

4%) of the feed to all of the plates. The plates and 

manifold are assembled in a manner to minimize 

thermally induced stresses. 

The new design is being taken to prototype 

fabrication through 3 parallel approaches: (1) using 

pre-existing heat-exchanger plates that provide most 

of the required functionality, (2) using soft-tooled 

plate stamping to produce an a priori design and (3) 

using a fin-folding technique to produce a design 

derived from gas turbine heat exchangers that show 

good transient performance. At least one but most 

likely two of the fabrication approaches will be 

selected to produce a prototype unit in the 1 to 10 

kW(e) range for demonstration testing. 

Conclusions 

•	 Computer simulation has demonstrated that plate 

reactor designs provide very efficient reactor 

performance for steam reforming, water gas shift 

and preferential CO oxidation arising from the 

ability to control the catalyst temperature to a 

desired range. 

 FY 2003 Progress Report 

•	 Catalyst systems have been developed that can 

be applied as a washcoat onto heat exchange 

surfaces and can provide the required 

performance for plate reactor fuel processor 

systems. 

•	 Direct steam reforming of gasoline with 10 ppm 

sulfur has been demonstrated. The gasoline 

plate reformer would be the first reactor in a fuel 

processor, and a design approach has been 

developed to demonstrate startup including fast 

startup and transient operation. Design and 

fabrication of prototype plate reactors is in 

progress. 

FY 2003 Publications/Presentations 

1. J. M. Zalc, H. Liu, R. Dalla Betta; "System 

Integration Issues for a Plate Reactor-Based 

Automotive Fuel Processor", Am. Institute of 

Chemical Engineers Meeting, 8 November 2002, 

Indianapolis, IN. 

2. "Plate Based Fuel Processing System", 

FreedomCAR Technical Team Review, 19 March 

2003, Detroit, MI. 

3. V. Sokolovskii, J. Zalc, D. Poojary, T. Ho, D. 

Taube, G. Malukhin, R. Dalla Betta; "Non-noble 

Metal Water-Gas Shift Catalysts for Automotive 

Fuel Cell Application", American Chemical 

Society Meeting, April 2003. 

4. "Plate Based Fuel Processing System", 2003 DOE 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Review Meeting, 19-22 

May 2003, Berkeley, CA. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Quick-Starting Fuel Processors - A Feasibility Study 

S. Ahmed (Primary Contact), R. Ahluwalia, S.H.D. Lee 

Argonne National Laboratory 

9700 S. Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-4553; Fax: (630) 972-4553; E-mail: ahmed@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Determine the feasibility of starting a practical fuel processor in 60 seconds or less. 

•	 Identify technical barriers that limit the fast-start capabilities of fuel-flexible fuel processors. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Startup/Transient Operation 

•	 M. Fuel Processor System Integration and Efficiency 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

Approach 

•	 Working with multiple national laboratories, universities, and commercial organizations, design a 

gasoline fuel processor that can meet DOE's performance targets. 

•	 Develop a start-up strategy that will enable the fuel processor to deliver >90% of its rated hydrogen 

production capacity in 60 seconds or less. 

•	 Demonstrate start-up performance of key fuel processor components and the performance of the 

integrated fuel processor in laboratory tests. 

•	 Analyze test results to evaluate performance. 

Accomplishments 

•	 Designed a laboratory-scale (10 kWe) fuel processor. 

•	 Provided project partners with component specifications for fuel processor fabrication. 

•	 Modeled fuel processor, demonstrating the feasibility of an 84% steady-state efficiency and a 60-sec 

start-up time. 

Future Directions 

•	 Demonstrate 60-sec start-up in a fuel processor that delivers 90% of rated hydrogen capacity. 

•	 Demonstrate greater than 80% fuel processing efficiency under steady-state operation. 

•	 Analyze data for processor performance, start-up fuel consumption, and process limitations. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

To be capable of start-and-go driving, all 

propulsion power components must be operational 

shortly after the driver turns the key. For a fuel cell 

vehicle with an on-board fuel processor, this means 

that the fuel processor must produce and deliver 

sufficient hydrogen to the fuel cell on this basis. This 

requirement is relaxed somewhat in a hybrid vehicle 

operated by a fuel cell and a battery, since the battery 

can provide initial traction power while the fuel cell 

system warms up to its operating temperatures. 

For the on-board fuel processor, the Department 

of Energy has targeted start-up times of 60 seconds 

and 30 seconds (from ambient temperature of 25°C) 

for the years 2005 and 2010, respectively. 

Considering the significant mass of the fuel 

processor, some of which must be heated to several 

hundred degrees centigrade, the start-up process 

warrants attention at the early design stage. 

Reducing the thermal mass will reduce the energy 

needed (fuel consumption) during start-up, and a 

consistent, reproducible, and durable fuel processor 

that can meet the start-up time targets can be ensured 

through suitable heating strategies. 

Approach 

A subscale (10-kWe) fuel processor system will 

be designed, fabricated, and tested in the laboratory 

to demonstrate that it can convert gasoline and 

deliver 90% of its hydrogen production capacity in 

60 seconds. The fuel processor will be designed for a 

steady-state fuel processing efficiency (defined as the 

lower heating value of hydrogen produced divided by 

the lower heating value of the gasoline feed) greater 

than 80%. The experimental unit will be thermally 

integrated and will include several heat exchangers 

and air and water injection ports. 

This is a collaborative project with contributions 

from Los Alamos National Laboratory (LANL), Oak 

Ridge National Laboratory (ORNL), Pacific 

Northwest National Laboratory (PNNL), and a 

number of universities and private organizations. 

The fuel processor will be assembled and tested at 

Argonne National Laboratory (ANL). 

Results 

A laboratory-scale 10-kWe fuel processor has 

been designed to operate at an efficiency of greater 

than 80%. The fuel processor (see Figure 1) consists 

of an autothermal reformer (ATR) followed by a 4­

stage water-gas shift (WGS) reactor and a 3-stage 

preferential oxidation (PrOx) reactor. A total of 6 

heat exchangers are located in the reformate flow 

path to cool the reformate gases. The cooling needed 

before the fourth WGS stage is achieved by injecting 

liquid water. The higher steam concentration 

improves the low-temperature shift conversion. 

HE1, the heat exchanger between the ATR and WG1, 

is a microchannel heat exchanger designed and 

fabricated by PNNL to handle a heat load of 3.6 kW. 

The five other carbon foam heat exchangers are 

designed and fabricated by ORNL. The preferential 

oxidation reactor zones are designed and fabricated 

by LANL. 

Table 1 lists some of the key design and operating 

parameters of the fuel processor. At the rated capacity 

Figure 1. A Simplified Schematic of the Fuel Processor 

Table 1. Design and Operating Point for the 10-kWe 

Fuel Processor to be Studied 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

of 10 kWe, the overall gas hourly space velocities 

(GHSVs) in the ATR, WGS (combined), and PrOx 

(combined) are 74000, 6200, and 12300 per hour, 

respectively. With these catalyst loadings and 

operating conditions, the model predicts a fuel 

processing efficiency of 84%. This value assumes no 

heat loss and that sufficient heat is available from the 

anode gas burner to vaporize and heat fuel vapor to 

150°C and supply liquid water at 90°C. 

Table 2 lists the mass of each of the catalyst 

zones and the heat exchangers in the 10-kWe 

experimental fuel processor and their respective 

average temperatures at the steady-state design point. 

Based on these masses and temperatures, the 

minimum fuel energy that will be needed to heat up 

the fuel processor components during start-up from 

25°C is 1.5 MJ. 

The start-up strategy relies on the ATR 

component reaching its operating temperature very 

quickly. Assuming this can be achieved by operating 

at a high O/C ratio [ratio of oxygen (from air) to 

carbon in the ATR feed stream] without damaging 

the catalyst, the resulting reformate (containing 

combustible gases H2, CO, and light hydrocarbons) 

Table 2. Masses of Components in the Experimental 

Fuel Processor (10-kWe) and the Minimum 

Energy Needed to Reach Operating 

Temperatures 

 FY 2003 Progress Report 

will be oxidized just ahead of WG1, WG2, and WG3 

by injecting controlled amounts of air, as shown in 

Figure 1. The start-up strategy requires that only the 

ATR and the first three zones of the shift reactor are 

brought up to temperature. The PrOx units have 

been sized to compensate for the higher CO (up to 

4%) from the shift reactor during start-up. 

Figure 2 shows the temperature progression 

predicted from the simulation of a start-up 

algorithm. The ATR temperature reaches 800°C in 

less than 2 seconds, and temperatures in WG1, 

WG3, and P3 are close to their design temperatures 

in 60 seconds. The sharp rise in ATR temperature 

seen in this simulation is considered somewhat 

risky for catalyst durability. Even though the 

strategy does not call for heating HE1, the hightemperature reformate from the ATR does 

contribute to its warm-up. Figure 3 shows that the 

hydrogen production rate reaches ~90% of capacity 

within 60 seconds. Experimental measurements 

Figure 2.	 Simulation of a Start-Up Algorithm 

Showing Temperature Progression of 

Selected Components (at exit) 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Simulation of a Start-Up Algorithm 

Showing Hydrogen Production During the 

Start-Up Period 

will be used to develop an acceptable fast-start 

algorithm. 

Conclusions 

Argonne National Laboratory is leading a 

collaborative effort to study the feasibility of faststarting a fuel processor. A fuel processor has been 

designed to deliver 90% of its rated capacity for 

hydrogen in 60 seconds. A model of the fuel 

processor projects that the targeted start-up goals can 

be met and that the fuel processor will operate at a 

steady-state efficiency of greater than 80%. These 

calculated results will be validated experimentally 

with the fuel processor being fabricated, and the 

results will be analyzed to identify technical barriers 

that limit the fast-start capabilities of fuel processors. 

FY 2003 Publications/Presentations 

1. C. Pereira, S. Ahmed, S.H.D. Lee, and M. 

Krumpelt, "Integrated Fuel Processor 

Development," 2002 Future Car Congress 

Proceedings, SAE Paper No. 02FCC-161, 

Arlington, VA (2002). 

Special Recognitions & Awards/Patents 

Issued 

1. R. Ahluwalia, S. Ahmed, and S.H.D. Lee, 

"Method for Fast Start of a Fuel Processor," 

Invention Disclosure filed with Argonne National 

Laboratory (2003). 

2. S. Ahmed, R. Ahluwalia, and S.H.D. Lee, "Fuel 

Processor for Producing Hydrogen from 

Hydrocarbon Fuels," Invention Disclosure filed 

with Argonne National Laboratory (2003). 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fast Start Reformer Components 

Greg A. Whyatt 

Pacific Northwest National Laboratory 

P.O. Box 999, MS K6-24 

Richland, WA 99352 

Phone: (509) 376-0011; Fax: (509) 376-3108; E-mail: greg.whyatt@pnl.gov 

April D. McMillan 

Oak Ridge National Laboratory 

1 Bethel Valley Road 

Oak Ridge, TN 37831-6087 

Phone: (865) 241-4554; Fax: (865) 576-8424; E-mail: mcmillanad@ornl.gov 

Michael A. Inbody 

Los Alamos National Laboratory 

P.O. Box 1663, MS J-579 

Los Alamos, NM 87545 

Phone: (505) 665-7853; Fax: (505) 665-9507; E-mail: inbody@lanl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Support the development of the Argonne National Laboratory (ANL) FASTER fuel processor project 

with the expertise developed at PNNL, ORNL, and LANL. 

•	 Design and fabricate a highly effective recuperator with low pressure drop to recuperate incoming 

steam and air with autothermal reformer (ATR) reformate. 

•	 Design and fabricate a microchannel mixer to uniformly add air to reformate ahead of the water gas 

shift (WGS) catalyst to accelerate heating of the WGS catalyst. 

•	 Design and fabricate a lightweight heat exchanger that meets system constraints and operational 

performance requirements. 

•	 Optimize heat exchanger assembly for insertion into the FASTER system. 

•	 Demonstrate a heat duty of at least 1 kW with a pressure drop of <0.1 psi. 

•	 Investigate and develop a preferential oxidation (PrOx) reactor component design for integration into 

the FASTER fuel processor. 

•	 Deliver these components as part of a compact assembly for installation into the FASTER reactor 

system. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-up/Transient Operation 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 M. Fuel Processor System Integration and Efficiency 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

•	 Design and fabricate a highly effective, low pressure drop recuperator. 

•	 Design and fabricate micro-channel mixer for introducing air into reformate during startup. 

•	 Deliver a compact recuperator/mixer assembly for installation into the FASTER experimental system. 

•	 Design a prototype heat exchanger (HX) meeting original specifications for Tier 1; fabricate a test rig 

to validate HX design. 

•	 Test prototype HX under operational constraints and measure all inlets and outlets, i.e., pressure, 

temperature, flow, etc. 

•	 Analyze the data to determine heat duty as a function of water flow rate at a given inlet gas temperature. 

•	 Identify and measure the performance of PrOx catalysts for use in a PrOx reactor component. 

•	 Collaborate on PrOx component design and fabricate PrOx components. 

•	 Measure PrOx component response to simulated startup conditions and events. 

Accomplishments 

•	 Design work on recuperator, mixer, and assembly complete. 

•	 Both microchannel units are currently being diffusion bonded. 

•	 Modeled design concept to estimate pressure drop and heat transfer of the graphite foam heat
 

exchanger at all sizes specified by project lead, ANL.
 

•	 Designed a prototype heat exchanger approximately 3-inch inner diameter and 5-inch outer diameter 

with a machined channel into which a cooling jacket was press fit. 

•	 Tested prototype and met or exceeded all specifications. Improvements in design of the prototype HX 

were made and a second iteration prototype was fabricated. 

•	 Delivered all of Tier 1 heat exchangers at the end of June, 2003. Fabrication of Tier 2 heat exchangers 

is on schedule; anticipated delivery date is the end of July, 2003. 

•	 Measured kinetic parameters of PrOx catalysts for reactor design. 

•	 Investigated performance of PrOx reactor under simulated startup conditions. 

•	 Obtained catalyst substrates for unique PrOx component design and started fabrication. 

Future Directions 

•	 Complete fabrication and deliver assembly to ANL for inclusion in FASTER prototype. 

•	 Evaluate performance as part of the FASTER experimental effort. 

•	 Test Tier 1 HX at higher gas inlet temperatures; measure heat duty as a function of water flow rate at 

higher inlet temperature(s). 

•	 Evaluate different avenues for further reducing the weight of the graphite foam heat exchanger 

assembly while maintaining heat transfer and pressure drop. 

•	 Verify design performance in multi-stage PrOx experiments. 

Introduction 

The major technical challenge for the 

development of a successful onboard fuel processor 

for fuel cell systems is the 2010 technical target for 

startup in less than 30 seconds. Overcoming this 

technical challenge is the objective of the FASTER 

(Feasibility of Acceptable Start Time Experimental 

Reactor) project led by Argonne National Laboratory 

(ANL), whose goal is to design, build, and test an 

experimental fuel processor to demonstrate concepts 

for rapid startup. The FASTER project is a 

2 
 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

collaborative effort which includes the contributions 

of three additional national laboratories that have 

developed significant expertise for the DOE 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program. Pacific Northwest National 

Laboratory (PNNL) has expertise in the development 

of microchannel heat exchanger technology for 

reforming components, Oak Ridge National 

Laboratory (ORNL) has expertise in the development 

of graphite foam heat exchanger technology, and Los 

Alamos National Laboratory (LANL) has developed 

preferential oxidation (PrOx) technology for the 

removal of carbon monoxide. The contributions of 

these three national laboratories are reported here. 

Recuperator/Mixer Assembly - Between the outlet 

of the autothermal reformer (ATR) and the entrance 

to the water gas shift (WGS) reactor is an assembly 

being provided by PNNL. The assembly is designed 

to fit within the FASTER geometry and contains a 

recuperator and a mixer. The recuperator will 

recover heat from the ATR reformate to preheat the 

air and steam feed to the ATR. This cools the 

reformate to a temperature suitable for the WGS 

catalyst. The effective recovery of heat from the hot 

reformate allows the system to be energy efficient. 

The micro-channel mixer is positioned at the 

reformate outlet of the recuperator. During startup, it 

will mix air into the reformate, causing oxidation of 

reformate on the WGS catalyst to accelerate heating 

of the WGS catalyst. A uniform reformate/air 

mixture is required to prevent local hot or cold spots 

on the WGS catalyst during startup. 

Graphite Foam Heat Exchangers – Within the 

WGS and PrOx reactors, temperature control is 

paramount to efficient operation. Heat exchangers 

(HXs) must be lightweight and capable of handling a 

heat duty of 1 kW at low pressure drops. These heat 

exchangers must meet the operational and physical 

constraints of the FASTER system design for 

effective catalysis downstream. ORNL is providing 

these HXs to facilitate fast start. 

PrOx - The preferential oxidation (PrOx) reactor 

component is typically the last component of the fuel 

processor, and its function is to control the outlet 

carbon monoxide to levels below 10 ppm. LANL is 

using its experience in PrOx research and design to 

develop a PrOx reactor to enable fast start. This 

 FY 2003 Progress Report 

includes reducing the thermal mass of the catalysts 

and components in contact with the flow, identifying 

a catalyst with a low light-off temperature for CO 

oxidation that also maintains CO selectivity over a 

wide temperature range, and identifying strategies to 

oxidize high concentrations of CO at startup before 

the WGS reactors become operational. The goal is to 

incorporate these features into PrOx reactor 

components to be fabricated and delivered for 

assembly into the FASTER fuel processor. 

Approach 

Recuperator/Mixer Assembly - The micro-channel 

components are made by etching metal sheets, 

stacking them in sequence, and then sealing 

contacting surfaces by diffusion bonding. The 

recuperator and portions in contact with hot 

reformate are being fabricated in Inconel 600. 

Within the recuperator, the fluids exchange heat in a 

series of counterflow, laminar channels. Lower 

temperature components including the mixer are 

being fabricated in 316L stainless steel. The 

microchannel mixer divides the reformate and air 

into numerous channels, interleaves them, and then 

allows them to exit the downstream face of the panel. 

Actual mixing occurs as the flows exit the closely 

spaced interleaved channels. Features are included 

to maintain uniform mixing despite temperature 

differences between the fluids. 

Graphite Foam Heat Exchangers - The approach to 

designing graphite foam heat exchangers capable of 

handling the heat duty and pressure drop 

requirements was to first use computational fluid 

dynamics (CFD) to model the foam under these 

constraints. From the model results, a corrugated 

design was fabricated. The model of the graphite 

foam capabilities was validated experimentally. 

Copper was chosen as the coolant jacket material due 

to its high bulk thermal conductivity and its ability to 

spread the heat in all directions, aiding in heat 

transfer. Initially, the inlet and outlet for the cooling 

water for the jacket were on the same side of the 

jacket. Infra-red (IR) imaging showed symmetric 

cooling about the jacket; however, this IR imaging 

also showed that the coolant two-phase flow could be 

improved. Thus, in the second iterative prototype, 

the flow is now bi-furcated, with the inlet and outlet 

180° from one another (Figure 1). This should 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

increase the two-phase flow and therefore enhance 

heat transfer in the assembly. 

PrOx - The approach to developing a PrOx reactor 

component has been to first identify PrOx catalysts 

that have desirable characteristics for startup 

performance. Laboratory PrOx reactor hardware is 

used to measure the kinetic parameters of the 

catalysts under simulated steady-state operating 

conditions and to measure the PrOx component 

response to simulated startup conditions and events. 

Kinetic parameters are supplied to ANL for use in the 

fuel processor design calculations. Based on the 

design, catalyst substrates are obtained, catalyzed, 

and fabricated into the reactor components for the 

FASTER fuel processor. 

Results 

Recuperator/Mixer Assembly – The thermal 

performance requirements for the recuperator are 

shown in Figure 2. In addition, a number of spatial 

requirements were placed on the design to allow the 

assembly to connect to the ATR, match desired 

connection locations, and fit within the 6-inch 

diameter core of the FASTER reactor system. The 

recuperator and mixer are designed and fabrication is 

under way. A key feature of the recuperator is 

turndown performance. The recuperator is predicted 

to maintain >85% effectiveness as the flow is 

decreased from 100% of design capacity to 10% of 

capacity. This feature prevents excessively high 

reformate temperatures (which could damage the 

WGS catalyst) under the normal range of operating 

rates. The weight of the components is estimated to 

be ~800 g for the recuperator, ~176 g for the mixer 

and ~1100 g for the total assembly. The assembly to 

be delivered to ANL is shown in Figure 3. 

 FY 2003 Progress Report 

Graphite Foam Heat Exchangers - Tests indicate 

that the heat duty is relatively constant for a given 

inlet gas temperature. Further, tests reveal that heat 

transfer through the graphite foam may be insensitive 

to water flow (Figure 4). This will allow for more 

flexibility in the control of the overall FASTER 

system; it may be possible to maintain critical 

Figure 2. Design Requirements for Recuperator 

Thermal Performance 

Figure 1. Tier 1 Graphite Foam Heat Exchangers for 

FASTER 

Figure 3. Recuperator/Mixer Assembly for 

Incorporation into FASTER ATR 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

temperature regimes for each catalyst while using 

supply water at low flow rates. Feedback may be 

used to more efficiently control the water flow rates 

to increase the overall system efficiency. 

PrOx - PrOx catalysts were obtained from various 

manufacturers on monolith, ceramic foam, and metal 

foam substrates. Based on preliminary testing, a 

catalyst was identified with low light-off temperature 

and good selectivity. The performance of the catalyst 

was measured over the range of expected operating 

conditions, and the data was provided to ANL for 

their fuel processor model and evaluation of kinetic 

parameters. 

A three-stage PrOx design was chosen to permit 

greater flexibility in removing higher CO 

concentrations (>1%). The first and second stages 

will operate to bring the outlet CO to 2000 to 1000 

ppm. The third stage will operate to bring the outlet 

CO to <10 ppm with a small temperature rise to 

avoid the reverse WGS reaction. Foam substrates 

were obtained for the unique geometry of the PrOx 

component dictated in the fuel processor design. 

Single-stage startup experiments were conducted 

to investigate the startup response of a PrOx catalyst 

monolith from room temperature. For these 

experiments, a primary gas flow consisting of 46.4% 

H2, 32.9% N2, 19.0% CO2, and 1.2% CO at a 

 FY 2003 Progress Report 

temperature of 20oC was established at a gas hourly 

space velocity (GHSV) .31,000 hr-1 through a 

600cell/in2

, 3-inch diameter, 5-inch long PrOx 

catalyst monolith. Air injection was started, and the 

resulting outlet CO concentration and monolith 

temperature profile were measured as a function of 

time. Figures 5 and 6 show the outlet CO 

concentration response and monolith temperature 

response as a function of time, respectively. The 

outlet CO decreases rapidly to its steady-state values 

in less than 30 seconds, while the temperature 

response takes longer to reach steady-state. The low 

Figure 5. PrOx Outlet CO Response as a Function of 

Time 

Figure 4. Performance of Tier 1 Graphite Foam Heat 

Exchanger 

Figure 6. PrOx Monolith Temperature Response as a 

Function of Time 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

light-off temperature of the catalyst is evident from 

the response. Similar responses were obtained for 

both higher (2.2%) and lower (2350 ppm) inlet CO 

concentration. Based on these experiments, fast 

startup of the PrOx reactor component appears 

feasible. 

Conclusions 

•	 A compact, lightweight and efficient 

microchannel recuperator meeting the desired 

thermal performance, pressure drop and spatial 

requirements is possible. 

•	 A microchannel mixer provides a method to 

uniformly mix air into reformate during startup 

to accelerate heating of the WGS catalyst. 

•	 Graphite foam has met or exceeded 

specifications for performance in the FASTER 

system. 

•	 Graphite foam heat exchangers appear to be 

relatively insensitive to water flow, especially at 

higher gas inlet temperatures. 

•	 Further decreases in weight of the heat 

exchanger assembly may be possible. 

•	 PrOx catalysts have been identified and 

characterized, and a three-stage PrOx design is 

being fabricated. 

•	 Outlet CO concentrations could be reduced to 

steady-state values in less than 30 seconds in 

PrOx single-stage startup experiments. 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Whyatt, G. A., Poster: Micro-Channel 

Recuperator and Mixer for FASTER (Feasibility 

of Acceptable Start Time Experimental Reactor) 

Autothermal Reformer. Presented at the 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program 2003 Merit Review and 

Peer Evaluation Meeting, May 19-22, 2003, 

Berkeley CA. 

2. Inbody, M. A., R. L. Borup, et al. (2002). 

Transient Control of Carbon Monoxide with 

Staged PrOx Reactors. 224th National Meeting of 

the American Chemical Society, Boston, MA, 

American Chemical Society. 

3. Inbody, M. A., R. L. Borup, et al. (2002). Transient 

PrOx Carbon Monoxide Measurement, Control 

and Optimization. 2002 Fuel Cell Seminar. 

4. McMillan, A.D., Romanonski, G.R., Klett, J.W., 

Armstrong, T., and Stinton, D., Annular Graphite 

Foam Heat Exchangers Were Developed for 

FASTER. Presented at the Hydrogen, Fuel Cells 

and Infrastructure Technologies Program 2003 

Merit Review and Peer Evaluation Meeting, May 

19-22, 2003, Berkeley, CA. 

Special Recognitions & Awards/Patents 

Issued 

1. Patent Application: Greg A. Whyatt, #60­

471,130, Microchannel Mixing Device, 5/16/03 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Reformate Cleanup: The Case for Microchannel Architecture 

Ward E. TeGrotenhuis (Primary Contact), K.P. Brooks, J.M. Davis, C.M. Fischer, D.L. King, L.R. 

Pederson, G.C. Rawlings, V.S. Stenkamp, R.S. Wegeng, G.A. Whyatt 

Pacific Northwest National Laboratory (PNNL) 

Post Office Box 999 

Richland, WA 99352 

Phone: (509) 376-0011; Fax: (509) 376-3108; E-mail: ward.tegrotenhuis@pnl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

The overall objective of the effort at PNNL is to apply microchannel architectures where appropriate in 

fuel processing systems for transportation, stationary, and portable applications to reduce size and weight, 

improve fuel efficiency, and enhance operation. Specific objectives for this project are focused on CO 

cleanup and balance of plant, including 

•	 Demonstrating 90% conversion of CO in a single-stage water-gas shift (WGS) reactor that scales to 

less than three liters at full-scale (50 kWe), 

•	 Evaluating the potential importance of microchannel architectures in reducing the size and weight and 

improving performance of preferential oxidation (PROX) reactors, 

•	 Exploring the ability to improve H2S adsorption with conventional sorbents through improved 

temperature control, and 

•	 Developing compact microchannel heat exchange technology for the recovery and recycle of water in 

fuel processor/fuel cell systems. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 J. Durability 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 R. Thermal and Water Management 

Approach 

•	 Demonstrate a compact differential-temperature microchannel water-gas shift reactor 

- Select and characterize a high activity shift catalyst 

- Calculate the optimal temperature profile 

- Design and test a multi-channel microreactor with integrated heat exchange to demonstrate the 

advantage of the approach 

- Demonstrate lifetime and durability of the engineered catalyst 

- Integrate with a steam reforming fuel processor 

•	 Investigate approaches for PROX reactor enhancements with microchannels 

- Evaluate industrial PROX catalysts for fast kinetics 

- Confirm favorable operational characteristics with effective temperature control at the 2-kWe scale 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- Investigate weight reductions through use of low-density alloys 

- Investigate transient and startup characteristics 

- Integrate with a steam reforming fuel processor 

•	 Explore effectiveness of controlling temperature profile to enhance H2S removal in conventional 

adsorbent materials 

- Quantify H2O sorption kinetics as a function of temperature for commercial sorbent materials 

- Calculate optimal temperature profile for differential temperature adsorber 

- Construct microchannel unit and obtain experimental performance data under differential
 

temperature conditions
 

- Compare results with isothermal performance 

•	 Integrate microchannel heat exchange and phase separation technology to recover and recycle water in 

fuel processor/fuel cell systems 

Accomplishments 

•	 Performed extended operation and thermal cycle testing of precious metal water-gas shift catalyst in 

engineered form 

•	 Continued efforts toward demonstrating differential temperature WGS operation in a multi-channel 

counter-flow reactor 

•	 Designed and built a prototype first-stage microchannel PROX reactor at the 2-kWe scale and 

demonstrated effective operation up to 4 kWe 

•	 Demonstrated a multi-channel air-cooled partial condenser with integrated phase separation on a 

simulated cathode effluent at the 1.5-kWe scale 

Future Directions 

•	 Continue catalyst development with focus on durable engineered forms of commercial WGS catalyst 

•	 Design, build and test a second generation differential temperature microchannel reactor 

•	 Evolve PROX reactor concepts for higher productivity and improved thermal control 

•	 Demonstrate differential temperature H2S sorption 

•	 Integrate WGS, PROX, and sulfur removal in an integrated steam reforming fuel processor 

•	 Pursue fabrication alternatives to facilitate low cost manufacturing targeting low temperature 

components 

Introduction 

A critical aspect of attaining size and weight 

objectives for on-board fuel processors is achieving 

rapid heat and mass transfer rates, which is made 

possible by microchannels. This has been 

demonstrated in the past for the highly endothermic 

steam reforming reaction in microchannel reactors 

having integrated heat exchange to supply the 

necessary heat. This project extends the effort to the 

areas of reformate cleanup and balance-of-plant, in 

order to identify other elements of a fuel processing/ 

fuel cell system that can benefit from the 

microchannel architecture. 

The water-gas shift (WGS) reaction is the 

conventional processing step after the fuel reformer 

to convert carbon monoxide to carbon dioxide, 

thereby reducing CO as a poison for PEM fuel cells 

while increasing hydrogen yield. The WGS reaction 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

is exothermic, so that high temperature operation 

favors kinetics but equilibrium is more favorable at 

low temperature. The conventional approach is to 

operate a high temperature shift (HTS) reactor above 

400°C, followed by a low temperature shift (LTS) 

reactor operating below 300°C to achieve the 

necessary conversion, with a heat exchanger in 

between to cool the reformate. A more optimal 

temperature profile could reduce the size of the shift 

subsystem and reduce the amount of catalyst 

required. The preferential oxidation (PROX) reactor 

is used to reduce carbon monoxide to levels that can 

be tolerated by PEM fuel cells by selectively 

oxidizing CO with air. Typically, PROX catalysts 

have a relatively narrow temperature window where 

CO conversion and selectivity are high. 

Microchannel approaches for integrating heat 

exchange within a PROX reactor offer potential 

improvement in PROX reactor performance. 

The conventional approach for removing 

hydrogen sulfide, a poison for downstream catalysts 

and the fuel cell, from the reformate stream is 

adsorption using zinc oxide. H2S adsorption also 

exhibits a temperature trade-off between sorption 

equilibrium and increased mass transfer rates, so 

improved localized temperature control is expected 

to improve performance. Finally, because fuel 

processors and fuel cells require water, recovery and 

recycle of water is necessary, and partial 

condensation is an appropriate topic for 

microchannel heat exchange as a means for 

achieving water balance. Each of these topics 

represents opportunities for applying microchannels 

to CO cleanup and balance-of-plant needs, which are 

under investigation in this project. 

Approach 

The general approach is a logical sequence of 

steps designed to demonstrate feasibility and 

potential benefits for overcoming programmatic 

technical barriers. This typically involves selecting a 

catalyst material from available sources through a 

screening process. The selected material is then 

characterized in an engineered form suitable for 

microchannel reactors through a series of tests over a 

range of operating conditions. A kinetic model may 

be developed from detailed finite element analysis of 

the reactor to support subsequent reactor engineering 

and design. The next step is to build and test a 

prototype microchannel reactor as a concept 

demonstration and to provide experimental data for 

scale-up and system integration. Finally, a 

microchannel reactor is designed and built based on 

integrated system specifications and tested within an 

integrated fuel processor to validate system 

performance. 

Water-gas shift and hydrogen sulfide adsorption 

have similar temperature trade-offs that suggest 

performance can be enhanced by monotonically 

decreasing the temperature as the process proceeds. 

For these applications, the approach is to utilize 

integrated microchannel heat exchange to actively 

cool the reformate stream as it passes through a 

microchannel reactor. For example, theoretical 

calculations suggest the amount of water-gas shift 

required can be reduced by up to half with this 

approach. For PROX, a two-stage reactor approach 

is adopted with at least the first stage actively cooled 

to remove heat generated by the reactions and control 

the temperature of the catalyst within a range where 

high conversion and high selectivity are obtained. 

Results 

Water-Gas Shift Reactor – Efforts in water-gas 

shift microchannel reactor development have 

included continuing catalyst characterization, 

lifetime testing, and deactivation investigations, and 

progress has been made in demonstrating a multichannel WGS reactor with a decreasing reaction gas 

temperature profile. Two new formulations of SudChemie precious metal catalysts were tested as 

possible improvements over the PMS5 catalyst 

adopted by the project in FY 2002. 

The 7-channel reactor shown in Figure 1 was 

tested in FY 2002, and the results showed 

significantly lower catalytic activity than found 

previously in single-channel testing. This catalyst 

was removed from the reactor, and individual 

catalyst pieces were tested in an isothermal singlechannel reactor. Single-channel results confirmed 20 

times lower activity than expected, and issues with 

loading the catalyst into the reactor were identified as 

possible causes. 

A second attempt was made to demonstrate 

differential temperature operation in a multi-channel 

counter-flow microreactor, and the results are 

3 
 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

summarized in Figure 2. Most significantly, the anticipated for the second stage to further reduce the 

ability to maintain the activity of the catalyst was CO level to 10 ppmv. 

demonstrated. In one test at 107,000 GHSV, with the 

feed end temperature at 375°C and the outlet end at 

325°C, 79% conversion of the CO was achieved, 

decreasing the dry gas CO concentration from 12.4% 

to 2.6%. However, differential temperature 

performance did not provide the advantage over 

isothermal operation that was expected, as illustrated 

in Figure 2. When the reactor was operated with the 

feed end at 375°C and a decreasing temperature 

profile, greater CO conversion and a lower outlet CO 

concentration was achieved when compared to 

isothermal operation at the colder outlet temperature. 

However, when compared to isothermal operation at 

the feed temperature of 375°C, performance was 

diminished. Flow maldistribution between the 

channels in the multi-channel reactor was identified 

as the cause of unexpected performance. Future 

efforts will target improving flow distribution while 

also optimizing catalyst loading and reactor 

configuration. 

Preferential Oxidation -- Commercially available 

catalysts were characterized in engineered form in a 

single-channel microreactor, including both precious 

metal and non-precious metal catalysts. Based on 

these results, a 2-stage approach was adopted, with a 

lower cost, non-precious metal catalyst selected for 

the first stage capable of achieving 97% conversion 

of CO from 1% to 300 ppmv with high selectivity 

when operated within a 20°C temperature range 

centered at 200°C. A precious metal catalyst is 

Figure 1.	 Seven-Channel WGS Reactor with Interleaved 

Counter-Current Heat Exchange Microchannels 

for Isothermal and Differential Temperature 

Operation 

A prototype reactor was designed and built for 

first stage PROX at the 2-kWe scale. The reactor 

shown in Figure 3 has four chambers, each with 

separate air addition. A microchannel heat 

exchanger within the reactor removes the heat 

generated from the reaction. Quasi-isothermal 

conditions are maintained within the PROX catalyst 

by the heat exchanger and by modulating air addition 

to each chamber. The operational characteristics of 

this reactor were determined by varying the 

reformate flow rate, operating temperatures, O2/CO 

ratios in each chamber, and inlet CO concentration 

(between 1-2% on a dry basis). The flow rate range 

corresponded to between 2 and 4.7 kWe equivalent 

fuel cell power output. Conversion profiles through 

the reactor are shown in Figure 4 for four power 

levels. Over 97% CO conversion was achieved at the 

Figure 2.	 Comparison of Isothermal and Differential 

Temperature Operation with Steam Reformate 

Feed (12.4% CO and 14.3 CO2, dry gas) at 

100,000 GHSV and 0.65 Steam to Dry Gas 

Showing CO Conversion (�) and CO 

Concentration (�) under Isothermal Operation 

and CO Conversion (�) and CO Concentration 

(✧) under Differential Mode with the 

Reformate Feed at 350°C with the Equilibrium 

CO Conversion Line Shown at the Top 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

4-kWe power level, which was twice the design 

objective. 

Desulfurization – Development of microchannel 

desulfurization technology was initiated in FY 2003, 

and efforts to date have been focused on developing 

experimental and analytical capabilities to support 

testing. Initial studies are underway to characterize 

Figure 3.	 Prototype PROX Reactor with Microchannels 

for Quasi-Isothermal Operation and Multiple 

Compartments for Staged Air Injection 

Figure 4.	 Carbon Monoxide Conversion Profiles through 

the Prototype First-Stage PROX Reactor 

Operated with an Overall O2/CO Ratio of 1.0, 

Feed CO Concentration of 1.14% (dry), 0.3 

Steam to Dry Gas Ratio, and Reformate Flow 

Rates Corresponding to 2 kWe (�), 3 kWe 

(�), 4 kWe (▲), and 4.7 kWe (X) 

CO uptake onto zinc oxide materials as a function of 

temperature to support calculations of optimal 

temperature profile to balance kinetics and sorption 

equilibrium. 

Partial Condensation with Phase Separation – A 

prototype multi-channel partial condenser with phase 

separation was tested over a range of flows, water 

content and temperatures. The cross-flow, air-cooled 

device was designed to recover water from the 

effluent stream from the cathode of a PEM fuel cell 

at approximately the 1.5-kWe scale. Design 

conditions include hot feed at 80°C, coolant air at 

30°C, and air-side pressure drop of 2.2 inches of H2O 

that would require an estimated 14 W of parasitic 

load at full scale. The aluminum device is extremely 

lightweight and includes a phase separator to remove 

the condensate separate from the gas effluent. The 

device is shown in Figure 5, and the results of testing 

are compiled in Figure 6, including comparison to 

theoretical prediction. Actual performance exceeds 

predicted performance, and specific power exceeded 

2000 Wt/kg at 74% water recovery. Water separation 

efficiency was 90-100%, and the coolant side 

pressure drop was about 4 inches of H2O, which was 

about twice the design value. 

Conclusions 

•	 Although additional work remains in 

demonstrating 90% conversion in a single-stage 

water-gas shift reactor using the differential 

temperature microchannel reactor concept, the 

approach remains valid for achieving a WGS 

Figure 5.	 Aluminum Microchannel Partial Condenser 

Containing 3 Sets of 0.020-inch Condensing 

Microchannels Interleaved with Cross-Flow 

0.024-inch Cooling Channels 

5 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 6.	 Specific Power versus the Water Content of the 

Prototype Microchannel Partial Condenser at 

Condensing Stream Air Flows of 32 SLPM (●) 

and 48 SLPM (�) with Trend Lines Shown 

through the Predicted Performance Values at 

the Same Operating Conditions that Produced 

the Experimental Data for Both 32 SLPM Air 

Flow (- - -) and 48 SLPM Air Flow (nn). 

reactor that is less than 3 liters at the 50-kWe 

scale. 

•	 A prototype first-stage PROX having integrated 

microchannel heat exchange has been shown to 

have excellent thermal control and high 

productivity. 

 FY 2003 Progress Report 

•	 Improving desulfurization using conventional 

sorbent materials is viable by optimizing thermal 

profiles using microchannels. 

•	 Lightweight, high thermal conductivity metals, 

such as aluminum, can be used in fabricating 

microchannel devices having high specific 

power for lower temperature components, 

including microchannel partial condensers for 

water management in fuel processors and fuel 

cell systems. 

FY 2003 Publications/Presentations 

1. TeGrotenhuis, W.E., K.P. Brooks, D.L. King, R.S. 

Wegeng, “Optimizing the Water Gas Shift 

Reaction in Microchannel Reactors by TradingOff Equilibrium and Reaction Kinetics through 

Temperature Management”, poster presentation at 

the 2002 Fuel Cell Seminar, November 18-21, 

Palm Spring, California. 

2. TeGrotenhuis, W.E. and V.S. Stenkamp, “Testing 

of a Microchannel Partial Condenser and Phase 

Separator in Reduced Gravity”, presented at First 

International Conference on Microchannels 

and Minichannels, April 24-25, 2003, Rochester, 

New York, USA (proceedings in print). 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Microchannel Steam Reformation of Hydrocarbon Fuels 

Greg A. Whyatt (Primary Contact), Kriston Brooks, Jim Davis, Chris Fischer, Dave King, Larry 

Pederson, Susie Stenkamp, Ward Tegrotenhuis, Bob Wegeng 

Pacific Northwest National Laboratory 

Post Office Box 999 

Richland, WA 99352 

Phone: (509) 376-0011; Fax: (509) 376-3108; E-mail: greg.whyatt@pnl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Evaluate the increase in productivity of steam reforming at temperatures greater than 650°C. 

•	 Evaluate increase in sulfur tolerance at temperatures >650°C. 

•	 Design and build low-pressure drop reactor, vaporizer and air recuperator that can maintain efficiency 

while exhibiting very low air side pressure drop. 

•	 Test rapid start strategy for steam reforming reactor and associated heat exchangers. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-Up/Transient Operation 

•	 J. Durability 

•	 M. Fuel Processor System Integration and Efficiency 

Approach 

•	 Assemble high temperature reforming components including an Inconel 625 reactor and recuperator to 

allow testing of microchannel steam reforming at reformate outlet temperatures >650°C. 

•	 Measure reforming capacity as a function of temperature for methane, isooctane and benchmark fuel at 

~1 kWe scale. Evaluate capacity at conversion levels of ~99.9% and >99.995% (no detectable nonmethane hydrocarbons). 

•	 Evaluate reformer performance with up to 30 ppmw sulfur in the fuel. 

•	 Design and build low pressure drop microchannel reactors and associated heat exchangers to enable 

testing of an approach to rapid startup. 

•	 Perform initial testing of the rapid start approach. 

Accomplishments 

•	 Completed measurement of reformer capacity vs. temperature above 650°C for reforming methane, 

isooctane and benchmark fuel. 

•	 Measured productivity vs. temperature above 650°C while reforming benchmark fuel with no
 

detectable non-methane hydrocarbons in the reformate (conversion > 99.995%).
 

•	 Completed preliminary testing using sulfur spikes. 

•	 Completed initial testing of combustor (atomized gasoline) to provide heat to fast-start system. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Microchannel components for low pressure drop reforming system (reactors, water vaporizer, air 

recuperator, reformate recuperator) are designed and fabricated through the diffusion bonding step. 

Future Directions 

•	 Continue sulfur tolerance and carbon formation testing at elevated temperatures. 

•	 Evaluate reforming performance of low pressure drop reactor design. 

•	 Evaluate a potentially improved (lower-cost, increased durability) reforming catalyst which is now 

available. 

•	 Evaluate fast-start approach using stainless steel fast-start components. 

•	 Once data collection for high temperature sulfur tolerance and carbon deposition testing is complete, 

revise fast-start design to utilize smaller, lighter high-temperature reformer. 

•	 Integrate fast start reformer system with water gas shift (WGS) and preferential oxidation (PrOx) 

reactors at 2 kWe scale. 

Introduction 

This project is applying the rapid heat and mass 

transfer attainable in microchannels to the 

development of a highly compact and efficient steam 

reformer. Once developed, the steam reformer will 

fit on-board a highly efficient fuel cell vehicle and 

provide hydrogen to a proton exchange membrane 

(PEM) fuel cell, which in turn will produce 

electricity to power the vehicle. By reforming to 

produce hydrogen on-board the vehicle, the fuel can 

be gasoline, providing vehicle range, and the need to 

purify and compress hydrogen is eliminated. Also, 

an automobile with on-board reforming could be 

fueled using the existing gasoline infrastructure, an 

important advantage if a hydrogen refueling 

infrastructure is not available. 

In past work, this project demonstrated that 

steam reforming, normally considered a slow 

reaction, can achieve rapid kinetics in a 

microchannel reactor. In addition, it was 

demonstrated that this technology could be scaled up 

(10-25 kWe equivalent) and that the reforming 

reactor along with an integrated network of highly 

efficient microchannel heat exchangers could be 

highly compact and yet efficient. An approach to 

build water vaporizers having very low air side 

pressure drops was developed and demonstrated. A 

water vaporizer using this design sized for a 50-kWe 

fuel processor was delivered to McDermott as part of 

a fuel processing demonstration. Evaluation of 

microchannel reforming data indicated significant 

increases in reformer capacity might be available at 

higher temperatures than initially tested. The 

potential increase was judged to be sufficient in 

magnitude that the reduction in reactor mass might 

justify use of higher-priced alloys in place of 

stainless steel. In addition, the reactor tolerance for 

sulfur, a contaminant found in gasoline which must 

be removed prior to the PEM fuel cell, was expected 

to improve at higher temperature. Reforming the 

fuel and removing the sulfur from reformate is 

expected to be easier than removing the sulfur from 

liquid fuel. The current work examines the extent to 

which the reformer productivity and sulfur tolerance 

improve at temperatures above 650°C. In addition, 

work to develop a rapid-start capability, critical for 

an on-board automotive application, is being pursued 

(an earlier prototype required ~15 minutes for a cold 

start). The effort is aimed at assembling and testing a 

steam reforming system including the reformer and 

its associated heat exchangers that can cold start 

within ~30 seconds. Once demonstrated, the system 

will be expanded to include the WGS and PrOx 

reactors. 

Approach 

Reforming Capacity at High Temperature - The 

testing of reforming productivity was performed on 

an ~1 kWe test stand which has been shown to relate 

well to performance obtained in larger scale reactors. 

The reforming reactor shown in Figure 1 was 

integrated into a system of heat exchangers and 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

tested at temperatures above 650°C. In a typical 

reforming test, the temperature and flow of the 

combustion stream were held constant. The feed 

rates of hydrocarbon and steam were then increased 

(or decreased) while maintaining a fixed 3:1 steam to 

carbon ratio until there was a small but easily 

measurable residual of non-methane hydrocarbon in 

the reformate. For isooctane and benchmark fuel, 

this translated to a conversion level of 99.7% to 

99.9%. When reforming methane, the approach to 

equilibrium methane content was used, and the 

approach was 96% to 99%. After operating at each 

point for sufficient time to assure short-term stability, 

the combustion side temperature was changed and 

flows readjusted to obtain another point on the 

productivity vs. temperature curve. After completing 

the curve for benchmark fuel, an additional curve 

was generated in which the flows were reduced until 

there were no detectable non-methane hydrocarbons 

in the reformate (>99.995% conversion). 

Sulfur Tolerance at High Temperature - The same 

reactor and test system used for the productivity vs. 

temperature experiments is now being used to test the 

sulfur tolerance at temperatures above 650°C. Sulfur 

spikes equivalent to 30 ppmw sulfur in the liquid fuel 

are being introduced by adding H2S to the vaporized 

fuel and steam and by spiking the liquid fuel with 

benzo-thiophene and thiophene. 

Fast Start Reformer - Calculations were performed 

to define a steam reforming system, including the 

reforming reactor and associated heat exchangers, 

which would be able to start up within 30 seconds. 

The design is based on maintaining a very low 

pressure drop through the heat exchangers and 

reactors. During startup, the combustion gases flow 

through the reactors and vaporizer in parallel so that 

the high air flow does not result in a high pressure 

drop. The flow during normal operation is then 

changed to pass through reactors in series to reduce 

the total air flow and maintain efficiency. The low 

pressure drop during the startup period results in the 

fan required to provide the air flow being relatively 

less expensive. In addition, the electrical power 

requirement is low enough to be within the reach of a 

conventional automotive battery. The low pressure 

drop during normal operation reduces the cost of the 

fan but, perhaps more importantly, significantly 

reduces the parasitic power associated with air 

 FY 2003 Progress Report 

compression compared to either a steam reformer 

with higher pressure drops or an autothermal 

reformer operating at multiple psi pressures. 

Results 

Reforming Productivity vs. Temperature - The test 

reactor used to explore high temperature reforming 

rates is shown with the reformate recuperator and 

combustor attached to it in Figure 1. Reforming 

results are shown in Figure 2. Dramatic increases in 

processing rate were observed as the reformate outlet 

temperature was increased from 650°C to 875°C. 

The reforming rate of benchmark fuel increases 

exponentially as temperature is increased with no 

indication of leveling off due to heat or mass transfer 

limitations. This translates into the potential to 

significantly reduce reactor size if reforming at 

higher temperature. 

Sulfur Tolerance vs. Temperature - Preliminary 

results of the improvement in sulfur tolerance with 

increased temperature are shown in Figure 3. 

Reforming at a temperature of 800°C or more 

significantly increases the ability of the catalyst to 

Figure 1.	 Inconel 625 Reactor Used for High 

Temperature Steam Reforming Tests 

(Reformate recuperator and combustor are 

shown attached.) 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

process the sulfur containing fuel without losing 

activity. Additional testing with spikes up to 30 

ppmw S in the fuel introduced as hydrogen sulfide 

(added as gas to vaporized steam/fuel), thiophene 

and benzothiophene have confirmed the ability of the 

catalyst to process this level of sulfur with moderate 

reduction in activity for short periods of time. 

However, an increase in pressure drop over time 

across the reactor when reforming sulfur-spiked 

benchmark fuel has been observed. The increase in 

pressure drop is halted if the spike is removed. It is 

believed that this is an interaction between the highFigure 2.	 Throughput of Inconel 625 Reactor as a 

Function of Reformate Outlet Temperature 

(Throughput is expressed as electrical output. 

This could support assuming 90% conversion 

of CO in a WGS reactor, 50% selectivity in a 

PrOx reactor and a PEM fuel cell operating at 

44% efficiency.) 

Figure 3. Increase in Sulfur Tolerance While Reforming 

Benchmark Fuel at 800°C vs. 650°C
 

 FY 2003 Progress Report 

nickel alloy Inconel 625 used to fabricate the high 

temperature reformer and the sulfur content in the 

fuel. This issue is being investigated further. 

Fast Start Reformer - The microchannel hardware 

required for testing the rapid start approach has been 

designed, and individual components have been 

fabricated through the diffusion bonding step. The 

microchannel components are shown in Figure 4. 

During normal operation, the 2-kWe system will 

require about 100 slpm of air flow with a pressure 

drop of 6.0 inches of water. During startup the 

system will utilize ~4000 slpm at a pressure drop of 

5.2 inches of water. The pressure drop is maintained 

low by routing combustion gases in parallel through 

components during the startup period. A startup 

combustor was tested and demonstrated to provide 

the required flow of 800°C combustion gas in ~2 

seconds. 

Conclusions 

•	 The exponential gain in steam reformer productivity with temperature while reforming benchmark fuel implies a reactor operating at 850°C 

can be less than 1/3 the size of a reactor operating at 650°C. 

Figure 4.	 Low Pressure Drop Reactor System 

Components to be Used in Rapid Start 

Testing (The reactor weighs 400 g and 

supports ~500 We at 650°C. If produced in 

high temperature alloy and operated >850°C, 

the reactor would be capable of 2 kWe. The 

vaporizer weighs 325 grams and supplies 

steam for 2 kWe reforming capacity.) 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

•	 The steam reformer can provide reformate with 

no detectable non-methane hydrocarbons over 

the temperature range tested. 

•	 The sulfur tolerance of the catalyst is significantly improved by operating at temperatures 

>800°C. 

•	 The addition of a sulfur to benchmark fuel 

resulted in increases in pressure drop over time 

across the Inconel 625 steam reformer. This is 

being investigated. 

•	 The approach to achieving rapid start of the 

steam reformer appears feasible. 

FY 2003 Publications/Presentations 

1. Whyatt, G. A., K. Brooks, J. Davis, C. Fisher, D. 

King, L. Pederson, S. Stenkamp, W. 

Tegrotenhuis, B. Wegeng. Progress in 

Microchannel Steam Reformation of 

Hydrocarbon Fuels. Presented at the Hydrogen, 

Fuel Cells and Infrastructure Technologies 

Program 2003 Merit Review and Peer Evaluation 

Meeting, May 19-22, 2003 Berkeley CA. 

Special Recognitions & Awards/Patents 

Issued 

1. Patent Application: System for Rapid Cold 

Startup of Microchannel Steam Reformer. 

#60-471,286, G. A. Whyatt. 

 FY 2003 Progress Report 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Processors for PEM Fuel Cells 

Levi Thompson (Primary Contact) 

University of Michigan 

Department of Chemical Engineering 

3026 H.H. Dow Building 

Ann Arbor, MI 48109-2136 

Phone: (734) 647-7150; Fax: (734) 763-0459; E-mail: ltt@umich.edu 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Subcontractors: 

Osram Sylvania, Towanda, Pennsylvania 

Ricardo, Inc., Plymouth, Michigan 

Objectives 

•	 Demonstrate high performance desulfurizer, catalyst, micro-reactor and microcombustor/ 

microvaporizer concepts that will enable production of compact fuel processors for proton exchange 

membrane (PEM) fuel cells 

•	 Design, fabricate and evaluate a 1-kWe fuel-flexible fuel processor during the first 36 months (one of 

the fuels capable of being reformed will be EPA Phase II reformulated gasoline) 

•	 Design, fabricate and evaluate a fuel-flexible fuel processor capable of producing up to 10 kWe 

hydrogen (one of the test fuels will be EPA Phase II reformulated gasoline) 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Startup/Transient Operation 

•	 J. Durability 

•	 M. Fuel Processor System Integration and Efficiency 

• N. Costs 	 

Approach 

•	 Tasks devised to accomplish the project objectives include: 

•	 Design and model components and systems that would meet power density targets; 

•	 Develop high capacity sorbents capable of removing sulfur to target levels; 

•	 Develop better performing autothermal reforming (ATR), water gas shift (WGS) and preferential 

oxidation (PrOx) catalysts and associated microreactors; 

•	 Fabricate highly efficient microcombustors/microvaporizers; 

•	 Fabricate microchannel reactors and system; 

•	 Evaluate components and fuel processing system; 

•	 Estimate cost for fuel processor. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Modeled several of the microchannel reactors (FEMLAB and FLUENT) and entire fuel processor 

system (ASPEN and Matlab Simulink); 

•	 Demonstrated Cu-Y zeolite sorbents that significantly out-performed other available sorbents; 

•	 Demonstrated ceria/zirconia-based ATR, carbide-based WGS and sol-gel derived PrOx catalysts that 

out-performed available commercial catalysts; 

•	 Developed methods to scale up production of carbide-based catalysts; 

•	 Designed fuel and water microvaporizers; 

•	 Fabricated and tested metal, ceramic and silicon-based micro-reactors; 

•	 Designed and began construction of prototype 1-kWe fuel processor system. 

Future Directions 

During this coming year, our goal is to fabricate at least two 1-kWe fuel processor systems. The first 

design is a hybrid system that includes micro- and conventional reactor technologies. The second design 

will be based primarily on ceramic micro-reactors. Specific tasks will include: 

•	 Fabricate highly efficient microcombustors/microvaporizers, 

•	 Fabricate microchannel reactors and system, 

•	 Evaluate components and fuel processing system. 

Introduction 

Fuel cells are being developed to power cleaner, 

more fuel efficient automobiles. The fuel cell 

technology favored by many automobile 

manufacturers is proton exchange membrane (PEM) 

cells operating with H2 from liquid fuels like 

gasoline and diesel. A key challenge to the 

commercialization of PEM fuel cell based 

powertrains is the lack of sufficiently small and 

inexpensive fuel processors. Improving the 

performance and cost of the fuel processor will 

require the development of better performing 

catalysts, new reactor designs and better integration 

of the various fuel processing components. These 

components and systems could also find use in 

natural gas fuel processing for stationary, distributed 

generation applications. 

Approach 

Prototype gasoline fuel processors will be 

produced and evaluated against the Department of 

Energy technical targets. Significant improvements 

over the present state-of-the-art will be achieved by 

integrating low-cost microchannel systems, high 

activity catalysts, π-complexation sorbents, and high 

efficiency microcombustor/microvaporizers being 

developed at the University of Michigan. The 

microchannel system will allow (1) more efficient 

thermal coupling of the fuel processor components 

and minimization of the heat exchanger 

requirements, (2) improved catalyst performance due 

to optimal reactor temperature profiles and increased 

heat and mass transport rates, and (3) better cold-start 

and transient responses. 

The project will be accomplished in 3 phases. 

The Phase I effort will focus on demonstrating 

compact desulfurizer, micro-reactor and 

microcombustor/microvaporizer components for a 1­

kWe fuel processor, and developing low-cost 

methods for the production of microchannel systems. 

The components will be third-party tested and will 

provide the basis for design and fabrication of an 

integrated 1-kWe ethanol or gasoline fuel processor 

during Phase II. We will scale up the smaller 

processor to up to 10 kWe during Phase III. 

Results 

Design and modeling. The modeling activities have 

been at three levels: detailed component modeling, 

modeling for simplified component integration and 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

thermal management, and system integration and 

optimization modeling. FLUENT is being applied to 

develop detailed computational fluid dynamics 

(CFD) models of the internal reacting flow process 

for the prototype reactor components. The results are 

being used to design the ATR, WGS and PrOx 

reactors. A general 1-D counterflow heat exchanger 

model has been formulated into a non-dimensional 

model to facilitate systematic thermal management 

studies over a wide range of operating conditions. 

One of the key design issues is to maintain good 

temperature control. Finally, based on the systematic 

detailed and 1-D modeling studies, an integrated 

system optimization tool was developed. Based on 

the counterflow heat exchanger model as a canonical 

unit to represent individual components, a first-order 

reaction model has been implemented to calculate 

accurate reaction and heat generation rates. Matlab 

Simulink is being used to integrate a network of the 

various components including the ATR, WGS, and 

PrOx reactors, to predict the system behavior and to 

optimize the overall performance. The detailed 

component models and the 1-D models described 

will continue to provide submodels for individual 

blocks that constitute the system integration model. 

Sorbent development. Cu-Y zeolite based sulfur 

sorbents have been developed and evaluated. 

Breakthrough curves for desulfurization of diesel for 

these sorbents are compared to those for several 

benchmark sorbents in Figure 1. Selexsorb CDX is 

an activated alumina specially formulated by Alcoa 

for the adsorption of polar organic compounds 

including sulfur-based molecules (mercaptans, 

sulfides, disulfides, thiophenes). The CuCl/γ-Al2O3 

sorbent was prepared by dispersing CuCl2 on an 

activated alumina surface with the aid of a dispersing 

agent followed by reduction of Cu2+ to Cu+ . The 

AC/Cu-Y sorbent is a layered bed of 15 wt% 

activated carbon followed by Cu-Y. The highest 

adsorption capacity was achieved for AC/Cu-Y. 

Approximately 82% of its original capacity was 

recovered after treatment with air at 350°C. The 

capacity loss could be due to modification of the 

carbon during calcination. 

Catalyst development. High activity ATR, WGS, 

and PrOx catalysts have been demonstrated. A 

material consisting of 10 wt% Ni on a Ce0.75Zr0.25O2 

support was identified as the best performing octane 

ATR catalyst. This catalyst yielded high H2 

production rates under the following conditions: O/C 

= 1.0, H2O/C = 2.0, space velocity (SV) ~290,000 

hr-1 (iso-octane flow ~ 0.2 mol/hr or 100 We). 

Carbide-supported WGS catalysts (M/Mo2C) 

were synthesized that significantly exceed important 

targets established by the DOE. In particular, at 

240°C, conversions exceeding 90% with H2 

selectivities greater than 99% were achieved at gas 

hourly space velocities in excess of 50,000 hr-1 

(reactant contained 38% H2, 16% N2, 10% CO, 6% 

CO2 and 30% H2O). Rate laws for the carbide-based 

catalysts are also conducive for use at low CO 

contents and high product concentrations. Assuming 

high activities, low reaction orders for the reactants 

and products are preferred. Table 1 compares power 

law reaction orders for commercial Cu/Zn/Al 

catalysts, two oxide supported precious metal 

catalysts, high surface area Mo2C and the carbidesupported catalyst. 

Table 1. Reaction Orders for the Following Power Law: 

Rate = k•PCO mPH2O n

PCO2 oPH2p 

Catalyst M n o P

Mo2C 0.55±0.05 0.19±0.07 -0.02±0.06 -0.01±0.07 

M/Mo2C 0.13±0.04 0.48±0.05 0.01±0.04 -0.24±0.04 

Cu/Zn/Al 0.94±0.05 0.72±0.12 -0.38±0.10 -0.42±0.06 

Cu/Zn/Al (1) 1.0 1.4 -0.7 -0.9 

Cu/Zn/Al (2) 1.07±0.16 0.55±0.18 

Pd/CeO2 (3) 0.0 0.5 -0.5 -1.0 

Pt/Al2O3 (4) -0.21±0.03 0.75±0.04 

Rate data for the carbide-based catalyst were 

adequately described by the following LangmuirHinshelwood rate law where r is the rate, k is a rate 

constant, Pi

 are the partial pressures and Ki are the 

adsorption constants: 

kPH 2O 

r = (1+ KH 2O PH 2O + KH 2 

PH 2 )

2 

This rate law is consistent with a dual-site 

reaction with H2O dissociation being the rate 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 Breakthrough Curves for Desulfurization of 

Diesel (measurements at room temperature and 

atmospheric pressure) 

Figure 2.	 Illustrations of (top) Experimental Test MicroReactor and (bottom) Target Design Based on 

Simulations Results 

determining step. Osram Sylvania has scaled up 

production of the carbide catalysts to nearly 1-kg 

batches. 

We identified two catalysts for use in the PrOx 

reactor: 5% Pt/15% ceria-85% alumina and 1% Au/ 

Fe2O3. The Pt catalyst gives greater than 98% 

conversion with 50% CO oxidation selectivity at 

high temperatures (120-180°C), and the Au catalyst 

gives 99% conversion with 58% selectivity at 50°C. 

These catalysts were wash-coated onto monoliths 

and silicon and aluminum micro-reactor structures. 

We also built honeycomb and microchannel reactors 

for PrOx. The honeycomb reactor was capable of 

reducing the CO content of ~10 L/min of reformate 

to less than 10 ppm. 

Microchannel System Development. The heat 

required from the burner is directly coupled to the 

degree of heat recuperation achieved by component 

integration throughout the rest of the system. As a 

result, detailed burner/vaporizer requirements were 

developed based on results from the integration 

simulations. On a 1-kW basis, the total heat needed 

for vaporization and stream heating to target 

temperatures is 948 W, while the total heat available 

from the ATR and WGS reactions is 1001 W. An 

additional 300 W is available from combustion of the 

anode tailgas. A tailgas burner thus suffices for 

steady-state operation and is being developed. The 

fuel vaporizer is being developed which derives heat 

directly from the tailgas burner. The water vaporizer 

recovers heat first from the reactors and then derives 

additional heat from the tailgas burner or from a noncatalytic fuel burner. 

Cost-effective manufacturing methods have been 

developed to mass produce the fuel processor 

components. A semi-solid forming process has been 

identified as one of the most promising candidate 

processes. This process has good capability for 

creating the complex micro/meso-scale geometries 

required for the reactor components. 

Conclusions 

Significant progress was made last year. Several 

better performing fuel processing materials were 

developed. The deployment of these sorbents and 

catalysts should result in significant reductions in the 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

fuel processor size, weight and cost. Novel reactor 

geometries were also demonstrated. (See Figure 2.) 

Efforts for the coming year will focus on fabricating 

an integrated, 1-kWe gasoline fuel processor with 

characteristics that exceed key Department of Energy 

performance targets. 

References 

1. Oveson, C. V., Clausen, B. S., Hammershøi, B. S., 

Steffensen, G., Askgaard, T., Chorkendorff, I., 

Nørskov, J. K., Rasmussen, P. B., Stoltze, P., and 

Taylor, P., J. Catal. 158, 170 (1996). 

2. Salmi, T., and Hakkarainen, R., Appl. Catal. 49, 

285 (1989). 

3. Hilaire, S., Wang, X., Luo, T., Gorte, R. J., and 

Wagner, J., Appl. Catal. A 215, 271 (2001). 

4. Grenoble, D. C., Estadt, M. M., and Ollis, D. F., J. 

Catal. 67, 90 (1981). 

FY 2003 Publications/Presentations 

1.	 "Autothermal Reforming of Isooctane Over 

Supported Nickel Catalysts", Tadd, A., Saraf, V., 

Schwank, J., Jundee, T., and Rirksomboom, T., 

Preprints, AIChE Annual Meeting, Indianapolis, 

IN, November 3-8, 2002. 

2.	 "Supported Nickel Catalysts for Autothermal 

Reforming of Hydrocarbons", Tadd, A., Saraf, 

V., Schwank, J., Jundee, T., and Rirksomboom, 

T., North American Catalysis Society Meeting, 

Cancun, June 2003. 

3.	 "High Throughput Evaluation of Novel 

Autothermal Reforming Catalysts for Fuel Cell 

Applications", Schwank, J., Tadd, A., Saraf, V., 

and Gould, B., EuropaCat-VI, Innsbruck, 

Austria, August 31- September 4, 2003. 

4.	 "Deactivation Mechanisms for Supported Gold 

WGS Catalysts", Kim, C. H., Bej, S. K., and 

Thompson, L. T., AIChE Annual Meeting, 

Indianapolis, IN, November 2002. 

 FY 2003 Progress Report 

5.	 "Function and Performance of Carbide Catalysts 

for the Water Gas Shift Reaction," Patt, J. J., and 

Thompson, L. T., AIChE Annual Meeting, 

Indianapolis, IN, November 2002. 

6.	 "Function of Carbide and Nitride Water Gas 

Shift Reaction Catalysts," Patt, J. J., Bej, S. K., 

and Thompson, L. T., Materials Research 

Society Fall Meeting, Boston, MA, December 

2002. 

7.	 "Deactivation Mechanisms for Supported Gold 

WGS Catalysts", Kim, C. H., Bej, S. K., and 

Thompson, L. T., MRS Fall Meeting, Boston, 

MA, December 2002. 

8.	 "Deactivation of Supported Water Gas Shift 

Gold Catalysts", Kim, C. H. and Thompson, L. 

T., ACS Spring Meeting, New Orleans, LA, 

March 2003. 

9.	 "Deactivation and Regeneration of 

Nanocrystalline Gold WGS Catalysts,” Kim, C. 

H., Bej, S. K., and Thompson, L. T., North 

American Catalysis Society Meeting, Cancun, 

June 2003. 

10. “Desulfurization of Transportation Fuels with 

Zeolites Under Ambient Conditions,” R. T. 

Yang, A. J. Hernandez-Maldonado and F. H. 

Yang, Science, 301, 79 (2003). 

11. “Desulfurization of Commercial Liquid Fuels by 

Selective Adsorption via p-Complexation with 

Cu(I)-Y Zeolite," A. J. Hernández-Maldonado 

and R. T. Yang, Ind. Eng. Chem. Res., 42, 3103 

(2003). 

12. “Desulfurization of Liquid Fuels by Adsorption 

via p-Complexation with Cu(I)-Y and Ag-Y 

Zeolites,” A. J. Hernández-Maldonado and R. T. 

Yang, Ind. Eng. Chem. Res., 42, 123 (2003). 

13. “Desulfurization of Transportation Fuels with 

Zeolites Under Ambient Conditions,” Yang, R. 

T., ACS Spring Meeting, New Orleans, LA, 

March, 2003, Award Address of ACS Award for 

Separation Science and Technology. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Sulfur Removal from Reformate 

Xiaoping Wang, Theodore Krause (Primary Contact), Romesh Kumar 

Argonne National Laboratory 

9700 South Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-4356; Fax: (630) 972-4463; E-mail: krause@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop a sulfur removal process for on-board fuel processing to meet DOE targets for hydrogen sulfide 

(H2S) removal to <10 ppbv H2S in reformate by 2010, a reactor volume of <0.06 L/kWe and weight of 

<0.06 kg/kWe, and operation at a gas-hourly space velocity (GHSV) of 50,000 h-1 . 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 J. Durability 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

Approach 

•	 Identified Cu oxides as candidate materials based on the H2S equilibrium partial pressure for candidate 

adsorbents (metal sulfide-H2S equilibrium). 

•	 Synthesize mixed metal oxides consisting of CuO/Cu2O and another transition metal oxide to stabilize 

copper in its oxide forms. 

•	 Conduct experimental studies in a microreactor system to evaluate the H2S concentration in the 

effluent as a function of temperature, flow rate, water content, and the gas composition for candidate 

mixed metal oxides. 

Accomplishments 

•	 Synthesized various mixed metal oxides consisting of CuO/Cu2O and screened them for H2S uptake in 

a microreactor system. 

•	 Determined the effects of operating temperature, flow rate, water content, and gas composition on the 

performance of H2S removal by a copper oxides-based composition. 

•	 Demonstrated that a copper oxides-based composition reduced H2S concentration from 10 ppmv to 

<50 ppbv from a simulated reformate. 

Future Directions 

•	 Evaluate H2S uptake for the materials supported on the structured form. 

•	 Characterize materials to improve performance and address stability issues. 

•	 Optimize the composition and materials processing and work with industrial collaborator. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

On-board reforming of gasoline is one option 

being considered for supplying H2 for polymer 

electrolyte fuel cell (PEFC) powered propulsion 

systems for automobiles and light-duty vehicles. 

Under reforming conditions, the sulfur present in 

gasoline is converted to H2S. Although new 

Environmental Protection Agency (EPA) regulations 

will reduce the sulfur content of gasoline to <80 

ppmw beginning in 2006, reformate produced from 

these gasolines will still contain ~10 ppmv H2S. 

Concentrations of H2S as low as 50 ppbv have been 

shown to irreversibly poison the PEFC catalysts.1 As 

a consequence, DOE has established a target of <10 

ppbv H2S in reformate by 2010. 

Two different approaches, liquid-phase 

desulfurization of the fuel prior to reforming2 and 

gas-phase desulfurization of reformate after 

reforming, are being considered for on-board sulfur 

removal. There is a concern with liquid-phase 

desulfurization that H2S will still need to be removed 

from reformate. Gas-phase desulfurization requires 

that the reforming catalyst be sulfur-tolerant. Our 

focus is on developing adsorbents for gas-phase 

desulfurization. 

Zinc oxide (ZnO) is used for sulfur removal in 

the production of H2 from natural gas for ammonia 

and methanol synthesis. For on-board fuel 

processing using ZnO, thermodynamic equilibrium 

predicts that a temperature of <250o

C is required to 

reduce the H2S concentration to <10 ppbv. We have 

observed that the concentration of H2S in reformate 

increased as the temperature decreased below 300o

C 

due to unfavorable kinetics, making ZnO unsuitable 

for on-board fuel processing.3

 Copper oxides (CuO 

and Cu2O) have among the highest sulfidation 

equilibrium constants for metal oxides and can 

potentially achieve parts-per-billion concentrations 

of H2S in reformate. However, under fuel processing 

conditions, Cu2O/CuO are reduced to metallic Cu. 

The sulfidation equilibrium for metallic Cu is 

significantly less than that of Cu oxides, resulting in 

reduced desulfurization efficiency. Research has 

focused on combining CuO/Cu2O with other metal 

oxides to stabilize the oxide form,4 which is the 

approach that we are investigating. 

 FY 2003 Progress Report 

Approach 

Compositions consisting of Cu and a second 

transition metal oxide dispersed on a high surface 

area support, such as γ−Al2O3, were prepared by 

either co-impregnation or successive impregnation 

methods using nitrate salts as precursors. The H2S 

desulfurization performance of these compositions 

was evaluated in a microreactor system. In a typical 

test, a sample of up to 2 mL was exposed to a 

synthetic reformate (10-40 ppmv H2S, 29% H2, 

20% H2O, 6% CO, 6.1% CO2, 0.2% CH4, balance 

N2) at temperatures ranging between 200-400oC and 

at GHSVs ranging between 2000-50,000 h-1 . The 

H2S concentration in the effluent from the reactor 

was measured using a gas chromatograph (GC) 

equipped with a flame photometric detector (FPD) 

with a detection limit of 200 ppbv H2S and an on-line 

lead-acetate based H2S analyzer with a detection 

limit of 20 ppbv H2S. 

Results 

Figure 1 shows a typical H2S breakthrough curve 

(i.e., H2S concentration in the effluent as a function 

of time) for these sorbents at 350oC and a GHSV of 

2000 h-1 with a feed H2S concentration of 40 ppmv. 

All compositions tested, including Cu alone, 

exhibited two stages of H2S breakthrough. During 

the first stage, they reduced the H2S concentration 

below detection limit of the FPD. During the second 

stage, they reduced the H2S concentration to ~10 

ppmv. The second stage is believed to be associated 

Figure 1. The H2S Breakthrough Curve for Cu+B at 

350o

C and a GHSV of 2000 h-1 

2 
 

 

 

Cu/Al2O3 258.8 36.3

202.3

201.5

211.3

199.5

197.9

Surface area 

(m2/g)

Cu+D/Al2O3 44.0

Cu+E/Al 32.8 2O3

Cu+A/Al 37.3 2O3

Cu+B/Al2O3 57.9

Cu+C/Al2O3 53.9

Sulfur uptake (%, based 

on Cu content) Sorbent formulation a

Hydrogen, Fuel Cells, and Infrastructure Technologies

with the sulfidation of metallic copper since the 

observed H2S concentration of 10 ppmv is close to 

that predicted by thermodynamic equilibrium (7.2-

10.6 ppmv at 350-380o

C) for metallic Cu; however, 

this has not been experimentally confirmed. These 

materials did show different sulfur uptake capacities 

as shown in Table 1. The highest sulfur uptake 

capacities were shown by compositions identified as 

Cu+B and Cu+C. 

The Cu+C system was chosen for further study 

to determine the effect of various operating 

parameters including temperature, GHSV, and the 

water content in reformate on H2S removal. 

Temperature significantly affected H2S removal 

performance, as shown in Figure 2. The H2S 

concentration was reduced from 10 ppmv to <50 

ppbv at 200 and 300o

C; however, a longer 

breakthrough time was observed at 200o

C, indicating 

a higher H2S uptake capacity. At 200oC, the 

reduction of copper oxides to metallic Cu is less 

favorable, suggesting more of the Cu may be in the 

oxide form, which would favor desulfurization. 

The effect of GHSV at 200o

C is shown in Figure 

3. Although breakthrough time decreased 

significantly as the GHSV was increased from 10,000 

to 50,000 h-1, similar sulfidation efficiencies (~20 

ppbv) and Cu utilizations (~60%) were observed at 

both GHSVs. When the temperature was increased to 

350o

C, the performance decreased significantly at the 

higher GHSV. The sulfidation efficiency was 25 ppbv 

and the Cu utilization was 15% at a GHSV of 10,000 

Table 1.	 Copper Utilization for Sulfidation of 

Binary Oxides of Copper and a Second 

Transition Metal 

 FY 2003 Progress Report 

h-1, which decreased to 200 ppbv and 5%, 

respectively, at a GHSV of 50,000 h-1 . This implies 

that lower operating temperatures are desirable if the 

GHSV target is to be met. 

The effect of the H2O concentration in the 

reformate on H2S removal performance is shown in 

Figure 4. The pre-breakthrough H2S concentration 

increased as the H2O concentration increased from 

11 to 30 vol%, consistent with the reaction 

equilibrium (e.g., Cu2O + H2S(g) = Cu2S + H2O(g) ). 

Since H2O is a product of the sulfidation reaction, 

increasing the H2O concentration in the reformate 

shifts equilibrium towards the reactants, leading to a 

higher H2S concentration. 

Figure 2.	 The Effect of Temperature on H2S 

Breakthrough for Cu+C at a GHSV of 

10,000 h-1 

Sorbent formulation Surface area 

(m2/g) 

Sulfur uptake (%, based 

on Cu content)a 

Cu+A/Al2O3 197.9 37.3 

Cu+B/Al2O3 199.5 57.9 

Cu+C/Al2O3 211.3 53.9 

Cu+D/Al2O3 201.5 44.0 

Cu+E/Al2O3 202.3 32.8 

Cu/Al2O3 258.8 36.3 

a

Calculated based on H2S uptake until breakthrough occurs 

(1 ppmv H2S). 

3 

Figure 3. The Effect of GHSV on H2S Breakthrough 

for Cu+C at 200oC 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 4.	 The Effect of H2O Concentration in the 

Reformate on H2S Breakthrough for Cu+C at 

350o

C and a GHSV of 10,000 h-1 

Conclusions 

•	 Binary oxides containing Cu are capable of 

reducing the H2S concentration from 10 ppmv 

to <50 ppbv in reformates containing 30% H2 

and 20% H2O at temperatures ranging from 

200-350oC and GHSVs ranging from 10,000-

50,000 h-1 . 

•	 Lower operating temperatures, lower H2O 

concentrations, and lower GHSVs are desirable 

to meet DOE targets. 

References 

1. Uribe, F.; Zawodzinski, T.; Valerio, J.; Bender, G.; 

Garzon, F.; Saab, A.; Rockward, T.; Adcock, P.; 

Xie, J., Smith, W. "Fuel Cell Electrode 

Optimization for Operation on Reformate and 

Air," FY 2002 Progress Report for Hydrogen, 

Fuel Cells, and Infrastructure Technologies 

Program, U.S. Department of Energy, Office of 

Hydrogen, Fuel Cells, and Infrastructure 

Technologies, Washington, D.C. 

 FY 2003 Progress Report 

2. Bonville, L.J.; DeGeorges, Jr., C.L.; Foley, P.F.; 

Garow, J.; Lesieur, R.R.; Reston, J.L.; 

Szydlowski, Jr., D.F. U.S. Patent 6,159,256, 2000. 

3. Carter, D.; Krause, T.; Mawdsley, J.; Kumar, R.; 

Krumpelt, M. "Sulfur Removal from Reformate," 

2001 Annual Progress Report, Fuels for Advanced 

CIDI Engines and Fuel Cells, U.S. Department of 

Energy, Office of Transportation Technologies, 

Washington, D.C. 

4. Li, Z.; Flytzani-Stephanopoulos, M. Ind. Eng. 

Chem. Res. 1997, 36, 187-196. 

FY 2003 Publications/Presentations 

1. X. Wang, T. Krause, and R. Kumar, "Sulfur 

Removal from Reformate," extended abstract, 

pre-prints, Petroleum Chemistry Division, the 

225th ACS National Meeting, New Orleans, LA, 

March 23-27, 2003. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Selective Catalytic Oxidation of Hydrogen Sulfide 

Timothy Armstrong (Primary Contact), Nidia Gallego, Steve Overbury, Bill Shelton, Xianxian Wu, 

and Andrew Kercher 

Oak Ridge National Laboratory 

P.O. Box 2008 

Oak Ridge, TN 37831 

Phone: (865) 574-7996; Fax: (865) 574-5310; E-mail: armstrongt@ornl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (865) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Develop activated carbon catalysts with controlled microstructures for selective oxidation of H2S to 

elemental sulfur. 

•	 Identify key microstructural and surface chemistry features of activated carbons that promote
 

hydrogen sulfide removal.
 

•	 Characterize the catalytic performance and reaction kinetics of commercial and laboratory-created 

activated carbons in model reformate gas streams. 

•	 Understand reaction mechanisms, and explore the key microstructural features of activated carbons 

and the key reaction mechanisms for H2S removal to the ppb level. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Fuel-Flexible Fuel Processors Barriers 

•	 J. Durability 

Component Barriers 

•	 P. Durability 

Approach 

•	 Produce activated carbons for hydrogen sulfide removal that have various pore size distributions, 

functional groups, and inorganic impurity levels. 

•	 Characterize the structure of commercial and laboratory-created activated carbons to be tested for 

catalytic oxidation of hydrogen sulfide. 

•	 Perform catalysis tests on commercial and laboratory-created activated carbons in model reformate 

gases and isolate the effects of activated carbon structure and pertinent gaseous species on H2S 

removal. 

•	 Use in-situ analytical techniques and molecular modeling to determine the dependence of reaction 

mechanisms on activated carbon structure. 

Accomplishments 

•	 Characterized the pore structure and carbon structure of several commercial and laboratorysynthesized activated carbons.
 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Preliminary results imply that using in-situ techniques such as diffuse reflectance mid-infrared Fourier 

transform spectroscopy (DRIFTS) holds promise in studying catalytic removal of H2S. 

•	 Designed and constructed a catalysis test system for catalytic oxidation of hydrogen sulfide in model 

reformate gas streams. 

•	 Used Reverse Monte Carlo analysis of diffraction data to simulate the structure of activated carbon. 

Future Directions 

•	 Isolate the importance of surface functionality and impurities on pertinent reactions for hydrogen 

sulfide removal using catalysis experiments and in-situ analytical techniques. 

•	 Synthesize several typical carbon-based catalysts from different sources under controlled activation 

processes. 

•	 Establish processes for modifying the functional group content and impurity level of activated carbons. 

•	 Determine optimal pore size distribution for maximum sulfur removal capacity. 

•	 Evaluate the effect of reaction conditions on the activity and selectivity of selected catalysts. 

•	 Study catalytic reaction kinetics and explore reaction mechanisms. 

Introduction 

Hydrogen is commonly produced by reforming 

natural gas; however, reformate contains impurities, 

such as hydrogen sulfide (H2S), which can poison 

shift catalysts and fuel cell electrodes. Even a low 

concentration (a few ppm) of hydrogen sulfide 

dramatically shortens the life of fuel cell catalysts. 

Major ongoing research efforts are seeking to 

develop fuel cell catalysts that are more sulfur 

tolerant. The mission of this research project is to 

develop an oxidative process to reduce sulfur levels 

to the parts per billion range using low-cost carbonbased catalysts. This project is a new start in FY 

2003, starting in March. 

Selective oxidation of hydrogen sulfide to 

elemental sulfur on an activated carbon catalyst has 

been identified as a highly promising approach for 

the purification of fuel cell feedstocks [1]. While 

activated carbons are commercially used for 

hydrogen sulfide removal from gas streams, the key 

mechanisms for hydrogen sulfide removal and the 

critical features in an activated carbon catalyst are 

not well understood. Research efforts often have 

relied solely on commercial activated carbons, and 

none of the past development efforts have evaluated 

the use of carbon as a catalyst. In addition, the 

results reported by various investigators are often 

diverse and contradictory, especially concerning 

kinetics and reaction pathways. This project will 

emphasize the design and development of low-cost, 

regenerative, carbon-based catalysts that meet the 

required characteristics for reducing sulfur in fuel 

cell feedstocks to desired level. A variety of 

activated carbons from different sources of carbon 

and different activation processes will be synthesized 

and evaluated. The effect of operating parameters on 

the activity and selectivity of catalysts will be 

evaluated using DRIFTS (diffuse reflected infrared 

Fourier transform spectroscopy) (Figure 1). Based 

on the achievement of carbon materials with the 

Figure 1. Picture of DRIFTS System 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

desired structure and surface chemistry, new insights 

will be provided to clarify the reaction mechanisms. 

Approach 

The assembled research team allows for a 

processing-to-product approach to tackle the timely 

issue of hydrogen sulfide removal from reformate 

feedstocks of hydrogen. The feedback between 

materials processing, molecular modeling, reaction 

mechanism studies, and engineering evaluation 

provides a synergistic approach for the development 

of an activated carbon catalyst. 

Different precursors and variations in activation 

conditions can produce dramatically different 

microstructures in carbon materials. A focused effort 

to identify their relationships and the influence of the 

resultant pore structure (pore volume, pore size and 

distribution) on the performance of carbon catalyst is 

necessary. Surface functional groups play an 

important role in the catalytic activity of the catalyst 

[2]; thus, it is important to identify the initial surface 

functional groups and then develop techniques to 

modify or alter surface functionality. To produce an 

optimal activated carbon catalyst, the functional 

group content should be tailored to optimize 

hydrogen sulfide adsorption and minimize side 

reactions, such as adsorption of CO and H2O, that 

could result in the formation of sequestered hydrogen 

sulfide products. 

Inorganic impurities have also been shown to 

strongly catalyze hydrogen sulfide oxidation [3]. In 

order to understand the influence of catalytic 

impurities on the reactions of interest, highly pure 

carbons will need to be synthesized to isolate their 

effects. Inorganic impurities must also be added to 

activated carbons in order to elucidate their role in 

adsorption and catalysis. It is commonly accepted 

that metal impurities in activated carbons play 

important roles in catalytic performance. Key issues 

that must be clarified include 1) identification of the 

reaction mechanisms associated with specific 

impurities, 2) the activity and selectivity of those 

impurities, and 3) the efficacy of these impurities 

after extensive sulfur deposition and catalyst 

regeneration. 

 FY 2003 Progress Report 

Reaction mechanisms will be determined using a 

combination of catalytic reactor experiments on 

simple gas mixtures, in-situ analytical techniques 

(such as DRIFTS), and molecular modeling. 

Together, these techniques can isolate individual gascarbon reactions, explore competition between gases 

for reaction sites, determine the mechanisms for 

deleterious side reactions, and predict ideal carbon 

structures for H2S removal. This combination of 

analysis methods provides multiple perspectives of 

catalyst reactions, ranging from idealized 

thermodynamic reaction predictions to measured 

catalyst surface interactions to an overall perspective 

of downstream gas composition. Key reaction 

parameters include temperature, pressure, oxygen 

concentration, H2S concentration, water content, and 

the concentration of other impurities. 

Ultimately, an activated carbon catalyst is only 

successful for hydrogen sulfide removal if it can 

perform to required concentrations in an actual 

reformate gas stream for a reasonable time period 

using a practical reactor geometry. A catalyst must 

remove and retain hydrogen sulfide in the presence 

of the wide range of impurities found in reformate 

feedstocks. Optimized activated carbon catalysts 

will be tested on simulated reformate feedstocks of 

hydrogen. The potential of promising catalyst 

candidates for regeneration also needs to be 

explored. Partnering with laboratories and industry 

will be explored as a means to evaluate downselected catalysts on actual reformed gas streams. 

Results 

The porosity and carbon structure of several 

commercial and laboratory-created activated carbons 

have been determined. Typical results are listed in 

Table 1 and Table 2. The activated carbons are 

derived from different precursors (pitch-derived 

carbon, coconut shell carbon, coal, and low-ash 

charcoal) in order to determine the effects of 

common inorganic impurities. Also, preliminary 

experiments have sought to accurately determine 

their functional group content. 

An in-situ study has been initiated to understand 

the interaction of gas species such as H2S, O2 and 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

 Table 1. X-ray Diffraction Parameters of Assorted Commercial and Laboratory Activated Carbons 

Precursor Interplanar 

spacing (nm) 

Crystallite 

height (nm) 

Crystallite 

diameter (nm) 

Anshan 1000 m2

/g pitch fiber 0.3667 1.127 1.775 

Anshan 1500 m2

/g pitch fiber 0.3660 1.134 1.803 

Calgon Centaur 4x6 coal 0.3574 1.157 1.813 

Calgon OLC 12x40 coconut shell 0.3662 1.080 1.810 

Calgon OVC 4x10 coconut shell 0.3764 1.107 1.847 

ORNL SMM-19 carbon fiber monolith 0.3742 1.058 1.757 

ORNL SMS-48 carbon fiber monolith 0.3743 1.081 1.736 

PICA G55C-1 coconut shell 0.3737 1.037 1.821 

PICA VA507 coconut shell 0.3767 1.053 1.886 

Westvaco 

Ultramicroporous 

wood - - 1.720 

 Table 2. Pore Structure Characterization of Assorted Commercial and Laboratory Activated Carbons from Nitrogen 

Adsorption Analysis 

BET surface area 

(m2

/g) 

D-R micropore volume 

(cc/g) 

D-A average pore 

diameter (Å) 

Anshan 1500 m2

/g 1393 0.756 22.3 

Calgon Centaur 4x6 1144 0.506 21.3 

Calgon OLC 12x40 1110 0.506 21.3 

Calgon OVC 4x10 884 0.391 19.7 

ORNL SMM-19 1730 0.895 22.8 

ORNL SMS-48 1404 0.619 20.7 

CO with carbon surface and interpret the reaction 

mechanisms of H2S oxidation and undesired side 

reactions for the formation of COS and SO2. A 

DRIFTS reactor which is capable of in-situ 

measurement up to 500°C is being used to identify 

the change of carbon surface chemistry in various gas 

atmospheres. A preliminary study on the interaction 

of CO with activated carbon has provided positive 

support for this approach, and typical results are 

shown in Figure 2. 

Reverse Monte Carlo modeling has been applied 

to diffraction data to produce a theoretical activated 

carbon microstructure. By introducing select 

modifications to theoretical microstructures, carbon 

microstructural variables can be kept constant except 

for a specific feature of interest (functional group 

content, pore size, carbon structural order, etc.), and 

the effect of specific feature changes on the 

thermodynamics and kinetics of H2S removal can be 

predicted. Slight modifications of these theoretical 

microstructures will later be used to model the 

behavior of actual activated carbons by incorporating 

the measured microstructural features of activated 

carbons. 

A catalytic reactor system for hydrogen sulfide 

has been designed and is being constructed. A 

schematic representation of the system is shown in 

Figure 3. 

Figure 2. Preliminary Results on the Interaction of CO 

with Activated Carbon Observed by DRIFTS

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Schematic Representation of the Experimental 

Setup for Testing Carbon-Based Catalyst 

(FTIR=Fourier transform infrared) 

Conclusions 

•	 The microstructures of several activated 

carbon materials have been characterized for 

subsequent correlation to catalysis results. 

•	 Preliminary results imply a promise of using insitu techniques such as DRIFTS in studying 

catalytic removal of H2S. 

•	 Reverse Monte Carlo methods have been applied 

to diffraction data to create a theoretical model of 

the microstructure of activated carbon in order to 

identify reaction sites. 

FY 2003 Publications/Presentations 

1. Gardner TH, Berry DA, Lyons KD, Beer SK, 

Freed AD. Fuel processor integrated H2S 

catalytic partial oxidation technology for sulfur 

removal in fuel cell power plants, Fuel, 81, 2157­

2166 (2002). 

2. Rodriguez-Reinoso F. The role of carbon 

materials in heterogeneous catalysis, Carbon, 36, 

159-175 (1998). 

3. Steijns M, Mars P. Catalytic oxidation of 

hydrogen sulfide: Influence of pore structure and 

chemical composition of various porous 

substances, Industrial and Engineering 

Chemistry Product Research and 

Development, 16, 35-41 (1977). 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Effects of Fuel Constituents on Fuel Processing Catalysts 

John P. Kopasz (Primary Contact), Daniel Applegate, Laura Miller, Cécile Rossignol 

Argonne National Laboratory 

9700 South Cass Avenue 

Argonne, IL 60439 

Phone: (630) 252-7531; Fax: (630) 972-4405; E-mail: Kopasz@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Determine the effects of the major constituents, additives, and impurities in petroleum fuels on fuel 

processor performance and durability. 

•	 Collaborate with major oil companies on the development of future fuels for fuel cell vehicles. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Durability 

•	 K. Emissions and Environmental Issues 

•	 M. Fuel Processor System Integration and Efficiency 

• N. Cost 	 

Approach 

•	 Investigate reforming the major components of gasoline under controlled conditions in a microreactor. 

•	 Determine the dependence of product gas composition on temperature and space velocity. 

•	 Test simple mixtures of components, impurities, and additives to determine their synergistic or 

poisoning effects. 

•	 Test complex refinery blends to determine which streams are most attractive for on-board reforming. 

•	 Conduct long-term (1000-h) tests to determine catalyst poisoning and other degradation effects over time. 

Accomplishments 

•	 Determined that antioxidant additives have little or no effect on reforming at temperatures >750oC and 

gas-hourly space velocities (GHSVs) <50,000 h–1; however, they can decrease hydrogen yield at 

lower temperatures or higher GHSVs. 

•	 Discovered that pyridine decreases the rate of isooctane reforming, even at 800oC. 

•	 Examined reforming refinery streams and refinery blends supplied by major oil companies. 

•	 Investigated the long-term effects of detergent additives on reforming. 

•	 Developed an understanding of reforming binary mixtures in terms of the effects of competition for the 

limited number of active sites on the catalyst. 

•	 Demonstrated that aromatics and naphthenes decrease the rate of reforming of isooctane on advanced 

bimetallic catalysts, as well as on Pt-based catalysts. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Investigate the long-term effects of antioxidant additives and heterocyclic impurities. 

• Develop a reforming model that can predict the performance of complex fuel mixtures. 

• Investigate reforming binary/ternary mixtures and additives with advanced catalysts. 

Introduction 

Fuel cell vehicles offer the potential for very low 

emissions and high fuel economies. Efficiency and 

emissions, however, are affected by the fuel used. 

With hydrogen as the on-board fuel, the lowest 

vehicle emissions (zero) and the highest fuel 

economy can be obtained. In the absence of a 

hydrogen production, delivery, and marketing 

infrastructure, on-board reforming of hydrocarbon 

fuels (e.g., gasoline) is a potential transitional 

solution for the near-term introduction of fuel cell 

vehicles. The goals of this project are to identify the 

desirable and undesirable constituents of gasoline 

and develop specifications for a hydrocarbon fuel 

especially suitable for fuel cell vehicles. 

Our previous work indicated that there are 

significant differences in how readily the major types 

of hydrocarbons in gasoline (paraffinic, aromatic, 

naphthenic, and olefinic) can be reformed.1,2 Tests 

on refinery blends indicated that fuels high in 

aromatic content were more difficult to reform and 

that aromatics affected the rate at which paraffinic 

species could be reformed.2 We have expanded our 

study to investigate the effects of gasoline additives 

and impurities on reformer performance. 

Approach 

The reformability of various fuel mixtures was 

measured at Argonne National Laboratory (ANL) 

under autothermal reforming conditions. These 

studies were conducted at 600-800°C and GHSVs 

between 15,000 and 150,000 h-1 (corresponding to 

reactor residence times of approximately 200 to 

20 milliseconds) and involved various blends of 

isooctane with aromatic, naphthenic, N-containing 

heterocycle, and oxygenate compounds, as well as 

surrogates for the additives used in gasoline. 

Results 

Antioxidants. We investigated the reforming of 

isooctane-phenol solutions over a Pt-ceria-based 

catalyst to determine the effects of phenol-based 

antioxidants. The phenol concentration was 

~100 ppm, an order of magnitude higher than in 

gasoline, to accelerate catalyst degradation. A 

comparison of the product gas compositions from 

reforming these solutions at 800oC and various space 

velocities is shown in Figure 1. The hydrogen 

content of the product gas decreased with the 

addition of phenol for GHSV >50,000 h-1 . In 

addition, CO levels decreased throughout the GHSV 

range. Hydrogen yields for pure isooctane and 

isooctane + phenol were close to the theoretical 

maximum yields at 750 and 800oC and GHSVs 

below 50,000 h-1, but dropped off with decreasing 

temperature. The decrease accelerated with the 

phenol additive. 

A plot of the difference in the H2 yield between 

isooctane and isooctane + phenol as a function of 

Figure 1.	 Product Gas Compositions from Reforming 

Isooctane and Isooctane + 111-ppm Phenol 

over a Pt Catalyst at 800oC for Various Space 

Velocities 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

temperature and GHSV is shown in Figure 2 (% 

difference = (PH2(C8+phenol) – PH2(C8))/PH2(C8)×100). 

This plot shows that the additive had no effect on 

hydrogen yield at 750 to 800oC and 15,000 to 50,000 

h-1 GHSV. However, the phenol additive decreased 

the hydrogen yield at higher space velocities or lower 

temperatures. This is partly due to a decrease in the 

rates of feed hydrocarbon breakdown. With pure 

isooctane, no hydrocarbons higher than C6 were 

observed in the product gas, whereas with phenol 

present, fragments as large as C7H15 were observed. 

Heterocyclic impurities. The effect of pyridine, a 

nitrogen heterocyclic impurity in gasoline, was 

investigated by reforming mixtures containing 50­

ppm pyridine in isooctane. The difference in 

hydrogen yield with and without pyridine is shown in 

Figure 3. The hydrogen yield decreased substantially 

over most of the operating space, even at high 

temperatures and low space velocities. 

Fuel composition. Our previous work had shown 

that aromatic and naphthenic constituents decreased 

the rate of reforming isooctane over a Pt-ceria-based 

catalyst.2,3,4 To determine if this is true for 

autothermal reforming in general, we investigated 

the reforming of isooctane-xylene and isooctanemethylcyclohexane mixtures over a bimetallic Pt-Rh 

catalyst. This bimetallic catalyst has substantially 

higher activity than the Pt catalyst, yielding 80–90% 

of the theoretical maximum hydrogen yield at 600oC 

and 150,000 h-1 GHSV. In comparison, the Pt 

catalyst yielded less than 60% of the theoretical 

 FY 2003 Progress Report 

maximum hydrogen at 650oC and the same GHSV. 

The bimetallic catalyst was tested for reforming 

isooctane, isooctane + xylene (20%), and isooctane + 

methylcyclohexane (20%). 

The addition of xylene decreased the hydrogen 

yield at high GHSVs (>75,000 h-1) and low 

temperatures, as shown in Figures 4(a) and 4(b). 

Hydrogen yields fall below 90% of the theoretical 

maximum at 750oC and a GHSV of 150,000 h-1 . 

This decrease is believed to be due to competitive 

reactions at the catalyst sites. Aromatics interact 

more strongly with the metal centers and decrease the 

number of available reaction sites for the less 

strongly adsorbing paraffins. The naphthenes 

dehydrogenate to form aromatics, which then 

compete with the paraffins for the catalytic sites. 

Conclusions 

•	 Antioxidant additives in gasoline have been 

found to decrease hydrogen yield in the 

reformate, but only at high GHSVs and/or low 

reforming temperatures. 

•	 Pyridine decreased hydrogen yield, even at low 

GHSV and high temperature. 

•	 Aromatic and naphthenic components decreased 

the rate of paraffin reforming, even when using 

advanced bimetallic catalysts. 

Figure 2.	 Difference in the H2 Yield between Isooctane 

and Isooctane + Phenol as a Function of 

Temperature and GHSV 

Figure 3.	 Difference in the H2 Yield between Isooctane 

and Isooctane + 50-ppm Pyridine as a 

Function of Temperature and GHSV 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 4.	 Hydrogen Yield as a Percentage of the 

Maximum Theoretical Hydrogen Yield 

Obtainable from Reforming (a) Isooctane and 

(b) Isooctane + 20% xylene over an 

Advanced Bimetallic Catalyst 

References 

1. J. P. Kopasz, S. Ahmed, M. Krumpelt, and P. 

Devlin, "Challenges in Reforming Gasoline: All 

Components Are Not Created Equal," SAE 

Technical Paper Series, 2001-01-1915 (2001). 

2. J. P. Kopasz, L. E. Miller, S. Ahmed, P. Devlin, 

and M. Pacheco, "Reforming Petroleum-based 

Fuels for Fuel Cell Vehicles: CompositionPerformance Relationships," SAE Technical 

Paper Series, 2002-01-1885 (2002). 

3. R. Borup, M. Inbody, L. Brown, B. Morton, T. 

Semelsberger, L. Perry, and J. Parkinson, "Testing 

of Fuels in Fuel Cell Reformers," 2001 Annual 

Progress Report for Fuels for Advanced CIDI 

Engines and Fuel Cells, Energy Efficiency and 

Renewable Energy, Office of Transportation 

Technologies, U.S. Department of Energy, 

Washington, DC (2001). 

4. J. P. Kopasz, L. E. Miller, and D. Applegate, 

"Effects of Multicomponent Fuels, Fuel Additives 

and Fuel Impurities on Fuel Reforming," SAE 

Technical Paper Series, 2003-FTT-56 (2003). 

FY 2003 Publications/Presentations 

1. S. Ahmed, J. Kopasz, R. Kumar, and M. 

Krumpelt, "Water Balance in a Polymer 

Electrolyte Fuel Cell System," J. Power Sources, 

112, 519-530 (2002). 

2. M. Pacheco, J. Sira, J. Kopasz, and S. Ahmed, 

"Reaction Kinetics and Reactor Modeling for Fuel 

Processing of Liquid Hydrocarbons for Fuel Cell 

Applications: Isooctane Reforming," Applied 

Catalysis, accepted for publication. 

3. J. P. Kopasz, L. Miller, and D. Applegate, "Effects 

of Additives and Impurities on the Reforming of 

Gasoline," 2003 AIChE Spring National Meeting, 

2nd Topical Conference on Fuel Cell Technology, 

New Orleans, LA (2003). 

4. J. P. Kopasz, L. E. Miller, and D. V. Applegate, 

"Effects of Multicomponent Fuels, Fuel 

Additives, and Fuel Impurities on Fuel 

Reforming," SAE Future Transportation 

Technology Conference (2003). 

5. J. P. Kopasz, L. E. Miller, and D. V. Applegate, 

"How Fuel Composition Affects On-Board 

Reforming for Fuel Cell Vehicles," SAE 

Powertrain and Fluid Systems Conference and 

Exhibition (2003). 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Testing of Fuels in Fuel Cell Reformers 

Rod Borup (Primary Contact), Michael Inbody, Troy Semelsberger, José Tafoya, Will Vigil, 

Dennis Guidry and Susan Pacheco 

MST-11, MS J579 

P.O. Box 1663 

Los Alamos National Laboratory 

Los Alamos, NM 87545 

Phone: (505) 667-2823; Fax: (505) 665-9507; E-mail: Borup@lanl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-1637; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Quantify fuel effects on fuel processor performance and durability 

- Measure fuel component, impurity, additive effects 

- Examine fuel effects on fuel processor start-up 

•	 Understand parameters that affect fuel processor and stack lifetime and durability 

- Measure fuel processor catalyst stability and activity 

- Evaluate fuel effect and start-up effect on carbon formation 

- Identify chemical species limiting durability 

- Test durability to evaluate long term performance 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cell section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-up/Transient Operation 

•	 J. Durability 

•	 M. Fuel Processor System Integration and Efficiency 

• N. Cost 	 

Approach 

•	 Examine fuel effects on fuel processing by testing fuels in catalytic and gas phase oxidation and 

reforming reactors 

- Examine individual fuel components, component blends 

- Examine 'real' fuels (reformulated gasoline, naphtha) 

- Examine fuel additives (anti-oxidants, detergents, impurities) 

•	 Examine fuel effect on fuel reformer light-off and start-up 

- Measure fuel light-off temperature 

- Measure carbon formation during fuel processor light-off 

•	 Model and measure carbon formation 

- Model carbon formation equilibrium 

- Measure carbon formation during fuel vaporization 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- Measure carbon formation during start-up of fuel processor 

• Examine reforming of fuels at low temperatures for portable power applications 

Accomplishments 

• Measured carbon formation during vaporization process of hydrocarbon fuels 

• Measured carbon formation during start-up of fuel processor 

• Examined effect of fuel components on light-off temperature and start-up 

- Delineated straight-chained hydrocarbons vs. branched chains and aromatic compounds 

- Oxygenated fuel components 

- Additives and impurities such as detergents and sulfur 

• Compared gas phase oxidation and catalytic oxidation with different fuel components 

• Examined the reforming of fuels at low temperatures for portable power applications 

Future Directions 

• End task on Testing of Fuels in Fuel Cell Reformers 

- Summarize and publish final results 

• Focus on H2 durability of PEM Fuel Cells 

- Single cell MEA durability 

- Short stack Durability 

- Drive cycle testing of MEAs 

- MEA and GDL evaluation and characterization 

- Off-line and accelerated durability testing 

Introduction 

The goal of this research is to explore the effects 

of fuels, fuel constituents, additives and impurities on 

the performance of on-board hydrogen generation 

devices and, consequently, on the overall 

performance of a PEM fuel cell system using a 

reformed hydrocarbon fuel. Understanding the 

performance of fuels and their effects on the 

durability of PEM fuel cell systems is key for their 

commercial introduction and use. A fast start-up 

time of the fuel processor systems is crucial for their 

use in automotive fuel cell applications. Energy 

consumption, carbon formation, start-up time and 

limits on durability are all potential effects of fuel 

composition on the fuel processor during the start-up 

and light-off of fuel processors. 

Approach 

To examine the effect of fuel on hydrogen 

generation devices, various fuel components, 

mixtures, and real fuels have been tested in 

automotive-scale autothermal (ATR) fuel reformers. 

The focus of the testing is to examine fuel effects on 

start-up performance and factors that limit durability. 

Start-up time and durability are critical aspects of 

reformer performance for onboard vehicle operation. 

Carbon formation can significantly limit durability. 

Fuel effects on carbon formation were examined by 

measuring carbon formed during fuel vaporization of 

various fuel components and mixtures and by 

measuring carbon formed in the start-up of an ATR 

fuel reformer. The carbon formed was measured by 

2 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

physical collection and by in situ laser scatteringextinction measurements in the ATR experiments. 

The light-off temperature of the ATR catalyst is a 

significant factor in its start-up performance. Thus, 

light-off temperatures were measured for fuel 

components, component blends, and real fuels in an 

isothermal catalyst test reactor. 

The effect of fuel composition on fuel processor 

operating temperature and stability was compared 

between a catalytic partial oxidation reactor and a 

gas-phase partial oxidation reactor, both automotivescale. Fuel composition effects were delineated by 

matching performance of real fuels with blended 

component mixtures. 

Results 

In autothermal reforming, proper fuel/steam/air 

mixture preparation is critical to avoid hot/cold spots, 

carbon formation, and catalyst degradation and to 

obtain proper conversion of hydrocarbons. 

Vaporization is one method to introduce fuel into a 

reformer, however it may lead to fuel pyrolysis, thus 

forming particulates or carbon during vaporization. 

Figure 1 compares the carbon formation measured 

during vaporization and refluxing of fuels and fuel 

components. In general, pure hydrocarbons did not 

show carbon formation, while real fuels did show 

carbon formation during the vaporization. The 

higher hydrocarbon streams such as kerosene and 

diesel fuel had more carbon formation than 

reformulated gasoline (RFG) or kerosene and diesel 

fuel in which sulfur had been removed. To suppress 

carbon formation with these fuels that pyrolyze, 

direct fuel injection into the authothermal reformer 

may be required instead of prior fuel vaporization. 

The start-up of the fuel processor system is 

critical for commercialization. During the start-up 

process, water may not be available. Without water 

it is impossible to light off a fuel processor at rich 

operating conditions and avoid regimes where carbon 

formation is favored by chemical equilibrium. Fuel 

effects on carbon formation during start-up were 

quantified for different fuel compositions using an 

ATR reactor. These measurements were made at 

steam/carbon ratios of 0.0 and 0.5, simulating low 

water light-off of the reactors. The carbon formed is 

 FY 2003 Progress Report 

Figure 1.	 Carbon Formation Measured During Fuel 

Vaporization and Refluxing of Fuel 

Components 

summarized in Figure 2. Ethanol addition to isooctane and RFG helps suppress carbon formation, 

while the addition of aromatic compounds or longerchained hydrocarbon (dodecane) leads to increased 

carbon production. 

Under rich operating conditions, catalysts require 

pre-heating before the oxidation reaction lights off, 

creating a self-sustaining exothermic reaction. The 

amount of preheat required is a factor in the start-up 

time and energy. Figure 3 shows measured light-off 

temperatures for various hydrocarbon fuel 

constituents. Straight-chained hydrocarbons are 

observed to light off at lower temperatures than 

similar branched-chained hydrocarbons. Aromatics, 

such as xylene and methylnaphthalene, increased the 

light-off temperature. 

Figure 4 shows the change in the light-off 

temperature by the addition of oxygenated 

hydrocarbons and sulfur-containing hydrocarbons to 

iso-octane. The addition of oxygenated 

hydrocarbons, such as ethanol or methanol, to either 

Figure 2. Fuel Composition Effect on Carbon 

Formation During Start-Up of ATR Reactor 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Fuel Composition Effect on ATR Light-Off 

Temperatures by Straight-Chained Aliphatic, 

Branched-Chained Aliphatic and Aromatic 

Hydrocarbons Figure 5.	 Comparison of Fuel Composition Effect of 

Heavy And Light Straight-Chained 

Hydrocarbon on Gas Phase Partial Oxidation 

Figure 4.	 Fuel Composition Effect on ATR Light-Off 

Temperatures by Oxygenated Hydrocarbons 

and Sulfur Containing Hydrocarbons 

Figure 6. Comparison of Low-Temperature Reforming 

Fuels, Methanol And Dimethylether 

iso-octane or RFG reduced the light-off temperature, 

with greater concentrations reducing the light-off 

temperature to a greater extent. The addition of 

sulfur-containing hydrocarbons at low concentrations 

(100 ppm S) reduced the light-off temperature, while 

higher concentrations (1000 ppm S) increased the 

light-off temperature. 

In FY2002, we observed that during gas phase 

partial oxidation, real fuel blends operated stably at 

lower oxygen-to-carbon (O/C) ratios than pure 

components, such as iso-octane, opposite to the trend 

for catalytic partial oxidation. To delineate this 

effect, pentane (short-chained) and dodecane (longchained) hydrocarbons were added to iso-octane and 

tested over a range of O/C ratios in the gas phase 

partial oxidation reactor. Figure 5 shows that the 

addition of dodecane increased the range of O/C ratio 

at which the gas phase partial oxidation reactor could 

operate, while pentane did not. Thus the long-chain 

hydrocarbons in real fuels increase the range of O/C 

ratio for gas phase partial oxidation, which is 

reflected in the relative cetane number of the fuel, a 

measure of the ignition delay. 

Fuels such as gasoline and diesel fuel require 

high temperature reforming reactions. For portable 

power applications, there is interest in developing 

lower temperature reformers. Figure 6 shows a 

comparison of two fuels that reform at low 

temperature, methanol and dimethylether (DME). 

Full conversion of methanol was observed by about 

205o

C, while 360oC was required for DME. While 

DME requires a higher operating temperature, it does 

not have the toxicity issues that methanol has, and it 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

still reforms at a significantly lower temperature than 

hydrocarbons containing carbon-carbon bonds. 

Conclusions 

Fuel effect on catalytic light-off has been 

measured for a large number of different 

components. Straight-chained hydrocarbons have a 

lower light-off temperature than similar carbon 

number branched-chained hydrocarbons. Aromatics 

require higher light-off temperatures, while 

oxygenated compounds lower the light-off 

temperatures. 

Carbon formation was measured for various 

hydrocarbon compositions and operating conditions. 

Carbon formation was also measured during the fuel 

processor start-up transient. Aromatics show the 

highest tendency for carbon formation, while 

oxygenates help suppress carbon formation during 

light-off. 

Fuel composition effects have been measured for 

their relative kinetics during catalytic and gas phase 

oxidation and reforming. Gas phase oxidation favors 

real fuel mixtures with longer-chained hydrocarbons 

over gasoline-sized hydrocarbons such as iso-octane. 

Steam concentration has a large effect on gas phase 

 FY 2003 Progress Report 

oxidation, while its effect on catalytic oxidation is 

not large. Catalytic oxidation favors short-chained 

aliphatic hydrocarbons, while aromatics and longchained hydrocarbons have lower catalytic kinetics. 

FY 2002 Publications/Presentations 

1. 2002 American Chemical Society Meeting, 

Boston, Massachusetts, August 18-22. 

2. 2002 Fuel Cell Seminar Poster, Palm Springs, 

California, Nov. 17-21. 

3. Department of Defense Logistic Fuel Reforming 

Conference, Panama City Beach, Florida, August 

27. 

4. Spring 2003, American Institute of Chemical 

Engineers, New Orleans, Louisiana, March 30-

April 3. 

5. Hydrogen Production and Northwest 

Transportation Meeting, Seattle, Washington, 

June 16. 

6. 2003 SAE Powertrain & Fluid Systems 

Conference, October 27-30, Pittsburgh, 

Pennsylvania, SAE paper 2003-01-3271. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of Reaction Kinetics for Diesel-Based Fuel Cell Reformers 

David A. Berry (Primary Contact), Dushyant Shekhawat, Todd H. Gardner 

National Energy Technology Laboratory 

P. O. Box 880 

3610 Collins Ferry Road 

Morgantown, WV 26507-0880 

Phone: (304) 285-4430; Fax: (304) 285-4403; E-mail: david.berry@netl.doe.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop reaction kinetics, predictive models, and test methods for diesel fuel reforming and provide 

necessary tools and information to fuel reforming developers and fuel cell system integrators for 

technology development, performance optimization, and system control. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 M. Fuel Processor System Integration and Efficiency 

Approach 

•	 Conduct process optimization study for the diesel autothermal reforming. 

•	 Carry out kinetic measurements of representative model compounds. 

•	 Develop a level-1 kinetic model with a benchmark fuel (diesel). 

•	 Build liquid hydrocarbon characterization capability. 

Accomplishments 

•	 Tested three model compounds from the major representative functional groups in diesel fuel. 

•	 Developed surface response maps for steam reforming, partial oxidation and autothermal reforming 

(ATR) using Pt/γ-alumina catalysts for n-tetradecane, 1-methylnaphthalene, and decalin. 

•	 Built liquid hydrocarbon characterization capability. 

Future Directions 

•	 Evaluate other fuel compounds within a classification to examine if similar reforming behavior exists. 

•	 Conduct combinatorial fuel compound studies. 

•	 From response mapping, develop intrinsic reaction models for particular catalyst types. 

•	 Collaborate with Las Alamos National Laboratory to provide carbon deactivation kinetics. 

•	 Collaborate with Argonne National Laboratory to obtain experimental reactor performance data to 

validate reaction models and provide for fuel reactant mixing modeling capability suitable for 

computational fluid dynamic (CFD) modeling codes. 

•	 Develop a detailed kinetic model that incorporates CFD. 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

The fuel processor is a critical component of fuel 

cell systems. The processor must be able to provide 

a clean, tailored synthesis gas to the fuel cell stack 

for long-term operation. Key characteristics desired 

for the processor (and the system) include low cost, 

high efficiency, maximum thermal integration, low 

maintenance intervals, and acceptable startup and 

transient response. There are also several barrier 

issues that must be overcome to achieve these 

characteristics. Carbon formation, particularly upon 

startup, must be minimized to avoid coking of the 

catalysts in the reformer and downstream fuel cell. 

Fuels containing sulfur can poison both the 

reforming catalysts and the fuel cell anode. High 

thermal mass components (some of which may have 

heat-ramp restrictions) can limit startup times and 

transient response. And finally, cost targets must be 

achieved to ensure commercial success. 

Fundamental understanding for design and 

operation of reformers is important for successful 

technology development. One of the most 

fundamental engineering design parameters that can 

be measured in the laboratory is the intrinsic kinetics 

of a catalyst system. Once established for a 

particular feedstock and catalyst system, it can be 

coupled with computational fluid dynamics (CFD) 

code to effectively design, optimize, and minimize 

hydrocarbon slip in autothermal reformer systems. 

In principle, the kinetics of NOx formation, sulfur 

poisoning, carbon formation and catalyst aging can 

be added to allow for a complete predictive model for 

reformer performance and operation. 

However, modeling of reforming systems is 

extremely complicated. Diesel fuel consists of a 

complex variable mixture of hundreds of 

hydrocarbon compounds containing mainly olefins, 

saturates and aromatics. Empirical expressions for 

space velocity or simple power law-type models are 

typically used to design reformers. Unfortunately, 

these tend to be limited to a specific catalyst, fuel 

composition, and operating point. Therefore, the 

development of validated predictive models that can 

account for variations in these parameters is 

necessary. 

For the autothermal reforming of diesel with 

steam and oxygen, a complex reaction network is 

expected. Elucidation of this network and the 

development of a generalized complex network 

model for platinum catalysts will be the initial focus 

of this project. The overall kinetic approach 

employed will balance the level of detail that can 

accurately be accommodated by CFD code with the 

ability to easily update kinetic parameters for a new 

catalyst system. 

Approach 

To select an appropriate model, it is necessary to 

understand the reaction mechanisms and pathways 

for the chemical system. One approach to gaining 

that understanding is surface response mapping. 

This is a statistical technique used to map 

characteristic responses (e.g. yield, conversion, 

carbon buildup, etc.) to input variables (O2/C, H2O/ 

C, temperature, space velocity, etc.) over a defined 

region. It identifies the significance of parameters 

and their interactions. Also, it provides data that can 

lead to validation of kinetic models and can test the 

statistical significance of proposed reaction 

pathways. As the most important mechanisms and 

reaction pathways are defined, appropriate models 

will be selected to develop the model. Kinetic 

measurements of single component or individual 

reaction systems will be developed and used to 

validate the model. This will initially be done for a 

platinum catalyst and extended to other catalyst 

systems as needed to complete the model. 

A fixed bed reactor system was used to conduct 

the experiments. The reactor was operated 

continuously at steady state. γ-Alumina supported 

platinum (0.611 wt%) catalyst (surface area 103 

m2

/g) was used in this study as a base catalyst. A 

summary of reaction conditions is given in Table 1. 

Individual model compounds representing each 

organic class in diesel were subjected to autothermal, 

partial oxidation, and steam reforming at the 

temperatures and space velocities given in Table 1. 

Tetradecane, decalin, and 1-methylnaphthalene were 

identified as model compounds to represent 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

paraffins, naphthenes, and aromatics, respectively, 

found in diesel. 

Table 1. Experimental conditions 

Paraffin Aromatic Naphthene 

Model 

Compound 

nTetradecane 1-methyl 

naphthalene Decalin 

O2/C POX 0.5 0.5 0.5 

SR 0 0 0 

ATR 0.3 0.3 0.3 

H2O/C POX 0 0 0 

SR 3.0 3.0 3.0 

ATR 1.5 1.5 1.5 

T (°C) 750 - 900 750 - 850 750 - 850 

GHSV (h-1) 50,000 - 

200,000 

22,000 ­

66,000 

50,000 ­

150,000 

Gas chromatography was used to identify and 

separate the reaction products. The gases (N2, O2, 

CO, CO2, and CH4) were analyzed using a thermal 

conductivity detector (TCD), and the gaseous 

hydrocarbons were analyzed using a flame ionization 

detector (FID). Gas chromatography (Perkin Elmer’s 

AutoSystem XL) coupled with mass spectrometry 

(Perkin Elmer’s TurboMass Gold) was used to 

quantify and identify the complex liquid hydrocarbon 

product mixture that formed at various hydrocarbon 

conversions. Product yield is reported as a 

percentage of the theoretical yield based on moles of 

carbon in hydrocarbon fed to the reactor. For 

example, the yield of product A (H2, CO, and CO2) 

can be defined as 

Moles of A produced Yield of A (%) = *100 

N × moles of hydrocarbon fed to the reactor 

where N is the number of carbons in hydrocarbon 

fuel used in this study. In some cases, H2 yields may 

be higher than 100% since steam reforming and the 

water gas shift reaction also contribute to H2 

production apart from hydrocarbons. 

Results 

Statistical Analysis of Reforming Process 

The yields of individual species from 

hydrocarbon reforming, z, which depend on the 

space velocity (x) and reaction temperature (y), can 

be described by the equation 

z = b0 + b1x + b2y + b11x2 + b22y2+ b12xy (1) 

where z = the yield of individual species after 

completion of the reaction, x = gas hourly space 

velocity (hr-1), y = temperature (°C), and b0....b22 

are the coefficients of the model. The coefficients of 

Equation 1 were estimated by making use of the 

responses of experiments for the standardized values 

of x and y which varied in the range given in Table 1. 

A relationship between yields (z) and two 

quantitative variables x (space velocity) and y 

(reaction temperature) is represented by response 

surface curves as shown in Figures 1-5. Coefficients 

of quadratic Equation 1 are summarized in Table 2 

for H2 and CO yields from autothermal reforming of 

various types of raw materials used in this study. 

Quadratic fit of data from response surface mapping 

was excellent (>90%). 

Analysis of a response surface curve can be 

helpful in establishing the hypothetical kinetic 

schemes of the process. The effect of different 

parameters on the course of a process may vary from 

one organic class to another. That is why we decided 

to study each organic class separately. 

Model compounds representing each 

homologous series present in diesel were evaluated 

to develop surface response maps for steam 

reforming, partial oxidation and autothermal 

reforming over Pt catalysts. Each model compound 

behaved differently upon reforming under the same 

conditions. Aromatics were less active than 

aliphatics and required relatively higher contact time 

to convert into synthesis gas. The hydrogen 

production rates at the same conditions were 

observed in this order: Aromatics << Naphthenes < 

Paraffins. 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

 Table 2. Coefficients of Quadratic Equations for Autothermal Reforming of Model Components 

Fuel X Coefficients R2 

b0 b1 b2 b11 b12 b22 

Tetradecane H2 1313.8 -6.0e-4 -2.36 1.4e-9 -1.4e-7 1.2e-3 0.96 

CO 283.8 2.9e-4 -0.62 7.4e-10 -6.3e-7 3.9e-4 0.98 

1-Methylnaphthalene H2 1155.9 1.9e-3 -2.36 4.7e-9 -2.4e-6 1.2e-3 0.98 

CO 521.8 1.7e-3 -1.14 -6.1e-10 -1.6e-6 6.2e-4 0.96 

Decalin H2 627.4 -2.6e-4 -1.47 2.7e-9 -4.2e-7 8.7e-4 0.97 

CO 1975.2 -1.2e-3 -3.67 1.7e-9 -6.7e-7 1.7e-3 0.87 

Hydrocarbon product distributions depended 

greatly on the model compound, the type of 

reforming performed, and the process parameters 

(space velocity and reaction temperature). Generally, 

in addition to desired products (H2 and CO), the gas 

product streams also include CO2, C1 to C7 nalkanes, ethylene, propylene, iso-butane, isopentane, and benzene. Methane and CO2 were the 

major by-products present in significant amounts in 

the gas product streams. Furthermore, a series of 

oxygenated products such as aldehydes and ketones 

were observed in liquid product from partial 

oxidation of n-tetradecane, particularly at higher 

space velocities and lower temperatures. 

Figures 1-3 show the effect of temperature and 

space velocity on the yields of H2, CO, and CO2 

from the autothermal reforming of n-tetradecane 

(paraffin). Figures 4-5 show the yields of H2 from 

the autothermal reforming of 1-methylnaphthalene 

(aromatic) and decalin (naphthene), respectively. 

Generally, the yields of H2 and CO increased with 

increasing reaction temperature and decreasing space 

velocity. However, the yields of CO2 from 

autothermal reforming of n-tetradecane and decalin 

decreased with increasing temperature because the 

lower temperatures favor the water-gas-shift 

reaction, while the reverse of water-gas-shift reaction 

is facilitated at higher temperatures. 

Higher yields of methane (1-10%) were observed 

in the product gas from autothermal reforming of 

different feedstocks. Methane is not thought to be 

produced from the methanation reactions because 

those reactions are not thermodynamically favored at 

the temperature studied. It is probable that CH4 is 

formed by successive α-scission of the hydrocarbons 

on the metal catalysts, 

CnHm=>CH4+Cn-1Hm-4 (2) 

Figure 1. Yield of H2 from ATR of n-Tetradecane 

(O2/C = 0.3 and S/C = 1.5) 

Figure 2. Yield of CO from ATR of n-Tetradecane 

(O2/C = 0.3 and S/C = 1.5)

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Yield of CO2 from ATR of n-Tetradecane 

(O2/C = 0.3 and S/C = 1.5) 

Figure 5. Yield of H2 from ATR of Decalin 

(O2/C = 0.3 and S/C = 1.5) 

Figure 4. Yield of H2 from ATR of 1-Methylnaphthalene 

(O2/C = 0.3 and S/C = 1.5) 

Higher yields of methane compared to negligible 

other hydrocarbons coupled with the significant 

concentrations of naphthalene in the product stream 

from autothermal reforming of 1-methylnaphthalene 

suggests that the reforming of aromatics starts with a 

dealkylation reaction. 

Yields of cracking products, lower paraffins and 

olefins, decrease as temperature increases or space 

velocity decreases. Higher temperature facilitates 

the cracking reaction, but at the same time, it also 

increases the rate of reforming reaction. Increasing 

the residence time would increase the contact time 

between the catalyst and reactants, thereby 

increasing the conversion of cracking products into 

syngas and reducing the yield of cracking products. 

Isoparaffins or branched olefins were not 

observed, which suggests that isomerization 

reactions are not taking place during reforming of 

diesel fuel components. Also, naphthenes were not 

detected from the autothermal reforming of paraffins 

or aromatics. However, a series of olefins (alkenes, 

dienes, trienes, alkynes, etc.) formed from reforming 

of n-tetradecane, particularly at higher space 

velocities and lower temperatures. 

Production of olefins and aromatics was 

significant from autothermal reforming as well as 

partial oxidation of n-tetradecane at higher space 

velocity and temperature. Formation of compounds 

such as n-octyl benzene, but no naphthenic 

compounds from the paraffin reforming, suggests 

that the aromatics are produced primarily by 

cyclization reactions of poly-enes rather than 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

cyclization of paraffins to naphthenes and then 

dehydrogenation to aromatics. Reforming of decalin 

also produced significant concentration of aromatics, 

presumably via dehydrogenation reaction. 

Reforming of 1-methylnaphthalene at elevated 

temperatures (~900°C) produced significant coking 

on the catalyst and resulted in higher pressure drops 

and eventually reactor plugging. Aromatics 

contribute significantly to the catalyst deactivation 

compared to paraffins and cycloparaffins present in 

the diesel fuel. 

Conclusions 

Single component reforming studies were 

conducted on tetradecane, decalin, and 1-

methylnaphthalene. These model compounds 

represented the major organic classes found in diesel 

fuel (paraffins, naphthenes, and aromatics) and, 

studied individually, aided in analyzing the 

reforming characteristics and tendency of each 

species. Use of a surface response mapping 

technique was helpful in assessing the impact of 

space velocity (residence time) and temperature on 

reforming of the various compounds. Hydrogen, 

carbon monoxide, and carbon dioxide production 

were measured as a function of temperature, space 

velocity, and reforming type for a platinum-based 

catalyst. Intermediate species formation of various 

hydrocarbons including olefins and aromatics were 

observed during reforming. Carbon formation at 

various operating points and with certain fuel 

compounds point to the importance of understanding 

the mechanism or route for both reformer operation 

and catalyst design. Additional studies, including 

combinatorial fuel reforming, are needed to ensure 

successful development of this technology area. 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Rogers, W., Shi, S., Berry, D. A., Gardner, T. H., 

Shekhawat, D., "Modeling of Reformers for Fuel 

Cell Applications", First International Conference 

on Fuel Cell Science, Engineering and 

Technology, Rochester, NY, April 21-23, 2003. 

2. Shi, S., Rogers, W., Berry, D. A., Gardner, T. H., 

Shekhawat, D., "Numerical Simulation of Partial 

Oxidization Processing of Diesel for Fuel Cells", 

Fourth ASME/JSME Joint Fluids Engineering 

Conference, Honolulu, HI, July 6-11, 2003. 

3. Zinn, A. N., Gardner, T. H., Berry, D. A., James, 

R. E., Shekhawat, D., "Investigation of a Novel 

Reciprocating Compression Reformer for Use in 

Solid Oxide Fuel Cell Systems", First 

International Conference on Fuel Cell Science, 

Engineering and Technology, Rochester, NY, 

April 21-23, 2003. 

4. Berry, D. A., James, R. E., Gardner, T. H., 

Shekhawat, D., "Systems Analysis of DieselBased Fuel Cells", First International Conference 

on Fuel Cell Science, Engineering and 

Technology, Rochester, NY, April 21-23, 2003. 

5. Berry, D. A., Gardner, T. H., Shekhawat, D., 

"Development of Predictive Models for DieselBased Fuel Processors", 2003 Annual Merit 

Review Meeting of Hydrogen, Fuel Cells & 

Infrastructure Technologies Program, DOE Office 

of Energy Efficiency and Renewable Energy, 

Berkeley, CA, May 18 - 22, 2003. 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Reforming of Diesel Fuel for Transportation Applications 

John P. Kopasz (Primary Contact), D.-J. Liu, S. Lottes, R. Ahluwalia, V. Novick, S. Ahmed 

Argonne National Laboratory 

9700 S. Cass Avenue 

Argonne, IL, 60439 

Phone: (630) 252-7531; Fax: (630) 972-4405; E-mail: Kopasz@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Verify feasibility of diesel autothermal reforming (ATR) in engineering-scale reformer 

•	 Demonstrate operation with liquid fuel injection 

• Reduce H 	 2O:C ratio needed to prevent coking 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 J. Durability 

•	 M. Fuel Processor Integration and Efficiency 

• N. Cost 	 

Approach 

•	 Perform computational fluid dynamics (CFD) modeling of reactors to guide reactor design 

•	 Investigate reforming chemistry to determine how diesel fuel formulations, H2O:C ratio, and O2:C 

ratio affect reforming efficiency, coking, and catalyst lifetime 

•	 Optimize reactor engineering based on results from modeling and reforming chemistry 

Accomplishments 

•	 Demonstrated successful operation of liquid fuel injector 

•	 Determined effect of O2:C and H2O:C ratios on reforming efficiency for several different diesel 

components 

•	 Demonstrated that di-aromatic components are more difficult to reform than mono-aromatics 

Future Directions 

•	 Determine how fuel composition affects catalyst durability 

•	 Investigate reforming under partial oxidation (POX) conditions and in low H2O:C regimes 

•	 Provide data for National Energy Technology Laboratory (NETL) model development and validation 

1 
 

 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

Diesel fuel is widely distributed and has a high 

energy density. This makes diesel reforming an 

attractive option for hydrogen production on-board 

vehicles. The hydrogen-rich reformate gas produced 

from diesel reforming can be used to produce power 

with fuel cells or used to reduce NOx emissions from 

combustion engines using reformate feed to selective 

catalytic reduction units. Diesel reforming poses 

several unique technical challenges, however. These 

challenges result from the physical and chemical 

properties of diesel fuel. To better understand diesel 

reforming and the chemistry involved, we have 

investigated the autothermal reforming of several 

major diesel constituents in a kilowatt-scale reactor. 

Major technical challenges in reforming diesel 

fuel include preventing coking while maintaining 

high reforming efficiencies and extending the 

catalyst lifetime/durability. We have found that 

delivering the fuel and obtaining a well-mixed stream 

of fuel, steam, and air before the fuel begins to 

decompose thermally can affect catalyst durability 

and coking. Due to the high boiling point of diesel 

fuel, vaporizing the fuel and using gas-phase mixing 

prior to the reactor is not a viable option. Poor 

mixing leads to oxygen-starved regions, regions 

where the reactant ratios favor coke formation, and 

hot spots that accelerate catalyst degradation. To 

overcome this problem, we developed and tested an 

injection nozzle of a new design. This injector 

design led to well-mixed reactants that allowed us to 

reform diesel surrogates and obtain reformate 

compositions that closely match those predicted by 

equilibrium thermodynamic calculations. In addition 

to the reactant vaporization and mixing issues, the 

complex nature of diesel fuel also leads to several 

challenges in reforming. To understand better the 

chemistry of diesel reforming, we have investigated 

the reforming of representative compounds from the 

different classes of hydrocarbons present. 

Experiments were performed at gas hourly space 

velocities (GHSV) of 10,000 to 100,000 h-1 with 

varying oxygen-to-carbon (0.15<O2/C<0.5) and 

steam-to-carbon (1<H2O/C<3) ratios to determine 

the influence of these parameters on product gas 

composition and on reformer efficiency. 

 FY 2003 Progress Report 

Approach 

Computational fluid dynamics (CFD) modeling 

was utilized to study mixing of reactants and to guide 

improvements in a liquid injector system to deliver 

fuel to the reactor. The spray behavior of the new 

liquid injector nozzle was characterized with the help 

of a nonintrusive, laser-based phase Doppler particle 

analyzer (PDPA). After testing, the injector was 

installed in an engineering-scale reactor for the 

reforming tests. 

Model compounds of different types of 

hydrocarbon species found in diesel fuel were tested 

under autothermal reforming conditions in the 

engineering-scale reactor. No external heating was 

supplied to the reactor. The product gas 

compositions were determined with various steamto-carbon and oxygen-to-carbon ratios. 

Results 

We have performed CFD modeling studies that 

indicate that mixing of reactants is critical in 

avoiding hot spots and cold spots. The results also 

indicate that substantial variations occur in the 

H2O:C and O2:C ratios across the catalyst. The 

H2O:C ratio is critical in controlling coking. To 

address this problem and provide well-mixed 

reactants to the catalyst bed, we have developed an 

innovative injector nozzle that produces small 

droplets of diesel fuel with low air-side pressure 

drops. It intimately mixes the fuel, steam (or water at 

startup), and air prior to the catalyst bed. In tests 

with hexadecane, the corrected and fitted mass 

median diameter (MMD) determined from PDPA 

over the central 1.5" of the spray was 8.3±2.7 μm at 

high-flow conditions (10 ml/min hexadecane) and 

8.0±2.3 μm at low-flow conditions (3 ml/min 

hexadecane). 

We have initiated a study of reforming of the 

various types of chemicals found in diesel fuel using 

liquid injection. Reforming of species found in 

diesel fuel indicate that there are differences in how 

the different species react. The product gas 

composition from reforming dodecane, hexadecane, 

and xylene as a function of O:C ratio (oxygen 

coming from O2 in air) is shown in Figure 1. The 

hydrogen yield increases with increasing O:C to a 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 Effect of the O:C Ratio on the Product Gas 

Distribution from Autothermal Reforming of 

Dodecane (DDN), Hexadecane (HXN) and 

Xylene (XYL) in an Engineering Scale 

Reactor 

Figure 2.	 Effect of the H2O:C Ratio on the Product Gas 

Distribution from Autothermal Reforming of 

Dodecane (DDN), Hexadecane (HXN) and 

Xylene (XYL) in an Engineering Scale 

Reactor 

maximum at an O:C of approximately 1.0 for 

dodecane and hexadecane and 0.8 for xylene, then 

decreases. The increase occurs more rapidly for the 

shorter chain length dodecane than for hexadecane or 

xylene. Reforming efficiency also increases with 

O:C, reaching a maximum where the H2 

concentration maximizes, then levels off. Reforming 

efficiency is defined as: 

ηref = {CtH2∆HcH2 + CtCO∆HcCO}/Ctfuel∆Hcfuel 

Ct,i = Molar flow rate of i 

∆Hci

 = Heat of combustion of i 

The effect of the H2O:C ratio on reforming is 

shown in Figure 2. As the H2O:C ratio increases, the 

hydrogen content increases slightly, while the CO 

concentration decreases. This leads to an overall 

decrease in efficiency with increasing H2O:C ratio. 

The decrease is likely the result of the increased 

thermal load from the additional steam, which results 

in lower reactor temperatures. 

Xylene was more difficult to reform than the 

paraffinic species, providing lower hydrogen content 

and resulting in higher catalyst temperatures at 

similar O:C and H2O:C ratios. Methylnaphthalene 

was reformed to determine how the multi-ring 

aromatic species present in diesel fuel react during 

reforming. Reforming of the methylnaphthalene was 

more difficult than the reforming of xylene. 

Reforming efficiencies were lower, and coke 

deposits were more likely to form. 

Conclusions 

•	 Proper delivery and mixing of reactants are 

needed to obtain high efficiencies and avoid hot 

spots and areas of non-uniform H2O:C and O:C 

ratios. 

•	 The new liquid injector nozzle provided small 

(<10 micron) droplets of fuel under relevant 

reactor operating conditions. 

•	 Substantial differences were found and 

documented in how the major different diesel 

fuel constituents are reformed. 

- Aromatics result in higher maximum 

reforming temperatures and lower energy 

conversion efficiencies. 

- Di-aromatics are more difficult to reform than 

mono-aromatics. 

•	 Increasing H2O:C ratio reduces coking but 

decreases overall efficiency. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Publications/Presentations 

1. "Characterization of Kilowatt Scale Diesel 

Autothermal Reformer With Surrogate Fuels", 

Di-Jia Liu, Hsiu-Kai Liao, Laura Miller and 

Shabbir Ahmed, presented at 2003 AIChE 

Spring National Meeting, New Orleans, LA, 

March 30 - April 3, 2003. 

2. "Diesel Reforming for Fuel Cell Application in a 

1- to 5-Kilowatt ATR Reformer", Di-Jia Liu, 

Hsiu-Kai Liao, Laura Miller and Shabbir 

Ahmed, presented at 18th North American 

Catalysis Society Meeting, Cancun, Mexico, 

June 2 - June 6, 2003. 

3. "Diesel Reforming in a Kilowatt Scale 

Autothermal Reformer with Liquid Injection", 

Di-Jia Liu, Hsiu-Kai Liao, Laura Miller and 

Shabbir Ahmed, presented at 2003 Future 

Transportation Technology Conference, June 23­

25, 2003, Hilton, Costa Mesa, California. 

4. "Diesel Reforming in a Kilowatt Scale 

Autothermal Reformer with Liquid Injection", 

Di-Jia Liu, Hsiu-Kai Liao, Laura Miller and 

Shabbir Ahmed, SAE publication 03FTT-6. 

 FY 2003 Progress Report 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Advanced High Efficiency Quick Start Fuel Processor for Transportation 

Applications 

Prashant S. Chintawar (Primary Contact), Brian Bowers, Christopher O'Brien, Zhi-Yang Xue, James 

Cross, and William Mitchell 

Nuvera Fuel Cells, Inc. 

20 Acorn Park 

Cambridge, MA 02140 

Phone: (617) 245-7560, Fax: (617) 245-7511; E-mail: chintawar.p@nuvera.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811, E-mail: Valri.Lightner@ee.doe.gov 

ANL Technical Advisor: Walter Podolski 

Phone: (630) 252-7558; Fax: (630) 252-4176; E-mail: podolski@cmt.anl.gov 

Subcontractors/Partners: 

SudChemie, Inc. 

Engelhard Corporation 

Worcester Polytechnic Institute 

Calnetix 

Objectives 

With the STAR (Substrate-based Transportation Autothermal Reformer) and HiQ (High Efficiency Quick 

Start Transportation Fuel Processor) projects, Nuvera's goal is to develop an advanced fuel processing 

system for transportation applications. The HiQ concept combines a fuel processor, a fuel cell, and a 

turbogenerator for power generation and is also useful for stationary applications where high efficiency is 

critical. This is a combined report for both the STAR and HiQ projects. 

STAR 

•	 Develop technologies needed to improve the power density, specific power, and start-up time of fuel 

processors. These technologies include lightweight advanced low thermal mass catalysts, substrates, 

compact heat exchangers, and desulfurization media. 

•	 Design and test the STAR fuel processor to ensure that it meets or exceeds FreedomCAR targets. 

Identify areas of improvement. 

•	 Prove reliable operation of the fuel processor via integration with a proton exchange membrane (PEM) 

fuel cell. 

•	 Increase system durability via fuel purification, reformate clean-up, catalyst advances, and mechanical 

design iterations. 

HiQ 

•	 Design, develop, and test a high power density, multi-fuel processor system that enables high 

efficiency and quick start operation of an integrated fuel cell power system for automotive
 

applications. The concept will combine a low thermal mass catalytic fuel processor with a
 

turbogenerator, leading to a hybrid system.
 

•	 Develop low-cost, high space velocity water-gas shift catalysts with subcontractors. 

•	 Demonstrate rapid startup to low power and high net system efficiency. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-Up/Transient Operation 

•	 J. Durability 

•	 L. Hydrogen Purification/CO Clean-Up 

•	 M. Fuel Processor System Integration And Efficiency 

• N. Cost 	 

Approach 

STAR 

•	 Perform automotive system analysis and identify strategies to meet FreedomCAR targets. 

•	 Work closely with sub-contractors to develop key technologies and sub-components. 

•	 Design, build, and test a compact integrated multi-fuel processor to investigate efficiency, power 

density, emissions, and reformate purity. 

•	 Integrate the STAR fuel processor and a fuel cell, investigate the performance of the power system, 

and identify system level integration issues. 

•	 Deliver the integrated fuel processing system to Argonne National Laboratory for testing. 

HiQ 

•	 Integrate STAR-type fuel processor with a turbo-generator system to recover waste energy from the 

fuel cell stack and provide capability for rapid start (less than one minute) to partial power levels. 

•	 Design and build proof-of-concept fuel processor and turbo-generator system using conventional 

pelleted catalyst technologies. 

•	 Demonstrate rapid start-up and high-efficiency operation on proof-of-concept system. 

•	 Design and build high power density automotive multi-fuel fuel processor combining STAR and HiQ 

technologies. 

•	 Deliver the integrated fuel processing system to Argonne National Laboratory for testing. 

Accomplishments 

STAR 

•	 Continued to advance the compact fuel processor design using substrate-based catalysts, custom heat 

exchangers and burners, and innovative mechanical design. 

•	 Fuel processor achieved automotive volume (75 liters), power density (2.1 kW-H2/liter of fuel 

processor), and aspect ratio (<9 inch height). 

•	 Tested the complete compact fuel processor on gasoline, ethanol, and natural gas. 

•	 Achieved 200 kWth on gasoline with 80% hydrogen efficiency and CO < 50 ppm. 

•	 Evaluated STAR operation on natural gas at 175 kWth feed rate with 74% hydrogen efficiency and CO 

< 50 ppm. 

•	 Demonstrated STAR operation on ethanol at 180 kWth feed rate with 75% hydrogen efficiency and 

CO < 50 ppm. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Integrated the fuel processor with a fuel cell to achieve 35 kWe and a gross efficiency of 31% (31 kWe 

from 100 kWth). 

•	 Pushed the limits of the STAR design through durability testing and made significant advances in 

hours, thermal cycles, and mechanical design. The durability test results guided research into subcomponent tests that are now ongoing. 

HiQ 

•	 Modeled, designed and constructed a proof-of-concept fuel processor system incorporating the key 

new technologies for the Nuvera HiQ combined-cycle process. 

•	 Tested the HiQ proof-of-concept fuel processor in the laboratory with a stack simulator and a standard 

automotive turbocharger. 

•	 Demonstrated less than 60 second start-up time to net power availability. 

•	 Demonstrated fuel processor performance consistent with 40% net system efficiency. 

•	 Demonstrated low exhaust emissions over entire start-up transient, as well as at steady state. 

•	 Designed low cost integrated turbine-compressor-motor-generator system with sub-contractor and 

started development program. 

Future Directions 

STAR 

•	 Complete testing on ethanol and natural gas. 

•	 Continue fuel processor performance optimization on gasoline operation. 

•	 Continue sub-component development with sub-contractors. 

•	 Deliver fuel processor system to Argonne National Laboratory, complete STAR project, and submit 

final report. 

HiQ 

•	 Demonstrate proof-of-concept system over full load range. 

•	 Demonstrate proof-of-concept system integrated with turbine-compressor-motor-generator subsystem. 

•	 Design and build automotive fuel processor incorporating STAR technology advances. 

•	 Demonstrate start-up, efficiency, and emissions characteristics of automotive fuel processor in
 

conjunction with turbine-compressor-motor-generator.
 

•	 Deliver fuel processor with turbine-compressor-motor-generator to Argonne National Laboratory. 

Introduction 

Nuvera Fuel Cells, Inc. (Nuvera) is a leading 

developer and supplier of fuel cells, fuel processors, 

and integrated power systems for the stationary, 

industrial, and transportation markets. Nuvera is 

working with the U.S. Department of Energy (DOE) 

to develop efficient, low emission, on-board multifuel processors for the transportation application. 

The fuels of interest are gasoline, methanol, ethanol, 

and natural gas. 

Approach 

With the STAR and HiQ programs, Nuvera is 

addressing the goal of developing a high power 

density, quick start fuel processing system that also 

provides very high net direct current (DC) 

efficiencies when coupled with an appropriate fuel 

cell. The STAR project is focused on development 

of high power density substrate reforming 

technology, while the HiQ project to date has 

developed new system integration and power cycle 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

technology to enable quick start and high efficiency. 

The STAR project will end in 2003; the HiQ project 

will continue by incorporating the STAR technology 

into a novel system integration scheme, capitalizing 

on the benefits of both. 

Results 

STAR. Based on catalyst, burner, and heat exchanger 

technologies produced in previous years, Nuvera 

built and tested several iterations of the compact 

STAR fuel processing system. The design, which 

has a total volume of ~75 L, contains all the catalytic 

reaction zones, the steam generation system, and heat 

exchangers (Figure 1). This fuel processor also has 

the shape factor necessary for installation in the fuel 

cell vehicle. 

During this reporting period, Nuvera tested the 

STAR fuel processor on gasoline, ethanol, and 

natural gas. The design focus was gasoline, and the 

majority of the effort was spent on optimizing 

gasoline performance. The gasoline results exceeded 

targets, with a hydrogen efficiency of 80% and CO of 

less than 50 ppm at up to 200 kWth (Figure 2 shows 

180 kWth data) feed rate. The STAR fuel processor 

also showed successful operation on ethanol and 

natural gas, processing both fuels with less than 50 

ppm CO and hydrogen efficiencies of ~75%. Natural 

gas and ethanol testing focused on proving the fuel 

flexibility, and efficiencies were lower than gasoline 

only because time constraints prevented full 

optimization. 

The STAR fuel processor also underwent 

durability testing to investigate the limits of the 

design. Mechanical durability has been improved 

Figure 1. STAR Fuel Processor on Test Cart 

 FY 2003 Progress Report 

significantly - over five enhancements in the 

longevity (hours) and 100% improvement in thermal 

cycle capability as compared to the previous compact 

fuel processors (Figure 3). The durability results 

suggested areas of sub-component research, which 

are currently underway both at Nuvera and subcontractors. 

To ensure high quality of STAR reformate, the 

fuel processor was integrated with a fuel cell (Figure 

4). The integration was successful and produced 35 

kWe and was limited only by the laboratory air 

supply system. The gross efficiency achieved was 

31%, i.e. the system produced 31 kWe from the fuel 

cell with 100 kWth of gasoline fed to the fuel 

Figure 2. STAR Fuel Processor Operation on Gasoline 

(160-180 kWth) 

Figure 3. Durability Improvement of Nuvera STAR 

Fuel Processor 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

processor. There is significant room for improving 

the system efficiency; however, this is beyond the 

scope of the current project. The integration and fuel 

processor performance results indicate that the STAR 

fuel processor has the minimum rating of 62 kWe, 

exceeding the program target of 50 kWe. 

The STAR fuel processor program represents a 

culmination of four years of intensive R&D and 

design efforts. Nuvera started with basic component 

testing of the catalysts and developed custom heat 

exchanger and burner designs. Today, Nuvera has 

combined these components to produce an advanced 

automotive fuel processor that finally achieves the 

volume, power, efficiency, hydrogen production, and 

reformate quality targets for onboard fuel processors. 

HiQ. The focus of the HiQ project in the past year 

has been on proving the feasibility of increasing 

system efficiency and decreasing startup time via 

novel system integration strategy. The block 

diagram shown in Figure 5 outlines the HiQ system 

configuration. High system efficiency is achieved by 

using the waste heat from the stack to evaporate 

water into the cathode air. The resulting flow of 

water vapor is heated to an appropriate temperature 

in the combustor and passed through the turbine, 

where it generates mechanical power. The integrated 

generator on the turbine shaft converts this 

mechanical power into electrical output. Thus, the 

system converts heat that is ordinarily wasted into 

useful electrical power, which improves the overall 

system efficiency. 

 FY 2003 Progress Report 

The technical challenges involved include 

combustor, heat exchanger, and fuel processing 

improvements to enable this heat-to-power conversion 

to take place. A key aspect of the process is that the 

combustor technology developed by Nuvera in this 

project allows the use of high-temperature automotive 

turbine technology. Not only does this reduce cost, but 

it also allows quick start-up; the combustor and turbogenerator can be operated as a micro-turbine at startup, allowing for some power production even before 

the fuel processor is warmed up and the fuel cell is 

producing power. 

The feasibility demonstration was successfully 

carried out using a proof-of-concept fuel processor, 

stack simulator, and automotive turbocharger. 

Figure 5. HiQ System Integration Concept 

Figure 4. STAR Fuel Processor/Fuel Cell Integration 

Figure 6.	 Plot of HiQ system startup with automotive 

turbocharger used as placeholder for turbine/ 

compressor/motor/generator system. The 

system reaches a state that will correspond to 

net power output from the turbo-generator in 

less than 60 seconds from start-up. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies

Computational models were used to project fuel cell 

and turbo-generator power output levels based on the 

observed laboratory data. As shown in Figure 6, the 

start-up time to the low power micro-turbine mode 

has been demonstrated to be less than 60 seconds. 

Conclusions 

STAR 

•	 The substrate-based STAR fuel processor meets 

the volume (75 L), power (200 kWth), hydrogen 

efficiency (80%), and CO (<50 ppm) targets for 

onboard fuel processors. 

•	 Durability testing of the STAR fuel processor 

showed great improvements in mechanical 

design and suggested areas of research that are 

currently ongoing. 

•	 A STAR fuel cell/fuel processor integration 

proved high reformate quality with successful 

operation of the fuel cell. 

HiQ 

•	 A proof-of-concept fuel processor system has 

been developed and has demonstrated the 

feasibility of the HiQ system integration scheme. 

•	 Laboratory results support projections of start-up 

times of less than 60 seconds to partial power 

levels. 

 FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. Jian L. Zhao, William Northrop, Timothy Bosco, 

Brian Bowers, On-Board Gasoline Fuel 

Processor ---- STAR. AIChE 2003 Spring 

National Meeting – Topical Conference on Fuel 

Cell Technology, Session 99, New Orleans, LA, 

30 March-3 April 2003. 

2. Lawrence Clawson, James Cross, Christopher 

O’Brien, Development and Analysis of a 50 –100 

kW Hybrid Cycle Integrated PEM Fuel Cell and 

Fuel Processor System with High Efficiency and 

Rapid Start-up, presented at “Fuel Cell Advances 

2002,” Amsterdam, The Netherlands, 25-26 

September 2002. 

6 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a 50-kW Fuel Processor for Stationary Fuel Cell Applications 

Using Revolutionary Materials for Absorption-Enhanced Natural Gas Reforming 

(New FY 2004 Project) 

Jim Stevens, Ph.D 

Program Manager 

ChevronTexaco Technology Ventures 

P.O. Box 770070 

3901 Briarpark 

Houston, Texas 77042 

Phone: (713) 954-6341; E-mail: James.Stevens@chevrontexaco.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Objectives 

•	 Develop and test a fuel processor capable of producing a high hydrogen concentration (>98%) 

reformate containing inconsequential levels of carbon dioxide and carbon monoxide. 

•	 Develop high durability CO2 absorbents containing both high temperature water gas shift (WGS) and 

steam reforming catalysts. 

•	 Perform process design, system efficiency, and cost estimate studies. 

•	 Design, construct, and test a “stand alone” natural gas fed 50-kW fuel processor which will meet these 

performance targets: efficiency >85%, CO concentration <10 ppm, H2S concentration <50 ppb, 

system life >40,000 hours. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 I. Fuel Processor Start-Up Time 

•	 J. Durability 

•	 K. Emissions/Environmental Issues 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

• N. Cost 	 

Approach 

ChevronTexaco will develop a natural gas fueled 

50-kW fuel processor capable of producing a high 

hydrogen concentration (>98%) reformate containing 

inconsequential levels of carbon dioxide and carbon 

monoxide. This capability will be achieved using a 

new catalyst powder manufacturing technique which 

promises to breathe new life into an old fuel 

processing concept, adsorption-enhanced reforming 

(AER). ChevronTexaco will use a unique spraybased powder manufacturing approach to develop 

and produce powders that have been specifically 

designed for absorption-enhanced reforming using 

logical materials design concepts. The spray-based 

powder manufacturing approach allows the creation 

of materials with unique microstructures and 

compositions that cannot be achieved by competing 

powder manufacturing approaches. Initial results 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

indicate that this approach may lead to a major 

breakthrough in the development of high capacity, 

highly reversible CaO-based CO2 absorbents. The 

combination of Cabot Superior Micropowders’ 

(CSMP) unique powder manufacturing capabilities, 

ChevronTexaco’s refining catalyst experience, and 

Texaco Energy System LLC’s (TES) natural gas 

reforming/fuel cell experience presents the 

opportunity for higher fuel cell power plant 

efficiencies, reduced capital costs, and long term 

environmental benefits. 

The ChevronTexaco team will develop a single 

catalyst bed composed of high durability CO2 

absorbents, high temperature water gas shift catalysts 

and steam reforming catalysts. Process design, 

system efficiency, and cost estimate studies will be 

performed leading to the design, construction, and 

testing of a “stand alone” natural gas fed 50-kW fuel 

processor. This approach is in contrast to the high 

capital and operating costs associated with pressure 

swing adsorption or membrane separation. 

The major benefits of this approach are the 

reduced cost combined with an increase in 

performance and reliability of the whole fuel cell 

system. The production of a high purity hydrogen 

feed stream based on the reaction CH4 + 2H2O + 

CaO 6 4H2 + CaCO3 leads not only to a lower cost, 

highly efficient fuel processor, but also reduces the 

cost (higher H2 content = less precious metal in the 

 FY 2003 Progress Report 

membrane electrode assembly) and improves the 

durability of the fuel cell stack through reduction of 

CO (poison) and CO2 (reverse WGS and acidity 

enhancer). The system will comprise two or more 

AER beds, some of which are recycled while one is 

used to reform the natural gas. In addition to the 

reactor, the system will contain heat exchangers, a 

methanation unit, a desulfurization unit and a tail gas 

oxidizer. We estimate this system will achieve at 

least 85% energy efficiency with less than 10 ppm 

CO and less than 50 ppb H2S in the reformate and 

with durability of more than 40,000 hours. Our 

current estimate of the reactor volume is about 80 

liters with three reactors required. 

Past work has proven the concept, but 

commercialization has failed due to the poor 

durability of the carbon dioxide absorption material. 

Materials that were produced in a cooperative 

program between CSMP and ChevronTexaco 

researchers have shown the feasibility of greatly 

improved durability. The extrudates made with 

powders manufactured by CSMP’s spray technology 

retain their original CO2 absorption capacity and 

carbonation/de-carbonation kinetics through many 

cycles. Tests of the process in TES’s automated 

small scale reactors confirm the ability of the process 

to produce >98% purity H2 with inconsequential 

levels of CO2 and CO. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Integrated Manufacturing for Advanced Membrane Electrode Assemblies 

Emory S. De Castro (Primary Contact) 

De Nora N.A., E-TEK division 

39 Veronica Ave, Somerset, NJ 08873 

Phone: (732) 545-5100 ext 112; Fax: (732) 545-5170; E-mail: emory.decastro.etek@denora.com 

Mark G. Roelofs 

DuPont Company 

Chestnut Run 

Wilmington, DE 

Phone: (302) 695-7342; Fax: (302) 695-2503; E-mail: mark.g.roelofs@usa.dupont.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: Benjamin@cmt.anl.gov 

Subcontractors: 

DuPont Company, Wilmington, DE 

Nuvera Fuel Cell, Cambridge, MA 

Northeastern University, Boston, MA 

Objectives 

•	 Create improved cathode structures and catalysts for proton exchange membrane fuel cells (PEMFCs) 

at temperatures less than 100o

C that allow a significant reduction of precious metal (PM) without loss 

in performance 

•	 Develop a durable membrane for fuel cell operation at higher temperature and low water vapor 

pressure (>120oC, <25% relative humidity, >5000 hrs) 

•	 Incorporate the advances of (1) and/or (2) with advanced membrane electrode assembly (MEA) 

fabrication processes that are amenable to mass production 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

•	 R. Thermal and Water Management 

Approach 

•	 Fabricate highly controlled fine gradient gas diffusion layers through machine coating methods; 

exploit a new structure-function approach to designing improved catalysts and catalyst alloys; 

combine the gas diffusion layers and the improved catalysts to create enhanced electrode structures 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Synthesize and evaluate small-molecule organic electrolytes to test functional groups; incorporate 

promising functional groups into polymeric electrolytes and evaluate 

•	 Develop new machine-based or ion beam coating methodologies to create ultra-low loaded precious 

metal MEAs 

Accomplishments 

•	 Introduced a lower-cost method for preparing a more active platinum on carbon black compared to 

standard commercial preparations 

•	 Elucidated details on the structure-activity relationship behind the platinum alloy’s enhanced activity 

for oxygen reduction 

•	 Demonstrated proof-of-principle of the fine gradient ELAT® gas diffusion electrode (GDE) fabricated 

on a developmental coating machine (20% increase in current density at 0.6 V) 

•	 A combination of new catalyst and improved control of gradient on an experimental carbon cloth has 

shown a 50% decrease in cathode platinum needed per kilowatt power output in machine fabricated 

structures 

•	 Verified 10-30% increase in power density of new improved cathode materials in a Nuvera short stack 

•	 Determined specific organic electrolyte functionalities that provide conductivity at low relative 

humidity (RH) 

•	 Synthesized ionomers with conductivity significantly improved vs. benchmark Nafion® and evaluated 

their thermal stability 

Future Directions 

•	 Achieve lower total PM loadings through ion beam assisted deposition (IBAD) on membrane 

•	 Use new GDE structures to lower metal load 

•	 Adapt new understanding on conductivity and thermal stability to increase the number of candidate 

ionomers; develop membranes from these candidate ionomers 

Introduction 

A continuing challenge for PEMFC technology 

is precious metal thrift and creating new ion 

exchange membranes that are capable of stable 

operation at temperatures exceeding 120o

C and, 

preferably, 150oC. The greatest barrier to reduction 

of platinum metal in the MEA is due to the cathode 

half reaction, which can be addressed through both 

improved catalysts and the electrode structure around 

the catalyst. In addition, there is a significant 

incentive to increase the operating temperature, the 

advantages being a) smaller radiators in 

transportation applications, b) more efficient use of 

by-product heat in stationary applications (e.g. hot 

water generation), c) potential for faster oxygen 

reduction kinetics at the cathode, d) increased 

tolerance to CO in reformed-hydrogen feed streams, 

and e) better kinetics for methanol oxidation in direct 

methanol fuel cells (DMFCs). For higher 

temperature operation, the need to limit the total 

stack pressure to 1 to 1.5 bar places a limit of ~0.5 

bar on the water partial pressure, which corresponds 

to only 25% RH at 120o

C – a significant challenge in 

designing new membrane materials. 

During this report period, we have focused on 

new platinum catalysts, elucidation of structureactivity relationships for alloys, new GDE structures, 

and new high temperature polyelectrolytes. Our work 

on new electrolytes that provide the requisite 

conductivity at high temperature and low RH has 

identified candidates with improved conductivity 

over the benchmark. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

In the last report, we identified a series of 

innovative catalyst preparation techniques and 

described linking electrochemical activity to detailed 

bulk structural information derived from 

spectroscopic determinations. During this report 

period, we have focused on the most promising 

preparation methodologies and exploited these 

methodologies to produce highly active platinum on 

carbon black, as well as prepare alloy structures that 

led to additional insights on the structural properties 

that control catalytic oxygen reduction. 

Our program proposed the “fine gradient” 

ELAT® as a new design for the GDE or gas diffusion 

layer (GDL) that would facilitate both gas and proton 

transport to the catalyst. By reducing undesired 

variations in coating quality, we were able to create 

fine gradients of architectural features such as pore 

size distribution and hydrophobicity within the gas 

diffusion layer structure. All these structures are 

fabricated on a sophisticated developmental coating 

machine so they are readily assessed for suitability 

towards high volume manufacturing. Lastly, the 

most promising structures were advanced to Nuvera 

Fuel Cell for short stack testing/verification. 

For higher temperature membranes, a wide 

variety of organic functional groups were explored 

and small molecule model compounds synthesized. 

The model electrolytes were examined for their 

ability to conduct protons at low RH, by dint of either 

“holding on” to more water than Nafion®, or by 

having a different conduction mechanism that does 

not require as much water in the electrolyte. The 

scope at this point included some seven different 

types of acid groups with aromatic or fluorinated 

substrates. After discovering/identifying promising 

small-molecule electrolytes, the next step was to 

prepare polymeric electrolytes that “tie-down” the 

molecules, a necessity to reach the goal of no 

leachable components. At this point the thermal 

stability of the new polymers is evaluated using a 

thermo-gravimetric method. As of June 2003, we are 

about 60-80% finished with making the candidate 

polymers and evaluating conductivity and stability. 

The next step is to fabricate membranes from the new 

polyelectrolytes. We anticipate using cross-linking 

and/or composite membrane approaches to improve 

their mechanical properties and control water 

swelling and hydrogen crossover. Finally, MEAs 

will be fabricated and tested in single cells. In 

parallel with these efforts are smaller ones to 

benchmark the fuel cell performance of Nafion® and 

Nafion® inorganic composites at 120oC. 

Results 

Progress on developing higher power catalysts is 

summarized in Table 1. Generally, catalysts with 

smaller crystallite sizes are preferred. This 

preference is due to the much higher surface area 

inherent in what are essentially nanoparticles. 

However, electrochemical activity is more important 

than surface area, and the actual electrochemical 

surface area is a more effective measure of 

Table 1. Comparison of Commercial Platinum Catalyst to New Platinum Catalyst 

Crystallite Size (X-ray diffraction, nm) Electrochemical Surface Area (CO stripping, m2/g) 

%wt Pt/C(on 

Vulcan XC-72) 

Commercial Catalyst 

(E-TEKsm) New Catalyst Commercial Catalyst 

(E-TEK) New Catalyst 

10 2.0 - - -

20 2.5 2.2 - -

30 3.2 2.5 32 53 

40 3.9 2.8 - 39 

60 8.8 3.7 - 28 

80 25 4.9 - -

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

electrochemical activity. In comparing our findings 

for 30% Pt, one sees not only a significant decrease 

in crystallite size, but a large gain in electrochemical 

surface area. The commercial prep has 36% of the 

total platinum area electroactive, while the new prep 

has 47% of total area electroactive. Thus, we have 

created a catalyst with a greater proportion of active 

crystal faces. 

Extensive research of the oxygen reduction 

reaction (ORR) on platinum has shown that water 

activation by platinum produces surface species such 

as metal-OH that inhibit the ORR (1). Through 

efforts at Northeastern University, we have shown 

that the inhibition is highly dependent on structural 

features within a single alloy. These structural 

features are strongly determined by the method of 

preparation. Evaluation of the alloy’s performance 

for ORR in electrolyte solvents that contain low 

amounts of water helps mimic how these catalysts 

would perform in high temperature fuel cells. In 

analytical experiments, we show there is very little 

difference between platinum and platinum alloys for 

ORR in low water environments. 

Having established more facile control of 

deposition of the microporous layer, and applying 

this methodology to building the electrode layer, we 

systematically varied the porosity and 

hydrophobicity throughout the structure during a 

multi-layer build. We established a true fine gradient 

of porosity, whereby the total range of porosity (gas 

feed to electrode) was three orders of magnitude. For 

 FY 2003 Progress Report 

example, this contrasts with intermediate structures 

that achieved a porosity range of just under two 

orders of magnitude. The initial proof-of-principle 

for machine-made fine gradient ELAT® structures 

demonstrated a 25% increase in current under mass 

transport limited conditions (0.6 V, 70o

C, H2/air, 1.5 

atm total). 

The fine gradient approach has also allowed us 

greater flexibility in converting new web materials 

such as carbon cloth. Table 2 summarizes results 

formalized as the key technical target “grams of 

platinum per kilowatt of power,” whereby a 

combination of different carbon cloth webs, new 

improved catalyst, and more facile control of the 

gradient demonstrates our current status for reducing 

platinum content at the cathode. For comparison, a 

standard assembly containing commercially 

available components uses 1.8 g platinum at the 

cathode per kW of power when operating at 400 mA/ 

cm2 . By changing the underlying carbon cloth and 

incorporating a high definition microporous layer, we 

are able to reduce the amount of platinum needed per 

kilowatt power output to 1.29 g/kW. Our current best 

is 0.89 g/kW, whereby we gain the greater activity of 

the new platinum catalyst plus aspects of the fine 

gradient structure on a new carbon cloth substrate. 

Samples of various structures and improved catalyst 

have been evaluated at Nuvera Fuel Cell in short 

stacks (each MEA>200 cm2

, 70oC, 1.5 atmospheres 

total). Relative gains in performance from 10-30% 

were realized, depending on the operating current 

density, thus verifying single cell test results. 

Ta b l e 2 . Impact of Base Material and More Facile Control of the Gradient 

Cloth Web 

Cathode Cathode Total Pt Total Pt 

@ 100mA/cm2 @ 400mA/cm2 DOE goal 2005 DOE goal 2010 

g/kW g/kW g/kW g/kW 

Standard (st. Pt/C) 6.40 1.80 0.6 0.2 

Type 1 (st. Pt/C) 3.73 1.29 

Type 2 (new Pt/C) 3.11 0.89 

Type 3 (st. Pt/C) 6.69 2.50 

(single cell, 70oC, 1.5 atm. absolute, Air/C 1.5/2 stoich., Nafion 112) 

4 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

During the investigation of different types of 

organic acid electrolytes, the attempts to synthesize 

water-less electrolytes mostly failed to exceed mS/ 

cm conductivity. Only one electrolyte functionality 

was discovered which, when incorporated in two 

different compounds (candidates U and AB), gave 20 

- 40 mS/cm proton conductivity at 125 to 180o

C with 

either no water or at RH < 10%. Though promising, 

this electrolyte type had inferior conductivity to 

several others which still relied on water. Thus, 

several other small-molecule compounds were 

identified that had better conductivity relative to 

Nafion. In the last year, these electrolyte groups 

have now been successfully incorporated into 

polymeric electrolytes. The ionic conductivities of 

three of these candidate polymers are compared with 

that of benchmark Nafion in Figure 1. The 

conductivity is still decreasing with relative 

humidity, though the “rapid drop-off cliff” has been 

pushed to lower RH. Note that the mechanical 

properties of these polymers must be improved, e.g. 

by crosslinking or making composites, to arrive at 

thin membranes suitable for fuel cells. 

New polymer electrolytes are being screened for 

thermal stability using a thermal gravimetric analysis 

Figure 1. Ionic Conductivity of Benchmark Nafion® 

N117 and Three Experimental Ionomers at 

120o

C vs. Relative Humidity 

 FY 2003 Progress Report 

(TGA) kinetic method (2). TGAs are performed 

under air humidified at 22oC and heating rates 

between 1 and 10o

C/min. From this data, the 

activation energy for the first stage of thermal 

decomposition may be determined, and an upper 

limit on the lifetime of the polymer at the intended 

use temperature of 120o

C could be extrapolated 

(Table 3). 

Table 3. Thermal Stability for Nafion® and 

Experimental Polymer Electrolytes; Activation 

Energy, Preexponential Factor, and an Upper 

Limit to Life, in hours, Extrapolated to 120oC, 

Based on 10% of the First Stage of 

Decomposition to Be Completed 

Sample 

Activation 

Energy (Ea) 

(kJ/Mol) 

Log 

(A min-1) 

Upper Limit 

to Life @ 

120oC (hr) 

Candidate AE 290 24.3 4.0 X 1011 

Candidate AN 210 16.1 3.0 X 109 

Candidate AM 190 17.3 1.8 X 105 

Nafion® N112 160 12.9 1.3 X 105 

Candidate AF 40 14.0 1.4 X 102 

Candidate Z 80 7.4 2.0 X 100 

Caveats are that this test does not address 

electrochemical stability, nor does it detect 

degradation which does not result in weight loss (e.g. 

backbone scission), and the effect of the very low RH 

used has not yet been determined. The test can only 

alert one to a potential problem with the new 

polymers. Nafion® N112 has a predicted upper limit 

due to thermal degradation at 120oC of 1.3 X 105 hr, 

which exceeds the lifetime goals of 5 to 40 X 103 hr. 

Experimental polymers have been found to have a 

wide range of upper limits, with examples 

significantly higher, and several lower, than that of 

Nafion. 

Conclusions 

•	 Approach to structure-activity has yielded a 

more active platinum catalyst on carbon black 

with smaller platinum crystallite sizes and 

greater electrochemical surface areas. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Full potentials of the alloy catalysts are not 

realized in the “low temperature” fuel cell with 

the current electrode structure; under conditions 

of temperature above 100oC (low water), the 

ability for an alloy to inhibit poisoning due to 

absorption of oxygenates is no longer relevant, 

and these alloys may not realize the gain 

observed at lower temperature (high water) 

conditions. 

•	 The fine gradient ELAT® methodology 

provides a pathway to construct structures 

previously not attainable and will be used to 

recover some of the unrealized platinum 

alloy activity; this approach has also aided in 

reduction of the precious metal content in the 

cathode. 

•	 Using functional groups different from 

perfluorosulfonic acid ionomers, it is possible to 

make ionomers with significantly increased 

conductivity over that of Nafion® at 25% RH. 

•	 Ionomers can be made that pass a screening test 

for thermal stability. 

•	 Achieving both conductivity and thermal 

stability in the same ionomer is even more 

challenging, but is likely possible also. 

References 

1. S. Mukerjee, S. Srivanasan, M.P. Soriaga and J. 

McBreen, Electrochem. Soc. 142(1995) 1409 and 

references therein. 

2. J.H. Flynn and L.A. Wall, Polymer Letters, 4 

(1966) 323. 

FY 2003 Publications/Presentations 

1. “Integrated Manufacturing for Advanced 

Membrane Electrode Assemblies,” E.S. De 

Castro and M.G. Roelofs, DOE 2003 Merit 

Review and Peer Evaluation Meeting, May, 

2003, Berkeley, CA. 

2. “Reducing Overpotential Losses for Oxygen 

Reduction Reaction with Pt Based Alloys: a 

RRDE Investigation” - V. Srinivasamurthi, C. 

Urian, and S. Mukerjee (Northeastern University), 

203rd Electrochemical Society Meeting, Paris, 

France, 2003. Abstract No.1208. 

3. “Oxygen Reduction Kinetics on Pt and Pt Alloys 

under Lower Humidity, Rotating Disk Electrode 

Experiments,” V. Srinivasimurti and Sanjeev 

Mukerjee; in preparation for the Journal of the 

Electrochemical Society. 

4. “A Systematic Investigation of the Shift of H2O 

Binding Energy of Pt and Pt Alloys; Changes in 

the On-Set Potential of Oxygen Reduction,” A. F. 

Gullá and Sanjeev Mukerjee; in preparation for 

the Journal of the Electrochemical Society. 

6 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of High Temperature Membranes and Improved Cathode Catalysts 

Dr. Sathya Motupally 

UTC Fuel Cells (UTCFC) 

195 Governor's Highway 

South Windsor, CT 06074 

Phone: (860) 727-7175; E-mail: Sathya.Motupally@UTCFuelcells.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Subcontractors: 

High Temperature Membrane: 

Virginia Polytechnic Institute and State University, Blacksburg, VA 

Pennsylvania State University, University Park, PA 

Stanford Research Institute International, Menlo Park, CA 

IONOMEM, Marlborough, CT 

Princeton University, Princeton, NJ 

Cathode Catalysts: 

Northeastern University, Boston, MA 

University of South Carolina, Columbia, SC 

United Technologies Research Center (UTRC), East Hartford, CT 

Case Western Reserve University, Cleveland, OH 

Objectives 

•	 Develop and demonstrate an advanced polymeric membrane able to operate at near ambient (1-1.5 

atm.) pressure in the temperature range of 120~150×C that is able to meet DOE goals for performance. 

•	 Develop and demonstrate improved Pt cathode catalysts that will enable the reduction of Pt loading to 

0.05 mg/cm2

 and meet DOE goals for performance. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 P. Durability 

•	 Q. Electrode Performance 

•	 R. Thermal and Water Management 

Approach 

•	 Phase 1: High temperature membranes (HTMs) and improved Pt catalysts will be synthesized, 

characterized and compared with issued specifications. [In progress] 

•	 Phase 2: Laboratory-scale catalyst-coated membranes (CCMs) will be fabricated, optimized and 

tested using the Phase 1 down-selected membranes and catalysts. 

•	 Phase 3: Full-size CCMs with the down-selected and optimized HTMs and catalysts will be fabricated 

and tested in 2 individual multi-cell stacks. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

This project was initiated during the first quarter of 2002. The down-selection to retain promising catalysts 

and HTMs is scheduled for Q3 of 2003. All subcontractors are working towards optimizing their 

respective catalyst and HTM systems. 

•	 Four membrane systems with proton conductivity on the order of 10 mS/cm at 120°C and 50% relative 

humidity (RH) were synthesized: 

- Biphenyl sulfones (BPSH) from Virginia Tech, 

- Modified sulfonated polyetheretherketone (S-PEEK) from Stanford Research International, 

- Fluorinated polyether sulfone (FPES) from Penn State, and 

- Heteropolyacid (HPA) filled NafionÒ from IONOMEM. 

•	 IONOMEM has established a baseline for HTM performance of 0.6 V at 0.4 A/cm2 (120°C, 30% RH). 

•	 Slab band calculations using Vienna ab-initio slab program (VASP) project have provided insight into 

binary alloy skin effect. 

•	 Higher activity and more stable binary Pt alloys were synthesized using the colloidal-sol,
 

carbothermal, and pulse electrodeposition routes. 

•	 Reproducible and state-of-the-art (SOA) CCMs were fabricated using the decal transfer process. 

•	 All the requisite details and infrastructure for the catalyst and membrane down-selection process have 

been established. The down-selection process will commence during Q3 of 2003 and will be 

completed by the end of Q1 of 2003. 

Future Directions 

•	 Further optimize membrane systems and/or fillers required to improve conductivity at practical RH. 

•	 Develop a generalized stability template for HTMs. 

•	 Continue Pt-alloy synthesis using the various routes and optimize for activity and stability. 

•	 Investigate several methodologies to reduce Pt loading (e.g., ionomer gradient, etc.). 

•	 Initiate catalyst and HTM down-select process. 

Introduction 

Two main challenges in the proton exchange 

membrane (PEM) fuel cell arena are the reduction of 

cathode Pt loading and development of membranes 

that can operate over 120°C. Surmounting these two 

challenges will directly affect the cost, performance 

and the size of PEM fuel cell stacks. On the HTM 

project, new polymeric materials with negligible 

thermal degradation and acceptable proton 

conductivity in the 120-150°C range are required. 

On the improved catalyst project, a combination of 

higher activity catalysts and thinner catalyst layers is 

required to achieve the aggressive DOE performance 

targets. 

Approach 

To develop HTMs, UTCFC has teamed with 

research groups that possess competencies in the 

field of polymer chemistry and engineering. The 

subcontractors on the project are investigating 

modified Nafion and new non-Nafion based 

membrane systems (see Table 1). The subcontractors 

on the improved catalyst project and their individual 

approaches are given in Table 2. More details on 

both the approaches can be found in Reference. 

Results 

This project was initiated in June of 2002. Since 

then, all the subcontractors on the project have set up 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

the necessary infrastructure and have reported 

significant progress in the areas of catalyst and 

polymer synthesis. New catalyst systems with 

improved activity and stability relative to 

commercial pure Pt carbon supported systems have 

been identified. Under the HTM program, UTCFC 

has stressed the importance of developing polymers 

capable of conducting protons under practical 

relative humidity (RH) conditions. The HTM 

subcontractors are optimizing their polymeric 

materials for acceptable proton conductivity at 

120°C and 50% RH. A number of polymer systems 

whose proton conducitivities are on par with or 

exceed that of Nafion have been identifed. Salient 

progress details are presented below. 

High Temperature Membrane: On the HTM 

project, four of the five subcontractors have 

successfully synthesized polymer systems that yield 

finite proton conductivities at 120°C and 50% RH. 

One issue faced by most of the polymer subcontractors 

has been poor conductivity for their membrane 

systems at practical RH conditions. Prior to Q2 of 

2003, polymer membranes solely constituted by a 

Table 1. High Temperature Membrane Project 

Approach
 

 FY 2003 Progress Report 

blend of the basic sulfonated monomer showed 

excellent proton conductivity at 120oC and saturated 

conditions. However, the conductivity dropped off 

steeply as the RH was lowered below 100%. To 

overcome this issue and to minimize the dependence 

of the membrane proton conductivity on the humidity, 

all the subcontractors have tested the addition of 

hydrophilic conductivity enablers. These hydrophilic 

additives improve the water retention capability of the 

polymers at low RH. The types of fillers investigated 

to date include a wide variety of inorganic heteropolyacids and proprietary hydrophilic polymeric 

blends. With the aid of the the above types of fillers, 

the HTM subcontractors have consistently measured a 

proton conductivity greater than or equal to 0.03 S/cm 

(reference point of Nafion 117) at 120°C and 50% RH. 

An example of one class of filled polymers that 

shows good promise is the fluorinated sulfonated 

polythetheretherketone (FSPEEK) from SRI 

International (see Figure 1 for a schematic of the 

basic polymer). The sulfonated polymer is blended 

with a basic polymer to generate pseudo-crosslinking 

through an acid-base interaction, thus providing 

Table 2. Advanced Cathode Catalyst Project 

Approach 

Group Principal 

Investigator Approach 

IONOMEM Mr. Leonard 

Bonville 

Hygroscopic solid ion conductor 

(e.g., zirconium phosphate,etc) 

filled Nafion

Penn State 

University 

Prof. Digby 

Macdonald 

Sulfones and sulfoxides of 

aromatic PPBP and aliphatic PVA. 

Covalent sulfonic acid bonded 

PEEK, PBI and PPBP 

Princeton 

University 

Prof. 

Andrew 

Bocarsly 

Layered sulfonated Polystyrene/ 

Fluoropolymer system 

Stanford 

Research 

Institute 

Dr. Susanna 

Ventura 

Sulfonated PEEK-PBI-PAN 

Virginia Tech Prof. James 

McGrath 

Sulfonated Poly(arylene ether 

sulfone) 

Group Principal 

Investigator Approach 

North Eastern 

University 

(NEU) 

Prof. 

Sanjeev 

Mukerjee 

Micellar Pt nano cluster 

synthesis, colloidal sol 

synthesis of binary Pt alloys. 

University of 

South Carolina 

(USC)

 Prof. 

Branko 

Popov 

Pulse electro-deposition of Pt 

and Pt alloys on Carbon. [Pt and 

Pt-X, X=Fe, Ni, Co, Mn and Cu] 

UTC Fuel Cells 

(UTCFC) 

Mr. Michael 

Perry 

Carbothermal synthesis of 

ternary Pt alloys. [Pt-Ir-X and 

Pt-Rh-X, [X =Ni, Co and V]] 

Case Western 

Reserve 

University 

(CWRU) 

Prof. Alfred 

Anderson 

Quantum chemical modeling of 

Pt alloys and ORR. 

UT Research 

Center 

(UTRC) 

Dr. Ned 

Cipollini 

Reproducible and stack size 

CCM fabrication. 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

conducting polymer membranes with good 

mechanical stability. To minimize the dependence of 

the membrane proton conductivity on the humidity, 

SRI has tested two classes of hydrophilic polymers. 

Figure 1 illustrates the proton conductivity of several 

SRI polymer membranes at 120°C as a function of 

the RH. The conductivity of Nafion 117 (blue 

diamond) is shown as a reference line. The black 

line (hollow squares) shows the proton conductivity 

of the first-generation SRI membrane, where no 

additive was used in the polymer blend of the acidic/ 

basic polymer. The conductivity of this membrane 

drops quite significantly at RH lower than 80%. On 

the other hand, membranes containing hydrophilic 

polymer additives (14210-21c, 14210-25, and 14210­

53) showed significantly higher conductivity at low 

RH than the correspondent membrane without any 

additives. In particular, the conductivity at low RH 

for these membranes was found to be higher for 

additives with higher hydrophilic character. The SRI 

membrane 14210-53 was found to have the highest 

conductivity at 30 and 50% RH. For this membrane, 

proton conductivity values were 0.011 S/cm at 120°C 

and 30% RH and 0.038 S/cm at 120°C and 47% RH. 

These conductivities were higher than any other SRI 

membranes, as well as higher than Nafion 117. 

A summary of proton conductivities of other 

membrane systems developed under this project is 

shown in Figure 2. The 120°C and 50% RH proton 

conductivity metrics for biphenyl sulfones (BPSH) 

filled with hetero-polyacid from Virginia Tech., 

FSPEEK from SRI International, fluorinated 

polyethersulfones (FPES) from Penn State and 

Nafion filled with hetero-polyacid from IONOMEM 

are presented in the figure. The conductivity values 

of the membranes are compared to that of Nafion 

117. As seen from the figure, the conductivities of 

all the membrane systems on the project are higher 

than the corresponding Nafion value. It is also 

important to note that the glass transition 

temperatures of the membranes shown in Figure 2 

are higher than Nafion. Prior to the down-select 

process, the membrane subcontractors are further 

optimizing the thermal, mechanical and chemical 

stability of the membranes. 

Reproducible and SOA high temperature fuel 

cell performance has been established by 

IONOMEM. The IONOMEM technical approach 

for high temperature catalyzed membranes 

integrates, on a molecular level, the protonconducting Nafion polymer with hygroscopic 

hetero-polyacids such as phosphotungstic acid, or 

zirconium hydrogen phosphate. This nanocomposite material maintains low water vapor 

pressure, provides more water-independent proton 

conduction, and holds promise of satisfying DOE 

Figure 1.	 Conductivity Measured at 120°C as a Function 

of RH for Polymer Membranes with Variable 

Composition (blue [diamond] line: Nafion 117) 

Figure 2.	 Summary of Proton Conductivities Measured at 

120°C and 50% RH by the Various 

Subcontractors on the HTM Project (see Table 

1, SRI: FSPEEK, VA Tech.: BPSH, Penn State: 

FPES, IONOMEM: Nafion filled with heteropolyacid) 

4 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

performance requirements. At the project initiation, 

IONOMEM’s high-temperature membrane electrode 

assembly (MEA) demonstrated a consistent 

performance level of 0.454 volts at 400 mA/cm2 , 

operating at 120°C and ambient pressure on 

hydrogen and air both saturated near 90°C. The 

performance under the above-mentioned conditions 

was further enhanced to 0.6 V at the same current 

density during 2003. Polarization curves at 120°C 

and 35% RH for the IONOMEM membrane are 

shown in Figure 3. As seen from the Figure, the 400 

mA/cm2 performance at 120°C and 35% RH (albeit 

at low fuel and air utilizations) is 600 mV. The 

corresponding ohmic resistance at 120°C and 35% 

RH is 0.18 ohm-cm2 

. 

Advanced Cathode Catalysts: The advanced 

catalyst project is set up with three of the four 

subcontractors (Northeastern University, University 

of South Carolina, and UTCFC) synthesizing more 

active Pt alloy catalysts. Case Western Reserve 

University (CWRU) is supporting the catalyst 

synthesis task with fundamental molecular level 

simulations, and UTRC is fabricating and testing 

MEAs using the catalysts synthesized on the project. 

CWRU’s main goal on this project is to gain 

understanding of structure and electronic factors in 

oxygen electroreduction over platinum alloyed with 

transition metals. Their approach has been to predict, 

using quantum mechanical calculations, the 

reversible potentials for water oxidation on platinum 

alloys to form adsorbed OH, the surface species that 

Figure 3.	 IONOMEM's High Temperature Fuel Cell 

Performance at 120°C and 35% RH (The 

performance is compared to performance under 

80°C and saturated conditions.) 

 FY 2003 Progress Report 

is believed to block oxygen from reaching the 

electrode surface (Reference 2). During Q2 of 2003, 

Case completed calculations of H2O and OH 

bonding to various sites on the four layer slab models 

of the (111) Pt3Cr surface with and without a 

monolayer Pt surface “skin” which is found to form 

on supported alloy particle catalysts and on single 

crystal alloy surfaces (Reference 3). They found that 

their predictions for the Pt skin effect were in good 

agreement with the shift in overpotential for O2 

reduction and the apparent shift in onset potential for 

H2O(ads) oxidation to OH(ads) seen in the literature 

for Pt3Cr and other Pt alloys with metals from the 

first transition series. These results are currently 

being applied by UTCFC to develop novel shell-core 

structures for superior oxygen reduction activity. 

At UTCFC, in the ternary alloy area, we have 

completed the preparation and screening of 

Pt75Ir12.5X12.5 (X=Co, Ni, V) alloy systems using the 

carbothermal synthesis route (Reference 4). 

Electrochemical surface areas of the synthesized 

catalysts were in the 50-60 m2

/g range with particle 

size in the 2-5 nm range. Half-cell activity 

measurements indicate that the catalyst activities of 

Pt alloys are in the order of Pt75V25 > Pt75Ir12.5V12..5 

> Pt75Co25 > Pt50Ir25V25 > Pt75Ir12.5Ni12.5. The 

activity of Pt50Ir25V25 was 1.7 X greater than pure Pt 

catalyst. This could result in a kinetic improvement 

of 15 mV at 65°C. X-ray diffraction analysis 

confirms that Pt50Ir25Co25 and Pt50Ir25V25 are 

ordered, face-centered cubic structures with reduced 

Pt-Pt near-neighbor distance, which might be the 

reason that their activities are superior to pure Pt 

catalyst. The path forward for UTCFC is to scale up 

the best catalysts in a large quantity (>20 g) for 

further evaluation in subscale cells. 

In the binary alloy area, UTCFC has tested ca. 

50% weight loading Pt-Co catalysts and compared 

the performance, endurance and cyclic durability 

with pure Pt. Figure 4 contains the comparison of the 

Tafel plots obtained in a subscale cell for Pt-Co and 

Pt. Analysis of the Tafel plots shows that the ratio of 

the volumetric exchange current densities of Pt-Co 

and Pt is 1.25. The ratio of the surface area of the Pt 

and Pt/Co catalysts is approximately 1.75 (obtained 

using cyclic voltammetry). Therefore, the ratio of 

the true catalyst activity is approximately 2.2. The 

increased catalytic activity translated to an increase 

5 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

of ca. 10 mV at all current densities on the 

polarization curve. The stability of Co in the Pt-Co 

catalyst was investigated using electron microprobe 

analysis (EMPA) after 4000 cycles between 1.2 and 

0.8 V. In Figure 5, the scans are compared to those 

obtained with pure Pt cycled under the same 

conditions as above. The EMPA scans show no 

migration of Co into the membrane or to the anode 

side. The absence of Co migration is a strong benefit 

for the Pt/Co alloy system. 

Also, comparing the Pt dissolution fronts for Pt 

and Pt-Co catalysts shows that the Co incorporated 

into the catalyst stabilizes the Pt and reduces the rate 

of migration of the dissolved Pt. 

At the University of South Carolina (USC), Pt/C 

electrodes were fabricated by using pulse current 

electrodeposition methods. With the use of current 

pulses rather than direct current, a higher deposition 

current density could be used, and Pt deposits with a 

higher surface area and activity are possible. Figure 

6 compares the performance of USC's 

electrodeposited catalyst with a loading of 0.15 mg/ 

cm2

 to commercial ETEK catalyst of 0.4 mg/cm2 . 

The kinetic enhancement with the USC catalyst is on 

the order of 20 mV at all current densities.

 USC has identified the optimum current density 

and the duty cycle for the electrodeposition of higher 

activity Pt and Pt alloys and is currently fabricating 

subscale MEAs for testing at UTCFC. 

 FY 2003 Progress Report 

At UTRC, reproducible and SOA MEAs are 

being fabricated to aid in the catalyst down-selection 

process. Performance of some of the sample MEAs 

fabricated at UTCRC are presented in Table 3. As 

seen in the table, the air/H2 performance of the 

Figure 5. EMPA Images for Pt-Co and Pt Catalysts after 

500 hours of Endurance Hold at 0.5 A/cm2 

Figure 4.	 Comparison of the Tafel Behavior for Pt-Co 

and Pt Catalyst Systems (The kinetic 

enhancement obtained with Pt-Co is ca. 10 mV 

at all current densities.) 

Figure 6.	 Performance of USC’s Electrodeposited 

Catalyst with a Loading of 0.15 mg/cm2 

Compared to Commercial ETEK Catalyst of 

0.4 mg/cm2 (The kinetic enhancement with the 

USC catalyst is on the order of 20 mV at all 

current densities.) 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies

UTRC MEAs is comparable to the commercial 

MEAs, and the performance reproducibility is 

excellent. Also shown in Table 3 are the DOE targets 

for the reduced loading. Once the going forward 

catalyst systems are identified, UTRC will optimize 

the catalyst layers and aid in the reduction of the Pt 

loading. 

References 

1. 2002 UTCFC Annual Report (also the Q1 

Progress Report), 6/12/2002. 

 FY 2003 Progress Report 

2. Anderson, A. B., Albu, T. V. Catalytic Effect of 

Platinum on Oxygen Reduction. An Ab Initio 

Model Including Electrode Potential Dependence, 

J. Electrochem Soc., 147, 4229-4238 (2000). 

3. Stamenkovic, V., Schimdt, T. J., Ross, P. N. and 

Markovic, N. M., J. Phys. Chem. B, 106, 11970­

11979, 2002. 

4. US Patent 4,677,092, US 4,806,515, US 

5,013,618, US 4,880,711, US 4,373,014, etc. 

Table 3. Performance Comparison of UTRC MEAs 

CCM ID V, mV @ 400 mA/cm2 V, mV @ 100 mA/cm2 ECA, m2/g Pt 

Comments 

H2/O2 H2/Air H2/O2 H2/Air Cathode Anode 

DOE target 0.80 0.85 N/A Membrane thickness 

15μm 

REM 411 

Commercial 

0.824 0.786 0.885 0.857 - - Membrane thickness 

15μm 

REM 404 0.800 0.760 0.875 0.848 46 54 Membrane thickness 

15μm 

REM 413 0.795 0.757 0.879 0.845 44 69 Membrane thickness 

15μm 

REM 414 0.790 0.748 0.880 0.848 - - Membrane thickness 

15μm 

REM 415 0.810 0.767 0.887 0.854 54 65 Membrane thickness 

15μm 

REM 416 0.798 0.756 0.886 0.854 69 44 Membrane thickness 

15μm 

7 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

IV.E.3. Advanced MEAs for Enhanced Operating Conditions 

Mark K. Debe (Primary Contact), Steven J. Hamrock, Radoslav T. Atanasoski 

3M Company 

3M Center, Building 0201-01-N-19 

St. Paul MN 55144-1000 

Phone: (651) 736-9563; Fax: (651) 575-1187; E-mail: mkdebe1@mmm.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: benjamin@cmt.anl.gov 

Subcontractors: VAIREX Corporation, Boulder, CO; Case Western Reserve University, Cleveland, 

OH; Dalhousie University, Halifax, N.S., Canada; University of Illinois, Urbana, IL; University of 

Miami, Miami, FL; University of Minnesota, Minneapolis, MN 

Objectives 

Develop high performance, lower cost membrane electrode assemblies (MEAs) that 

•	 meet demanding system operating conditions of higher temperature with little or no humidification, 

•	 use less precious metal than current state-of-the-art constructions, and 

•	 are made by processes amenable to high volume manufacturing. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 Q. Electrode Performance 

•	 R. Thermal and Water Management 

Approach 

•	 Develop advanced cathode catalysts that have less precious metal and can be made by high volume 

compatible processes, building on the knowledge gained in the preceding 3M/DOE Cooperative 

Agreement, DE-FC02-99EE50582. 

•	 Develop membranes that are stable at operating conditions of 85 < T < 120°C, based on 3M’s 

hydrophilic ionomers that have shown greater stability at these temperatures than current commercial 

membranes. Optimize matching MEA components, flow field, and air management for these 

operating conditions. 

•	 Develop high temperature non-aqueous electrolyte membranes, stable catalyst constructions, 

optimized catalyst/membrane interfaces, and matching gas diffusion layer and flow field components 

for an operating range of 120 < T < 150°C and nearly dry operation. 

•	 Scale up and optimize MEA component fabrication processes amenable to high volume, high quality, 

low cost production for selected components from the above tasks. 

•	 Characterize selected MEAs in full-scale, short stacks. 

442 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Demonstrated reduced F- ion generation and longer lifetime of 3M's perfluorinated sulfonic acid 

ionomeric membrane compared with standard proton exchange membrane (PEM) ionomer. 

•	 Developed a "liquid H-pump" technique to measure the proton conductivity of ionic liquids and acids. 

•	 Developed liquid mixtures with no added water having proton conductivities of 40 mS/cm at 120oC 

with no water, which is 100 to 1000 times greater than anhydrous acids. 

•	 Demonstrated a membrane additive that reduces membrane weight loss occurring during a peroxide 

soak test by over a factor of 100 compared to a standard ionomer control. 

•	 Developed cathode catalyst compositions and structures having higher performance at a Pt loading of 

0.1 mg/cm2 than the baseline, using 3M nanostructured catalyst processes amenable to high volume 

manufacture. 

•	 Demonstrated higher chemical oxidative stability of the 3M nanostructured film supported catalysts 

compared with commercial carbon black supported Pt catalysts. 

•	 Demonstrated higher electrochemical stability of surface area and double layer capacitance of 

nanostructured ternary catalysts under either highly oxidative thermal or electrochemical potential 

conditions compared to carbon black supported catalysts. 

Future Directions 

•	 Continue the membrane and cathode catalyst development and screening and the fabrication and 

testing of integrated catalyst coated membranes (CCMs). 

•	 Optimize gas diffusion layers, flow fields, and air management to match the CCMs for higher 

temperature operation, building on previously developed computational models and test results. 

Introduction 

Poroton exchange membrane fuel cells 

(PEMFCs) have been developed sufficiently to 

demonstrate their feasible use for automotive and 

distributed stationary applications. However, several 

issues must be addressed to demonstrate commercial 

viability, including efficiency, durability, and cost. 

Overall, system efficiency is the critical factor 

affecting fuel usage and operating costs. The 

efficiency of a fuel cell is directly related to the cell 

operating voltage. The higher the voltage, the higher 

the efficiency, but the current density and power 

available are then lower, which affects stack size and 

cost. These factors are primarily affected by 

polarization of the cathode catalyst and stability of 

catalyst activity and surface area. Therefore, higher 

performing and more stable cathode catalysts are 

required to achieve the goals of increased 

performance with less precious metal catalyst. From 

a system perspective, operation at higher 

temperatures reduces thermal management 

constraints, thereby increasing overall efficiency. 

Greater tolerance of fuel impurities at high 

temperatures can also contribute to performance 

increases and, potentially, to lower costs of fuel 

processing components. However, the 

humidification requirements for higher temperature 

operation are significant. Designing an MEA to 

operate under hot, dry, pressurized conditions 

requires development of new membranes, catalysts 

and gas diffusion layers that are stable and durable at 

those conditions. The components must be matched 

to each other and integrated with a flow field design 

and air management strategy. In addition, the 

processes for making the MEA components must be 

consistent with high volume production. This project 

is directed toward development of MEAs that meet 

demanding system operating conditions of higher 

temperature and little or no humidification, use less 

precious metal than current state-of-the-art 

constructions, and are made by processes amenable 

to high volume manufacturing. 

443 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

The approach to higher temperature MEAs on 

this project involves the development of components 

for two sets of temperature ranges: 85 < T < 120o

C 

and 120 < T < 150oC. For the lower temperature 

range, proton exchange membranes are being 

developed based on modifications of existing 

perfluorinated sulfonic acid (PFSA) type membranes 

that still rely on water for proton conduction, such as 

NafionTM or 3M’s PFSA ionomeric membrane. 

These modifications include incorporation of 

functionalized additives to facilitate peroxide 

decomposition for better oxidative stability and 

enhanced water retention for higher conductivity 

under low humidification. For the higher 

temperature range, new membrane materials and 

non-water based proton conduction methods are 

being investigated, which utilize 3M perfluorinated 

acids, various proprietary liquids, and various 

inorganic additives. Work includes understanding 

how to incorporate those materials into polymer 

matrices to form effective membranes. The polymer 

matrices and process methods include both new and 

existing materials and methods. 

The approach to the development of advanced 

cathode catalysts that have less precious metal than 

current state-of-the-art constructions builds on the 

knowledge gained in 3M/DOE Cooperative 

Agreement DE-FC02-99EE50582. Cathode catalysts 

that significantly outperformed pure Pt were made 

using a 3M nanostructured, thin film catalyst support 

system and catalyst deposition process, which easily 

generates new compositions and structures via a dry, 

roll-goods process (roll-goods are made by a semicontinuous process and stored on a roll) amenable to 

high volume manufacturing. (See FY 2003 Progress 

Report on the above contract and also References 1 

and 2.) The catalyst structures and PtAB ternary 

materials developed under that contract exhibit unique 

electronic features and increased surface area. The 

3M nanostructured thin film supports (carbon free) 

show less susceptibility to oxidation and loss of 

catalyst surface area under highly oxidative conditions 

than commercially available carbon supported 

dispersed catalysts. Methods for generating new 

catalyst constructions include pilot-line production of 

large area catalyst formulations and a combinatorial 

method for generating and characterizing a wide 

latitude of ternary and quaternary compositions and 

structures using similar thin film catalyst deposition 

methods (with subcontractor Dalhousie University). 

Conventional dispersed catalysts with improved 

oxidatively stable carbon supports are also being 

investigated. 

For all the enhanced membrane and catalyst 

materials and process development work, a suite of 

critical property measurements is employed to guide 

development and down-selection of approaches. 

These include methods to measure the ionic and 

proton conductivity of the membranes, 

electrochemical impedance spectroscopy, chemical 

stability, PEM physical and mechanical properties, 

catalyst electrochemical surface areas and activities, 

and fuel cell tests under various protocols. Finally, 

methods to form effective interfaces of the catalysts 

with the new membranes for both operating 

temperature ranges are necessary for optimum MEA 

performance. 

Results 

As part of the effort to develop a more stable 

PEM for the range of 85oC < T < 120oC, a series of 

nearly 60 composite membranes was fabricated 

based on addition of inorganic dispersions to 

NafionTM in order to enhance water uptake. 

Extensive resistance testing by hydrogen pump and 

high frequency impedance at 120o

C, ambient 

pressure and 80oC dew point showed the effect of the 

majority of these additives was to make the 

resistance worse than the NafionTM control. Two of 

the additives made slight improvements under these 

challenging conditions. More recently, some of these 

same additives have been incorporated into the 3M 

ionomeric membrane. As shown in Reference 3, 

under identical test conditions of 80oC cell, 0.35 A/ 

cm2

, and H2/air at 27%/27% relative humidity (RH), 

3M roll-good fabricated membranes using 3M’s own 

PFSA ionomer had an 80% increase in lifetime over 

3M fabricated membranes made with NafionTM 1000 

ionomer. It is expected that incorporation of the right 

functionalized additives to the 3M ionomer should 

further enhance these stability properties and 

maintain conductivity with less humidification. This 

work will now focus on this new ionomer. 

444 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Peroxide generated at the anode in PEMFCs due 

to oxygen crossover is a serious mode of membrane 

degradation at high temperatures and dry conditions 

(Reference 4). Significant progress has been made 

developing and applying methods to evaluate the 

activity of membrane additives for peroxide 

decomposition. The key method uses weight loss 

measurements of membranes soaked in peroxide 

solutions for prolonged periods of time. Using 

literature and proprietary approaches, additives have 

been identified and screened for addition to the PFSA 

ionomers which, in addition to reducing weight loss 

in these accelerated tests, must not negatively impact 

ionic conductivity, electronic resistance, or fuel cell 

performance of the resulting MEAs. Figure 1 

illustrates the membrane mass loss of various 

additives versus controls, showing that Additive C 

can reduce the mass loss from the -10% seen for the 

non-additive control to zero within the +0.1% error 

of the measurement. Fuel cell performance and Fion release rates are being evaluated. 

A total of 53 different Pt based ternary cathode 

catalysts have been fabricated on large area, rollgood capable pilot-line equipment and evaluated by 

various fuel cell tests. The catalysts, all made on the 

3M nanostructured support films, differ by 

composition, non-noble metal type, and a structure 

factor tied to the catalyst deposition process. All 

have 0.1 mg/cm2 of Pt or less and for screening 

Figure 1.	 Comparison of the effect of various additives 

on PFSA membrane mass loss upon exposure 

to 1 M H2O2 at 90oC for 120 hours (refreshed 

every 24 hours), showing that one, Additive C, 

can reduce the mass loss from -10% seen for 

the non-additive control to zero within the 

+0.1% error of the measurement. 

 FY 2003 Progress Report 

purposes are tested with standard PFSA membranes. 

Figure 2 (top) illustrates comparative polarization 

curves under a pressurized oxygen test protocol for 

comparing the activity of the various catalysts, 

showing many performing better than pure Pt. 

Figure 2 (bottom) illustrates the range of precious 

metal loadings under investigation and the effect on 

H2/air fuel cell performance for one PtAxBy

construction. The anode catalyst is 0.14 mg Pt/cm2 

in each case of Figure 2 (bottom). A four-fold 

Figure 2.	 (A) Comparison of high pressure oxygen metric 

polarization curves from various 

nanostructured thin film ternary catalysts with 

0.1 mg/cm2 of Pt, unless noted. 

(B) Comparison of pressurized, constant 

stoichiometry (CS), constant current, 

polarization curves for two PtAB cathode 

catalyst constructions having 0.100 and 0.025 

mg Pt/cm2, with 0.14 mg/cm2

 of pure Pt on the 

anode. Cell T = 80oC, 30/30 psig, 1.5/2.2 H2/ 

air stoichiometry, galvanodynamic scans 

(GDS), 100%/60% anode/cathode inlet RH, 50­

cm2

 quad-serpentine flow field. 

445 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

reduction in cathode loading has cost approximately 

50 – 100 mV of cell performance over the 0.1 to 0.9 

A/cm2

 current range and illustrates the challenge of 

the DOE targets of 0.05 mg/cm2

 total per MEA 

producing 0.5 A/cm2 at 0.8 V. 

Significant progress has been made with our 

Dalhousie University subcontractor in applying 

combinatorial methodology for fabricating 50-cm2 

sized arrays of continuously varying catalyst 

compositions and structures, applied to the 3M 

nanostructured support films. A dozen of these 

catalyst arrays have been fabricated in triplicate and 

characterized by scanning X-ray diffraction and 

electron microprobe, formed into MEAs at 3M and 

tested using combinatorial and segmented cell 

screening methods as well as larger fuel cell tests. 

Baseline data have been obtained to establish the 

degree of correlation between the subcontractor’s 

and 3M’s deposition processes and identify issues 

with the combinatorial and segmented cell screening 

analyses that need to be resolved in order to usefully 

reveal catalyst activity differences seen in single cell 

constructions. 

Under high temperature and dry conditions, 

stability of all the MEA components is a challenge. 

The catalyst activity, its surface area and its support 

particle must all be stable, both chemically and 

electrochemically, particularly against oxidation. The 

thermal stability of the 3M nanostructured film 

supported catalysts was shown to be significantly 

greater than commercially available carbon supported 

Pt catalysts, using highly sensitive thermal gravimetric 

analysis weight-loss profiles over 20 hours at 170oC in 

air (see Reference 3). In-situ fuel cell measurements 

of catalyst electrochemical surface area (ECSA) 

before and after 90 hours under 120oC, 30 psig H2/air, 

and constant current conditions have shown a 

negligible loss in surface area for the 3M ternary 

catalysts, compared to a 42% loss in 70 hours from 

carbon supported Pt catalysts. More recent 

characterization of oxidative stability was completed 

by voltammetric polarization of cells to 1.2 V for 5 

hours at 80oC under saturated H2/N2, followed by 

complete cyclic voltammetry scans for ECSA 

measurements. As shown in Figure 3, over 

approximately 50 hours, the conventional dispersed 

carbon supported catalysts’ ECSA decreased 

significantly and progressively after each 5 hour 

period while its double layer capacitance increased, 

indicating carbon oxidation. In contrast, the 3M 

nanostructured film supported Pt catalysts’ ECSA 

progressively increased, consistent with catalyst cleanup, and the double layer capacitance was essentially 

unchanged, consistent with the increased thermal 

stability of the 3M catalyst support system. The loss 

of surface area is shown to be directly related to fuel 

cell performance, and the rate of surface area loss is 

temperature dependent. 

Good progress towards development of a high 

temperature membrane (120 < T < 150oC) that does 

not rely on water for proton conduction has been 

Figure 3. Comparison of cyclic voltammograms from 

(A) carbon supported Pt and 

(B) 3M nanostructured film supported Pt, taken 

every five hours during which the cell was 

polarized to 1.2 V at 80oC under saturated H2/ 

N2. The ECSA of the C/Pt catalyst decreased 

with time, and its double layer capacitance 

increased. The opposite is true for the 3M 

nanostructured film supported catalyst. 

446 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

realized through both development of critical 

characterization techniques and new materials 

synthesis. High proton conductivity, as opposed to a 

more general ionic conductivity measured by AC 

impedance techniques, in the absence of water is a 

first requirement for such materials, and a 

methodology was developed to measure the proton 

conductivity of liquid based cells containing the new 

electrolyte candidates. Figure 4 compares the proton 

conductivity as a function of temperature in the 

absence of water of five different combinations of 

fluorinated acids and liquid additives, none of which 

involves phosphoric acid. As seen, the combination 

of acid D with liquid X has already at 120oC 

produced conductivity sufficient for acceptable fuel 

cell performance at lower temperatures with standard 

PEMs. Work has recently begun on incorporating 

these proton conductive materials into useable solid 

polymer membranes and addressing the issues of 

forming effective catalyst/ionomer interfaces. More 

conventional high frequency impedance 

measurements of these membranes agree with the 

liquid cell proton conductivity measurements. 

Conclusions 

The 3M PFSA ionomeric membrane has shown 

longer lifetime and improved mechanical properties 

Figure 4.	 Illustration of the proton conductivity, measured 

in a special liquid cell with proton injection, of 

five different electrolyte combinations of 

perfluorinated acids and liquid additives, with no 

water in the system. The target range for 

adequate proton conductivity is > 0.030 S/cm. 

over membranes made with current commercial PEM 

ionomers for operation in the temperature range 85 < 

T < 120°C. There is the opportunity for further 

improvement with key additives. For the range 120 

< T < 150°C, the approach to development of new 

membranes using perfluorinated acids plus liquid 

additives is promising, based on actual proton 

conductivity results. Key issues will revolve around 

forming useful membranes and effective catalyst/ 

electrolyte interfaces with these new materials. The 

oxidative chemical stability and high temperature 

electrochemical surface area stability of 3M 

nanostructured catalysts and supports appear to be 

better than those of commercial carbon black 

supported Pt catalysts. The 3M nanostructured 

catalyst process and combinatorial approach to 

development of new catalysts are continuing to yield 

catalyst constructions having improved performance 

with lower loadings. 

References 

1. Hydrogen, Fuel Cells, and Infrastructure 

Technologies FY 2002 Progress Report, page 379. 

2. M. K. Debe, "Novel catalysts, catalyst support and 

catalyst coated membrane methods," in Handbook 

of Fuel Cells, Fundamentals, Technology and 

Applications, Vol. 3, eds. W. Vielstich, A. Lamm 

and H. Gasteiger, John Wiley and Sons, p. 576. 

3. 2003 DOE Hydrogen, Fuel Cells, and 

Infrastructure Technologies Program Review 

Meeting, May 19 - 22, 2003, Berkeley, CA, 

Project 72. 

4. A. B. Laconti et al., "Mechanisms of membrane 

degradation," in Handbook of Fuel Cells, 

Fundamentals, Technology and Applications, Vol. 

3, eds. W. Vielstich, A. Lamm and H. Gasteiger, 

John Wiley and Sons, p. 647. 

FY 2003 Publications/Presentations 

1. 2003 DOE Hydrogen, Fuel Cells, and 

Infrastructure Technologies Program Review 

Meeting, May 19 - 22, 2003, Berkeley, CA, 

Project 72. 

447 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Ultra-Thin Composite Membrane-Electrode Assembly 

For High-Temperature Proton Exchange Membrane Fuel Cells 

Chao-Yi Yuh (Primary Contact), Ray Kopp, Pinakin Patel 

FuelCell Energy, Inc. 

3 Great Pasture Road 

Danbury, CT 06813 

Phone: (203) 825-6112; Fax: (203) 825-6273; E-mail: cyuh@fce.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

ANL Technical Advisor: William Swift 

Phone: (630) 252-5964, Fax: (630) 972-4473; E-mail: swift@cmt.anl.gov 

Subcontractor: Ion Power, Inc., Bear, DE 

Objectives 

•	 Develop an ultra-thin (< 75 μm), durable membrane capable of operation at 100-140°C 

•	 Achieve <0.2 Ωcm2 membrane ohmic resistance and <1% crossover 

•	 Attain high ionic conductance with negligible electronic conductivity 

•	 Attain high mechanical strength 

•	 Demonstrate >0.6 V performance at 400 mA/cm2 under ambient reformate/air operation at 120°C 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Durability 

•	 F. Heat Utilization 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 R. Thermal and Water Management 

Approach 

Develop a solid superacid-Nafion® composite membrane electrode assembly (MEA): 

•	 Solid superacids as high-temperature proton conductors and moisture retainers 

• Nafion 	 ® phase as proton conducting binder phase 

•	 Stable support phase added to enhance strength 

Accomplishments 

•	 Developed an understanding of MEA performance-controlling factors 

•	 Demonstrated MEA performance of ~0.6 V at 400 mA/cm2 and membrane ohmic resistance of <0.2 

Ωcm2 under system operating conditions [atmospheric, low relative humidity (RH), hydrogen/air 

stoichs 1.2/2.0] at 120°C 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Achieved >750 mV performance at 400 mA/cm2 under 30 psig operating pressure 

• Successfully scaled up MEA to 300 cm2 

Future Directions 

• Understand MEA decay mechanisms in detail 

• Further enhance mechanical durability 

• Enhance catalyst utilization by further increasing proton conductivity in cathode 

Introduction 

Fuel cells are inherently very efficient and clean, 

and they offer the best alternative to conventional 

power generation technologies. For fuel cells to be 

commercially competitive, issues such as cost, size, 

and functionality need to be addressed. A desired 

commercial distributed/stationary fuel cell system is 

an atmospheric-pressure natural gas-fueled proton 

exchange membrane fuel cell (PEMFC) system with 

>35% higher heating value (HHV) efficiency, 

>100°C operation for cogeneration, simple 

construction, >40,000 h reliable life, and <$1000/kW 

system cost. For the PEMFC to be commercially 

viable, the performance of critical components, such 

as the polymer electrolyte membrane in particular, 

needs to be enhanced. At present, the operating 

temperature of the state-of-the-art PEMFC is 

approximately between 60 and 80°C. Carbon 

monoxide poisoning of the PEMFC anode’s precious 

metal catalyst is a major technical barrier for utilizing 

hydrocarbon feedstock. Since the poisoning by CO 

weakens considerably with temperature, one 

mitigation approach is to operate the PEMFC at 

higher temperatures. Many other advantages can 

also be realized, such as faster electrode kinetics, 

higher quality waste heat for cogeneration, cathode 

flooding mitigation, and greater ability to remove 

waste heat. 

The baseline Nafion® membrane is deficient in 

terms of ionic conductivity above 100°C and at low 

relative humidity (RH), conditions desired for 

atmospheric-pressure stationary applications. Such 

conditions tend to dry out the membrane, drastically 

reducing membrane proton conductivity. 

Furthermore, the loss of water causes membrane 

embrittlement, resulting in membrane cracking, 

reactant cross-leakage and poor electrode-membrane 

contact. Therefore, a cost-effective membrane, with 

proton conductivity that is less sensitive to change in 

water content, is needed. Another important issue for 

>100°C operation is significantly reduced cell 

voltage loss. Only a minor portion of cell voltage 

loss is caused by the membrane ohmic resistance 

increase. The majority of the voltage loss increase is 

due to the increase in cathode polarization. 

Approach 

The overall objective is to operate a PEMFC at 

100-140°C to improve CO tolerance, mitigate water 

and thermal management challenges and reduce 

membrane cost. The basic approach is to develop a 

composite membrane consisting of mechanical 

support and high-temperature proton conduction 

phases. In order to improve cathode performance, 

incorporating promising solid superacids into the 

cathode is also pursued. 

Results 

A number of ultra-thin composite membranes and 

MEAs have been developed to improve water 

retention and proton conduction at 120°C (Figure 1). 

Additives/modifiers with specific properties have been 

synthesized. The performance of the fabricated MEAs 

in laboratory-scale cells has been characterized to 

screen promising formulations. About 0.6 V 

performance and <0.2 Ωcm2 resistance at 120°C and 

400 mA/cm2

 under system operating conditions 

(atmospheric, low RH, high utilizations) have been 

achieved (Figure 2). The anode polarization loss is 

negligible (~10 mV) under these conditions. The 

MEA Pt loading was 0.4 mg/cm2

 for each electrode. 

This represents one of the best cell performances ever 

reported in the literature under these conditions. 

Greater than 750 mV performance at 120°C was also 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

achieved under pressurized operating condition (30 

psig) (Figure 3). The promising MEA has been 

successfully scaled up to nominal 300 cm2

 (Figure 4). 

The AC-impedance data revealed that the cathode is 

under mixed ohmic-kinetic control, while masstransfer loss is minor (Figure 5). Therefore, enhancing 

proton conductivity in the cathode is expected to 

further improve cathode performance. This project 

was completed on June 30, 2003. 

Figure 1. High-performing Ultra-thin MEA (<75 μm) 

Figure 3. Performance of >0.75 V at 400 mA/cm2 

under Pressurized Operating Conditions Ha 

Been Achieved 

Figure 4. Promising MEA Has Been Successfully 

Scaled Up to 300 cm2 

Figure 2. About 0.6 V Performance and <0.2 Ωcm2 

Resistance at 120°C and 400 mA/cm2 under 

System Operating Conditions (atmospheric, 

low R.H., high utilizations) Have Been 

Achieved 

Figure 5.	 AC-impedance Data Show That the Cathode 

Is Under Mixed Kinetic-Ohmic Control at 

120°C 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Conclusion 

An MEA performance of ~600 mV at 400 mA/ 

cm2 under system operating conditions has been 

demonstrated, representing a major milestone 

towards developing a viable atmospheric PEMFC 

system. To further enhance cell performance (to a 

desired 0.8 V at 400 mA/cm2

), optimization of 

cathode structure and formulation to enhance proton 

conduction and cathode catalyst utilization is 

required. 

FY 2003 Publications/Presentations 

1. Yuh, P. Patel, R. Kopp, and L. Lipp, "MembraneElectrode Assembly for High-Temperature 

PEMFC," The American Chemical Society 226th 

Meeting, New York City, NY, September 7-11, 

2003. 

2. Yuh, "R&D on an Ultra Thin Composite 

Membrane for High-Temperature Operation in 

PEMFC," 2003 Hydrogen and Fuel Cells Merit 

Review Meeting, Berkeley, CA, May 19-22, 2003. 

3. Yuh, "R&D on an Ultra Thin Composite 

Membrane for High-Temperature Operation in 

PEMFC," Annual Report to US DOE, for the 

Period of September 2000 to August 2001. 

4. Yuh, "R&D on an Ultra Thin Composite 

Membrane for High-Temperature Operation in 

PEMFC," Annual Report to US DOE, for the 

Period of September 2001 to August 2002. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of High-Performance, Low-Pt Cathodes Containing New Catalysts 

and Layer Structure 

Paolina Atanassova (Primary Contact), David Dericotte, Bogdan Gurau, Paul Napolitano, Jim 

Brewster, Rimple Bhatia, Bryan Apodaca, Mark Hampden-Smith (Cabot Superior MicroPowders); 

JoAnn Schwartz, Lin Wang, John Gantzhorn (DuPont Fuel Cells); and Sandip Mazumder (CFDRC) 

Cabot Superior MicroPowders 

3740 Hawkins Dr. NE 

Albuquerque, NM 87109 

Phone: (505) 342-1492; Fax: (505) 342-2168; E-mail: paolina@cabot-corp.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Subcontractors: DuPont Fuel Cells, Wilmington, DE; CFDRC, Huntsville, AL 

Objectives 

•	 Develop and apply combinatorial powder synthesis platform based on spray pyrolysis for discovery of 

high-performance, low-Pt cathode electrocatalysts. 

•	 Develop engineered cathode layer structures containing the new electrocatalysts. 

•	 Demonstrate enhanced performance of membrane electrode assemblies (MEAs) with low Pt content 

towards the DOE goals of 0.6 g Pt/kW in automotive applications for the year 2005. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 Q. Electrode Performance 

•	 P. Durability 

Approach 

•	 Design and build a Combinatorial Powder Synthesis System (CPSS) capable of generation of large 

numbers of electrocatalyst powders with variable composition and microstructure. 

•	 Design and build rapid ink formulation and electrode deposition equipment to screen electrocatalysts 

generated by the CPSS for their activity in oxygen reduction reaction (ORR) in half-cell configuration. 

•	 Establish baseline for performance of Pt electrocatalysts in ORR based on rapid screening; establish 

go/no-go criteria for binary and ternary alloy electrocatalysts synthesized in the combinatorial system. 

•	 Continue optimization of the MEA structure with benchmark Pt-based supported catalysts with 

various Pt loadings in the catalysts and in the cathode layer. 

•	 Model the electrode structure to reveal effects of layer porosity and gas humidification levels at 

different fuel cell operating conditions (temperature and pressure). 

Accomplishments 

•	 The assembly of the CPSS was completed, fully automated and integrated to achieve the initial 

planned rates of electrocatalyst samples production (between 100 and 150 samples per week). 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 The assembly of the rapid ink formulation and electrode deposition equipment was completed, and 

testing rates are compatible with electrocatalyst production rates. 

•	 Baseline performance of Pt electrocatalysts was evaluated for a broad range of Pt loadings. Go/no-go 

criteria were established for newly synthesized alloy electrocatalysts. The half-cell rapid screening 

technique is exclusively used for screening electrocatalysts for their ORR activity. 

•	 Combination of the best ternary alloy catalyst (Effort 1) and the best MEA structure/printing approach 

(Effort 2) delivers single MEA performance of less than 1 g Pt/kW at 0.8 V (100% improvement 

compared to best results of 2002, 2 g Pt/kW), see Figure 1. 

•	 Modeling of cathode layer porosity and pore size distribution provides guidance for electrocatalyst 

structure modification. 

Figure 1.	 Summary of Performance Achievements in 

FY 2003 Compared to FY 2002 

Future Directions 

•	 Apply the CPSS and rapid screening equipment to the production and screening of a large number of 

electrocatalyst powders with variable compositions and microstructures. 

•	 Characterize electrocatalysts by structural and electrochemical techniques to provide further focus of 

the combinatorial workflow and choice of compositions. 

•	 Perform single MEA testing at various fuel cell operating conditions (gas utilization, humidification 

and pressure). 

•	 Perform long-term testing. 

•	 Demonstrate performance of best-performing electrocatalyst and the optimal MEA structure in a short 

stack fuel cell. 

•	 Design and start assembly of rapid screening equipment in MEA configuration. 

•	 Complete modeling of ionomer distribution within the cathode layer structure. 

Introduction 

The overall project goals, as stated previously, 

are to significantly improve both the kinetic 

performance of the electrocatalyst powder at low 

noble metal loadings (Effort 1: Combinatorial 

discovery of low-Pt compositions with microstructure 

optimization using spray-based catalyst 

manufacturing) and its utilization in the cathode 

layers through layer structure development (Effort 2: 

Development of engineered particles and layers). 

Approach 

The approach relies on the integration of 

combinatorial synthesis of ORR electrocatalysts by 

spray conversion and optimized electrode structures 

enabled by the unique morphology of these 

electrocatalysts. The majority of the second year’s 

effort was focused on the design, assembly and 

benchmarking of the combinatorial equipment for 

electrocatalyst synthesis and the high-throughput 

equipment for testing in half-cell configuration. 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

These equipment additions will allow for a 

significant increase in the number of compositional 

and micro-structural electrocatalyst variations that 

can be screened during Year 3 of the project. In 

parallel, the correlation between rapid half-cell 

screening test data and MEA performance for multicomponent (alloys and mixed oxides) 

electrocatalysts was addressed. 

The combined progress of both Effort 1 and 

Effort 2 were demonstrated in a single 50 cm2 MEA. 

Stack testing criteria have been established and 

include stability testing of alloys in acidic media and 

long-term testing in a single MEA. Testing in the 

MEA configuration was expanded to cover broader 

variations of the operating conditions recommended 

by the fuel cell manufacturers in addition to the 

standard testing conditions. 

Results 

Combinatorial Synthesis. The assembly and testing 

of the Combinatorial Powder Synthesis System 

(CPSS) was completed in March 2003, and the CPSS 

is currently being used for combinatorial 

electrocatalyst synthesis (Figure 2). The CPSS was 

designed based on an R&D platform that leverages 

SMP’s knowledge base of system scale-up, which 

ensures a pathway to high-volume manufacturing 

once promising candidates have been identified from 

an experimental campaign. The CPSS system is 

highly automated; an operator is required only to 

prepare feedstock precursor solutions (which are 

Figure 2. Combinatorial Powder Synthesis System 

(CPSS) 

 FY 2003 Progress Report 

combined on-the-fly in controlled amounts) and to 

respond to operating excursions. To execute a run, 

the CPSS reads a database containing the physical 

data of the precursor solutions and the critical 

operating parameters (including processing 

temperature, gas flow rates, precursor feed rates and 

elemental composition of the target materials). For 

each individual run, the CPSS maintains and 

monitors the set points for all critical parameters. 

Graphical, numerical and statistical data for each run 

are presented in real-time charts and spreadsheets. 

Individual powder samples are isolated in the 

collection system to prevent cross-contamination and 

losses. The powders can be easily removed from the 

collection system and packaged for characterization, 

storage or shipment. 

The CPSS has been engineered to accommodate 

up to four metal sources and two carbon sources for 

each campaign. As a result, a wide variety of 

compositions can be explored with minimal 

downtime for system cleaning or re-configuration. 

Depending on testing requirements and material 

systems, 100 to 150 samples per week can be 

produced, with a potential to further increase the 

number of samples to 300 per week. Furthermore, 

the CPSS greatly reduces the volume of paperwork, 

man-hours and quantity of raw materials required to 

accomplish a rigorous study while providing a higher 

level of data quality. Baseline performance of the 

system was evaluated against the conventional unit. 

Specifically, physical characteristics (e.g. metal 

crystallite sizes, particle sizes, morphology) of test 

powders were examined, and it was determined that 

the combinatorial system can reproduce results from 

the scale-up units for benchmark Pt-based catalysts. 

Long-term testing of the system demonstrated that 

the CPSS operates consistently and accurately with 

minimal input from the operator. Data (with 

statistical analysis) are automatically collected and 

reported by the supervisory control and data 

acquisition (SCADA) system to ensure 

reproducibility and accountability. 

Rapid screening of the electrochemical 

performance. DuPont Fuel Cells designed and 

completed the assembly of the rapid ink formulation 

and electrode deposition equipment in June 2003. 

The new equipment can automatically mix and 

deposit electrode inks with rates comparable to those 

3 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

of the electrocatalyst synthesis achieved by the CPSS 

at Cabot Superior MicroPowders (Cabot SMP). The 

samples are then tested in half-cell 3-electrode 

configurations in parallel using a variety of 

electrochemical techniques. Between 75 and 150 

electrocatalysts can be screened per week, and test 

results are presented as current density normalized by 

the amount of Pt in the electrocatalyst (Figure 3). In 

parallel, cyclic voltamograms are recorded to 

facilitate a more detailed understanding of the active 

phase structure, such as active surface area and type 

and uniformity of surface features formed. The 

preparation of electrode inks was further optimized 

for electrocatalysts with different Pt and alloy 

compositions. An excellent correlation was 

established between the half-cell screening data and 

the performance of alloy electrocatalysts in MEA 

configuration. 

Based on extensive testing of Pt baseline 

catalysts supplied by Cabot SMP, a go/no-go criteria 

for the mass activity of the electrocatalyst was 

established for each group of electrocatalysts (10, 20, 

30, 40, 50, 60 wt.% Pt in combination with various 

carbon supports). The main goal of establishing 

adequate go/no-go criteria for this primary screen of 

newly synthesized electrocatalysts was to minimize 

the more time-consuming testing in MEAs and the 

number of false negative (or marginally positive) 

results. Currently, in order to qualify for testing in an 

MEA configuration, the specific mass activity of a 

new multi-component electrocatalyst needs to exceed 

that of the best pure Pt catalyst by at least 20% 

(Figure 3). The go/no-go criteria could be further 

increased to ensure that the testing in the MEA 

configuration will be focused mainly on electrode 

layer optimization. 

Binary and ternary Pt alloys. In order to establish 

and improve the combinatorial approach 

methodology, the spray pyrolysis processing of 

several binary and ternary compositions supported on 

Vulcan XC-72 was further optimized. The efforts 

were directed towards variations of metals loading 

(20, 40, 60 wt.%) and types of carbon support. The 

effect of spray processing and post processing 

conditions on the metal crystallite size and degree of 

alloying were also evaluated. Post processing of the 

electrocatalysts was further optimized, and testing of 

the stability of the alloys in acidic media is 

underway. For the best-performing 20 wt.% metal 

ternary alloy catalyst, an increase of the mass activity 

of up to 70% (in terms of mA/mg Pt) was observed 

when alloyed catalysts were compared to pure Pt in 

the rapid half-cell testing (supported alloys close to 2 

times more active than pure Pt, Figure 3). Figure 4 

compares the MEA performance of 20 wt.% 

PtM1M2/Vulcan XC-72 electrocatalyst compared 

with 20 wt.% Pt/Vulcan XC-72 at identical total Pt 

loadings of 0.13 mg Pt/cm2 . At 0.8 V, the 

performance of the ternary alloy catalyst is 220 mA/ 

cm2

, as compared to 100 mA/cm2 for the pure Pt 

electrocatalyst. If compared at constant current 

density of 0.2 mA/cm2, the alloy catalyst delivers 

approximately 30 mV higher potential. Initial 

Figure 3.	 Test Results from Half-Cell Rapid Screening 

for Mass Activity of 20 wt.% Pt and Alloys 

Supported Electrocatalysts (SCE = saturated 

calomel electrode) 

Figure 4.	 Polarization Curves for MEA with Total 

Loading of 0.13 mg Pt/cm2 (Comparing 

performance of 20 wt.% PtM1M2 ternary 

alloy catalysts and 20 wt.% Pt/ Vulcan XC 

72, test conditions described in the text; 

bottom left, TEM image of alloy catalyst.) 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

structural analysis of the ternary alloy 

electrocatalysts demonstrates excellent dispersion of 

the active phase (Figure 3). 

MEA test conditions. Test MEAs (50 cm2) were 

used for the evaluation, using Nafion 112 (DuPont) 

membranes. The MEAs were tested at 80oC, with 

flows corresponding to 1 A/cm2 at 1.5 stoichiometry 

for hydrogen and 2.5 stoichiometry for air on the 

anode and cathode, respectively. H2 and air (100% 

humidified) were used at 30 psig pressure on both the 

anode and cathode. 

MEA structure development. The development of 

the electrode structure was focused on optimization 

of the electrode deposition method with Pt and Ptalloy electrocatalysts that demonstrated best 

performance in the rapid half-cell screening. Figure 

5 shows charts for the MEA performance in terms of 

current and power density and in g Pt/kW at 0.8 V for 

50 wt.% Pt/C and 20 wt.% ternary alloy catalyst as a 

function of the total Pt loading in the MEA. For the 

50 wt.% Pt/high surface area carbon electrocatalyst, 

the performance in terms of current density at 0.8 V 

for the whole range of Pt loadings (0.55 to 0.35 mg 

Pt/cm2) is above 400 mA/cm2, and it achieves 1 g Pt/ 

kW for 0.35 mg Pt/cm2 loading. The ternary alloy 

catalyst supported on Vulcan XC-72 demonstrates 

300 mA/cm2

 at 0.8 V with 0.2 mg Pt/cm2 total Pt 

loading and below 1 g Pt/kW. These results 

demonstrate significant improvement in the overall 

MEA performance compared to last year’s 

benchmarked MEA performance of 2 g Pt/kW (over 

100% improvement). 

Figure 5. Summary of MEA Performance 

Characteristics 

Modeling effort. During the past year, CFDRC 

developed models to address the impacts of pore size 

distribution and active phase placement within 

various pore sizes on the overall performance of the 

fuel cell. These models are based on detailed 

reaction-diffusion balance of species at various 

length scales and include such effects as Knudsen 

diffusion. The models were used for parametric 

studies involving variation of catalyst fractions 

within four different pore sizes of interest to Cabot 

SMP. The results clearly demonstrate the sensitivity 

of the MEA performance to the distribution of the 

active phase in various pore sizes and provide 

valuable guidance for modification of porosity of the 

electrocatalysts and electrode layer. CFDRC also 

performed several parametric studies to address the 

effects of global parameters such as temperature, 

pressure, relative humidity and gas stochiometries on 

cell performance. These studies showed good 

correlation to the experimentally observed trends and 

provided guidance on the optimization of fuel cell 

operating conditions and/or MEA structure. 

Conclusions 

During the second year of the project, several 

significant milestones were met, and progress was 

demonstrated on all main tasks. In Effort 1: 

Combinatorial discovery of low-Pt compositions with 

microstructure optimization using spray-based 

catalyst manufacturing, two critical tools for the 

combinatorial workflow were designed and their 

assembly completed: Combinatorial Powder 

Synthesis System (Cabot SMP) and Rapid Ink 

Formulation and Electrode Deposition Equipment 

(DuPont Fuel Cells). In Effort 2: Development of 

engineered particles and layers, further improvement 

in the MEA performance was achieved due to 

optimization of the cathode structure and deposition 

method. Most importantly, it was demonstrated that 

a combination of the best-performing ternary Pt alloy 

catalysts (Effort 1) and the best electrode layer 

structure (Effort 2) had an additive effect and 

delivered MEA performance of less than 1 g Pt/kW 

at 0.8 V, representing over 100% improvement over 

last year’s benchmarked performance of 2 g Pt/kW 

(Figure 1). In addition, the synthesis of bestperforming ternary Pt alloy catalyst was scaled to 

commercial powder production levels. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Publications/Presentations 

1. P. Atanassova, D. Dericotte, P. Napolitano, R. 

Bhatia, J. Brewster, M. Hampden-Smith, C. 

Lundgren, L. Wang, S. Mazumder, Hydrogen, 

Fuel Cells and Infrastructure Technologies FY 

2002 Progress Report, p.423 

2. P. Napolitano, D. Dericotte, R. Bhatia, P. 

Atanassova, M. Hampden-Smith, T. Kodas, 

“Combinatorial Synthesis of Oxygen Reduction 

Electrocatalysts by Spray Pyrolysis”, 

presentation, 2002 ECS Meeting, October 20-24, 

2002, Salt Lake City, Utah, Meeting abstracts, 

p.729 

 FY 2003 Progress Report 

3. P. Napolitano, D. Dericotte, B. Apodaca, R. 

Bhatia, P. Atanassova, M. Hampden-Smith, T. 

Kodas, “A New Focused, Scaleable 

Combinatorial Synthesis and Discovery Platform: 

Applications to Fuel Cell Electrocatalysts”, 

presentation, 5th Annual International Symposium 

on Combinatorial Approaches for New Materials 

Discovery, February 10-21, 2003, San Jose, CA 

4. M. Hampden-Smith, P. Atanassova, P. Atanassov, 

T. Kodas, “Manufacture of Electrocatalyst 

Powders by a Spray-based Production Platform”, 

Handbook of Fuel Cells, 2003 John Wiley & 

Sons, Eds. W. Vielstich, H. Gasteiger, A. Lamm, 

Vol.3, p. 497 

6 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Design and Installation of a Pilot Plant for High-Volume Electrode Production 

James Arps (Primary Contact) 

Southwest Research Institute (SwRI) 

P.O. Drawer 28510 

San Antonio, TX 78228-0510 

Phone: (210) 522-6588; Fax: (210) 522-6220; E-mail: jarps@swri.org 

DOE Technology Development Manager: JoAnn Milliken
 

Phone: (202) 586-2480; Fax: (202) 586-9811; E-mail:JoAnn.Milliken@ee.doe.gov
 

Subcontractors: 

General Motors, Warren, MI
 

W.L. Gore & Associates, Inc., Elkton, MD 

Objectives 

•	 Significantly reduce overall membrane electrode assembly (MEA) cost by developing vacuum 

catalyzation methods that can meet DOE precious metal loading targets of 0.2 g/rated kW by 2010. 

•	 Improve prospects for practical implementation of fuel cell technology in high-volume applications by 

demonstrating scalable, high-throughput manufacturing technologies. 

•	 Evaluate performance of materials under relevant fuel cell operating conditions to confirm process 

viability. 

•	 Complete process development and qualification of a pilot manufacturing plant. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

Approach 

•	 Determine the impact of large-scale catalyzation methods on MEA performance, if any, and develop 

approaches to minimize them. 

•	 Establish in situ process control methods for catalyst deposition and demonstrate high-efficiency metal 

recovery approaches. 

•	 Benchmark MEAs fabricated at SwRI against commercially available products. 

•	 Incorporate SwRI-manufactured MEAs into two "short stack" fuel cells built by General Motors (GM) 

and deliver to Argonne National Laboratory for testing and evaluation. 

Accomplishments 

•	 Continued work with pilot manufacturing system, catalyzing over 3000 linear feet of electrode 

material as part of ongoing process optimization and production yield studies. 

•	 Completed assembly and initial testing of hydrogen-air and reformate-air fuel cell stacks at GM. 

•	 Conducted single-cell durability testing over 500+ hours in conjunction with Gore. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Deliver stacks to Argonne National Laboratory for further testing and evaluation. 

•	 Continue process development and optimization in anticipation of transitioning technology to fullscale production. 

•	 Adapt vacuum deposition methods to fabrication of ultra-thin Pd alloy membranes for hydrogen 

purification (new DOE project). 

•	 Examine feasibility of vacuum deposition methods in development of reversible fuel cells and nonprecious metal catalysts. 

Introduction 

Progress in the adoption of fuel cell technology 

in the automotive area will depend to a large extent 

on the economics of catalyst utilization, the MEA 

production system, and the resultant performance in 

a fuel cell system. Recent cost analyses have 

suggested that MEAs can constitute as much as 80% 

of the cost of a fuel cell stack. Hence, improvements 

in the inherent performance of MEAs while 

substantially reducing the catalyst content per unit 

area will contribute significantly to lowering the cost 

of producing fuel cell generated power. The 

development of manufacturing concepts permitting 

the continuous and high-speed catalyzation of 

electrodes should have a significant beneficial impact 

on the cost of the MEAs and the dollars per kilowatt 

of power produced by the fuel cell. 

Until recently, most MEAs were produced in 

time-consuming, batch-type processes. This 

situation has existed because of generally low 

volume purchases of MEAs and the large variety of 

MEA sizes and configurations required by the 

various fuel cell systems manufacturers. In effect, 

the industry is in a "chicken and egg" situation where 

low-price components, including MEAs, are required 

for high-volume commercialization of fuel cells, yet 

component suppliers need high volumes to attain low 

prices. Without a large present market, the 

investment risk is considerable and may be beyond 

the means of any industrial entity. 

High-volume, continuous operations capable of 

producing sub-components such as electrodes should 

dramatically reduce the cost of the finished product. 

Southwest Research Institute (SwRI) is investigating 

this proposition by developing large-area, vacuumbased electrode substrate coating technologies to 

reduce overall material content of the finished part. 

Specifically, "ultra-low" precious metal loaded 

electrodes with loadings of 0.10 mg/cm2

 or less have 

been fabricated using state-of-the art polymer 

electrolyte membranes and electrode substrates 

procured from Gore. The best-performing MEAs 

have been delivered to General Motors for the 

construction and supply of two fuel cell "short 

stacks" to Argonne National Laboratory (ANL). 

Approach and Results 

Activities in the past year have focused on 

further investigations of optimal materials processing 

conditions using the vacuum roll coater. Several 

thousand linear feet of additional intermediate 

electrode material has been supplied by Gore over 

the past year for use with this system. Pilot 

quantities of catalyzed electrode material (Figure 1), 

up to 500 linear feet per run, have been prepared and 

Figure 1. Vacuum-Catalyzed Intermediate Electrode 

Material 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

evaluated using standardized test methods. These 

materials have in turn been used to fabricate fullscale MEAs utilizing state-of-the-art GORESELECT® membranes (Figure 2). 

A small number of fuel cell "short stacks", each 

typically 803 cm2 active area and consisting of 14 

cells using composite plates, have been assembled 

and tested at GM. Each stack contains both baseline 

and experimental MEAs that can be individually 

monitored for "side-by-side" testing and comparison. 

The hydrogen-air stack utilizes a total precious metal 

loading of 0.2 mg/cm2 and has generated a peak 

power of approximately 5 kW operating at 220 kpa 

pressure with hydrogen and air stoicheometries of 

1.2 and 2.0, respectively. In laboratory tests, smaller 

single cells (25-100 cm2) were fabricated with total 

Figure 2. Full-Scale MEA for GM Test Stack 

 FY 2003 Progress Report 

loadings of ~0.1 mg/cm2

 and have generated power 

densities of more than 1.0 A/cm2 at 0.6 V running at 

similar pressures and stoicheometries. In an effort to 

more fully characterize the performance of ultra-low 

load electrodes, the effects of cathode 

humidification, gas diffusion media, cell 

compression, and cell assembly have been 

investigated. In support of this effort, W.L. Gore and 

Associates has also been conducting performance 

and durability life testing of samples fabricated at 

SwRI. The results to date have suggested that, while 

durability goals may be even more challenging with 

low loading electrodes compared to high loading 

samples independent of the catalyst deposition 

method used, this particular technology has 

significant value in enabling low-loading MEAs to 

meet the required power density targets. 

Conclusions 

A pilot manufacturing facility has now been 

completed that has the capability to catalyze more 

than 100,000 square meters of electrode material on a 

three-shift basis - enough to facilitate the production 

of MEAs for tens of thousands of fuel cell-powered 

automobiles. Pilot quantities of catalyzed electrode 

material, up to 500 linear feet per run, have been 

prepared, with small scale (25-100 cm2

 active area) 

and full scale (up to 800 cm2 active area) MEAs 

fabricated using the prepared electrode materials. 

Selected examples have been provided to W.L. Gore 

and GM for testing, evaluation, and, incorporation 

into two fuel cell stacks. The first hydrogen-air stack 

has generated a peak power of approximately 5 kW 

and is being prepared for delivery to ANL. The 

second stack, configured to run on reformate, is 

scheduled for final test and shipment before the end 

of the fiscal year. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Scale-Up of Carbon/Carbon Composite Bipolar Plates 

David Haack (Primary Contact), Ken Butcher, Earl Robert Torre 

Porvair Fuel Cell Technology, Inc. 

700 Shepherd Street 

Hendersonville, NC 28792 

Phone: (800) 843-6105; Fax: (828) 697-7960; E-mail: dhaack@pamus.com 

DOE Technology Development Manager: Donna Lee Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: donna.ho@ee.doe.gov 

Subcontractor: UTC Fuel Cells, Inc., South Windsor, CT 

Objectives 

•	 Develop carbon/carbon composite materials for bipolar plates that meet or exceed targets 

•	 Evaluate the performance of the bipolar plate materials through fuel cell stack testing 

•	 Design and construct a research-scale production line for materials development efforts 

•	 Design and construct a pilot-scale production line to demonstrate high-volume, low-cost bipolar plate 

manufacturing 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

Approach 

Phase I 

•	 Design, construct and install material forming, pressing and thermal treatment equipment 

•	 Systematically investigate material forming techniques and composition ingredients 

•	 Systematically investigate material processing variables and test material properties 

•	 Perform fuel cell testing to evaluate plate performance at UTC Fuel Cells 

•	 Investigate forming techniques aimed at rapid, low-cost production 

Phase II 

•	 Design, construct and install pilot-scale production line for 300 plates per hour capacity 

•	 Design and implement quality assurance system for pilot line 

•	 Evaluate pilot line performance and estimate pilot and mass bipolar plate production costs 

•	 Evaluate pilot line bipolar plates for fuel cell performance and deliver fuel cell stack 

Accomplishments 

•	 Completed numerous fuel cell tests at UTC Fuel Cells, gathering invaluable information regarding 

material design and functionality 

•	 Completed installation and demonstration of Phase I development line 

•	 Expanded line to manufacture materials in higher volumes to meet near-term demands for product 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Developed extensive quality assurance system to complement near-term product manufacturing 

(quality system audited by UTC Fuel Cells) 

•	 Began investigation into Phase II pilot production line processes; identified key process bottleneck 

areas in Phase II line 

•	 Developed detailed timeline and organized plan for Phase II line implementation 

•	 Continued development of improved bipolar plate materials 

Future Directions 

•	 Continue fuel cell testing at partner site 

•	 Continue product development activities 

•	 Initiate Phase II line process investigations to address specific process bottlenecks 

•	 Accelerate Phase II line design and installation activities 

•	 Continue to develop materials and processes to increase product yield and product sensitivity to raw 

material and process variation 

Introduction 

In April 2001, Porvair Fuel Cell Technology, Inc. 

(PFCT) licensed a carbon/carbon composite bipolar 

plate formation technology from Oak Ridge National 

Laboratory. The goal of PFCT is to transfer this 

technology from the laboratory to full-scale, low-cost 

mass production to meet the emerging need of the 

rapidly developing fuel cell industry. This project is 

directed at further developing the carbon/carbon 

bipolar plate material to meet the performance, 

durability and cost demands of the fuel cell industry, 

and demonstrating a pilot-scale manufacturing line to 

produce this material in reasonable pilot quantities 

(300 plates per hour) at low cost. 

Approach 

The path to final production demonstration is 

split into two major parts in this project. Phase I 

focuses upon material and composition refinement to 

satisfy the fuel cell property and performance 

requirements. Phase II focuses upon the design, 

installation and operation of a fully functional bipolar 

plate production line capable of demonstrating high 

speed, low cost plate manufacturing. 

The approach taken in materials development 

utilizes information fed back to PFCT by our 

customers following product property and fuel cell 

testing. Specific needs and concerns of our 

customers are evaluated relative to the current state 

of the product or process development to guide 

improvements leading toward a better bipolar plate. 

Internally, materials development efforts are guided 

through the performance of statistically designed 

experiments. Key product or process variables are 

evaluated in an orthogonal array of experiments. 

Results are measured and analyzed to determine the 

degree of influence each variable has on the 

measured property. A statistical model is then built 

to aid in moving subsequent experiments into a nearoptimum range of investigation. 

The approach utilized in planning the Phase II 

production line utilizes external contract engineering 

assistance along with internal process development 

activities. A local engineering house has been 

contracted to assist with Phase II project planning 

and execution. The execution plan schedules 

specific milestone events, including the development 

of an overall project outline, the development of key 

Process Instrumentation and Control, Process Flow 

and Plant Layout Diagrams, the development of the 

governing quality system and the basics of plant 

layout and construction (tear-down and clear-out, 

utility plan, environmental permitting, equipment 

specifications and bids, etc.). 

Results 

Phase I of the project has been completed in the 

past year. Our Phase I objectives were met, including 

development of materials with properties that exceed 

DOE targets and successful fuel cell testing through 

our commercial partner, UTC Fuel Cells. Further, 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

because of the strong interest in the product, 

activities were performed to expand the Phase I 

development line, and quality system development 

activities were implemented for this line. PFCT and 

our customers provided the funds used to expand the 

Phase I line. 

Figures 1 and 2 show some of the expanded 

Phase I equipment. The accelerated manufacturing 

of the product enabled PFCT to accelerate the 

learning associated with product and manufacturing 

Figure 1. Expanded Development Equipment Used In 

Bipolar Plate Manufacture - Forming 

 FY 2003 Progress Report 

issues. These include raw material specification fit 

to the product, impurities and supply capability, and 

process variability and its effect on product 

properties and product yields. Much of this 

experience will transfer directly to the Phase II line 

and enable faster implementation of that line. 

Materials development activities continued in 

2003 with the goal of continued materials properties 

improvement and cost reduction. Through materials 

development efforts, electrical conductivity was 

increased while maintaining flexural strength, 

formability and low hydrogen permeability. Table 1 

shows the properties relative to DOE targets. 

Conductivity, strength and material purity (all carbon 

product) are the key advantages of the material 

developed at PFCT. Figures 3 and 4 show the range 

of conductivity and strength achieved versus final 

Figure 3. Product Conductivity as a Function Of Density 

Figure 2. Development Equipment Used in Bipolar Plate 

Evaluation - Laboratory Figure 4. Product Strength as a Function of Density 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 1. Carbon/Carbon Material Properties 

Property Value DOE Target 

Electrical Conductivity 

(S/cm) (ASTM C611) 

> 600 > 100 

Density (g/cc) 1.00 - 1.30 -

Flexural Strength (psi) >5000 > 600 

(crush) 

Flexibility (%)(deflection at mid-span) 1.5 - 3.5 3-5 

Hydrogen Permeability 

(cc/cm2/sec) (ASTM 

D1434) 

<2x10-6 <2x10-6 

product density, respectively. The conductivity of 

the product greatly exceeds that of competitive lowcost bipolar plate materials. Different bipolar plate 

designs have been fully embossed using the 

developed materials with good success, 

demonstrating the potential of this material in the 

manufacture of low-cost plates. 

In manufacturing products, sealing against 

hydrogen occurs through the chemical vapor 

infiltration process. In this process, carbon is 

deposited from a hydrocarbon gaseous precursor 

such that a hermetic skin is formed on the surfaces of 

the product. This yields a product that is sealed at a 

much lower overall density than competitive bipolar 

plates. Figure 5 is a micrograph of the sealed region 

of the product. 

Numerous fuel cell tests have been performed at 

UTC Fuel Cells to date. The goals have been 

focused at both investigating the product for basic 

performance and evaluating aspects of the product 

for acceptable fuel cell performance and durability. 

Both single cell and multiple cell testing has 

occurred. Much of this testing has been funded by 

UTC Fuel Cells, independent of this development 

project. Positive test results have led to a strong 

demand for the product, but specific data are 

proprietary. The chart shown in Figure 6 shows 

qualitatively the performance improvements that 

PFCT products have been able to achieve over the 

course of the project. In general, the number 

following Porvair in the chart is chronological. Later 

products performed well against the bill of material 

Figure 5.	 SEM Micrograph of a Molded Carbon/Carbon 

Composite Material (Figure shows thin skin 

coating on plate exterior to provide plate 

sealing.) 

Figure 6.	 Polarization Curve Showing PFCT Materials in 

UTC Fuel Cells Testing Relative to Bill of 

Material (BOM) Target (Numbers in chart 

reference product trials in approximate 

chronological order.) WTP = water transport 

plate; LD = low density; HD = high density; 

ASC = a/cm2 

machined graphite. Specific test results have been 

used by UTC Fuel Cells to evaluate product 

performance relative to competitive products and 

plate design. Specific feedback to PFCT has been 

used to guide product design and process changes to 

yield a better performing and more consistently 

manufactured product. 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Specific work has been done toward the Phase II 

line, including up-front planning and process scaleup development. Specific portions of the process, 

where equipment cost is prohibitive or where line 

bottlenecks exist, are receiving attention to simplify 

the required equipment and increase the processing 

time for that portion of the manufacturing cycle. A 

plan has been developed to investigate these 

processes to yield equipment specifications so that 

the necessary equipment can be ordered and installed 

for Phase II. 

The Phase II line will be semi-automated, where 

key processes are monitored and controlled with 

calibrated electronic equipment. Component transfer 

will be through use of conveyors or simple robotics 

where such operations are not complex. Initial cost 

analyses have been performed to evaluate the costeffectiveness of the line. As with any manufacturing 

process, final product cost depends greatly on the 

yield of the manufacturing line. The line 

implementation plan anticipates low yields to start, 

increasing to optimum levels over the first 4-6 

months of line operation. 

Conclusions 

Porvair Fuel Cell Technology has continued to 

develop materials and manufacturing processes to 

supply high quality bipolar plates to the fuel cell 

industry. Advancements in the past year have 

included continued mass manufacturing process 

investigation and Phase II production line planning. 

In addition, due to product demand, the 

laboratory system has been expanded, and a 

complete quality assurance system has been 

developed and implemented for this development 

line. The quality system will serve as the backbone 

for the Phase II production line. 

Fuel cell tests of PFCT's bipolar plate products 

have continued at a rapid rate at UTC Fuel Cells, as 

the products are evaluated for beta and preproduction units. Tests have taken place in singlecell, multi-cell and full stack arrangements. 

Special Recognitions & Awards 

1. Federal Laboratory Consortium for Technology 

Transfer, Excellence in Technology Transfer 

Award 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Carbon Composite Bipolar Plates 

T. M. Besmann (Primary Contact), J.W. Klett, and J. J. Henry, Jr. 

Surface Processing and Mechanics Group and Carbon and Insulating Materials Group 

Oak Ridge National Laboratory, P.O. Box 2008, MS 6063, Bldg. 4515 

Oak Ridge, TN 37831-6063 

Phone: (865) 574-6852; Fax: (865) 574-6918; E-mail: besmanntm@ornl.gov 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

ORNL Technical Advisor: David Stinton 

Phone: (865) 574-4556; Fax: (865) 574-6918; E-mail: stintondp@ornl.gov 

Objectives 

•	 Develop a slurry molded carbon fiber material with a carbon chemical vapor infiltrated sealed surface 

as a bipolar plate. 

•	 Collaborate with manufacturer/licensee with regard to testing and manufacturing of such components. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan 

•	 O. Stack Material and Manufacturing Cost 

Approach 

•	 Fabricate fibrous component pre-forms for the bipolar plate by slurry molding techniques using carbon 

fibers of appropriate lengths. 

•	 Fabricate hermetic plates using a final seal with chemical vapor infiltrated carbon. 

•	 Develop commercial-scale components for evaluation. 

Accomplishments 

•	 In coordination with licensee, have reduced thickness of plates from 2.5 mm to 1.5 mm. Determined 

influence of chemical vapor infiltration (CVI) temperature on depth of infiltration. 

•	 Further characterized and measured mechanical properties of carbon composite plate material. 

•	 Determined electronic properties, including effect of surface roughness on resistance. 

•	 Developed initial model of chemical vapor infiltration process that is scalable to production. The 

model was utilized to improve the flow pattern of gas used to deposit carbon on the plate. 

Future Directions 

•	 Support continued scale-up of the licensee's operation through modeling of fabrication processes. 

•	 Optimize mechanical properties through combination of pre-form material and CVI conditions. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

The challenges for PEMFC technology for 

automobiles lie in reducing the cost and weight of the 

fuel stack, an impediment to which is the cost and 

weight of the bipolar plate. The bipolar plate is the 

electrode plate that separates individual cells in a 

stack. A stack is formed when multiple cells are 

aligned one after another so as to work in series, with 

the bipolar plate providing an electrode for the cells 

on either side. The reference material for the bipolar 

plate is high-density graphite with machined flow 

channels. Both material and machining costs for 

graphite, however, are prohibitive for many fuel cell 

applications, and this has led to substantial 

development efforts to replace graphite. The 

requirements for a bipolar plate are stringent, 

including low-cost materials and processing, light 

weight, thin (<3mm), sufficient mechanical integrity, 

high surface and bulk electronic conductivity, low 

permeability (boundary between fuel and oxidant), 

and high corrosion resistance (in the moist 

atmosphere of the cell). 

The bipolar plate approach developed at Oak 

Ridge National Laboratory (ORNL) uses a low-cost, 

slurry-molding process to produce a carbon-fiber 

pre-form. The molded, carbon-fiber component 

could have an inherent volume for diffusing fuel or 

air to the electrolyte surface or impressed flow-field 

channels. The bipolar plate is made hermetic 

through chemical vapor infiltration (CVI) with 

carbon. The infiltrated carbon also serves to make 

the component highly conductive. 

The work during FY 2003 included efforts to 

reduce the thickness of the bipolar plate. Other 

research focused on determining the properties of 

bipolar plates prepared from pre-form material 

supplied by Porvair Fuel Cell Technology (the 

licensee) as well as ORNL, as a function of 

processing. This includes strength and fracture 

toughness, the depth of penetration of infiltrated 

carbon, and the effect of surface roughness on 

conductivity/resistivity. Also developed during this 

period was a first-order model of the CVI process 

based on the ORNL CVI system. These efforts were 

in cooperation with and in support of the work at 

Porvair to scale up and commercialize the 

technology. 

 FY 2003 Progress Report 

Approach 

At Porvair Fuel Cell Technology, pre-forms were 

produced that were reduced from 2.5 mm in 

thickness to 1.5 mm through an increased 

concentration of particulate material in the pre-form 

that resulted in a higher green density (density before 

infiltration with carbon). The effect of this higher 

green density on infiltration was investigated through 

intercomparisons with ORNL material, which did not 

contain particulates and was of lower density. Void 

volume as a function of through-thickness position 

was determined by digital analysis of images of 

polished cross-sections. The effect of processing 

conditions (CVI temperature) on density gradients 

through the plates were similarly investigated. 

The mechanical properties of the plates were 

determined through notch sensitivity. Holes of 

differing sizes were machined in plate specimens and 

tested under tension to failure. The characterization 

of the variation of strength with hole size provides 

information on fracture toughness. Ultimate strength 

is found from the zero intercept of the strength versus 

the ratio of hole diameter to sample width. 

The electrical properties as a function of surface 

roughness may be an issue in fuel cell stacks. This 

was investigated by producing samples with differing 

surface roughnesses due to different CVI 

temperatures, and by also evaluating polished and 

uninfiltrated samples. Two-point and four-point 

measurements were obtained which provide contact 

resistance and bulk conductivity, respectively. 

In order to allow efficient scale-up of the CVI 

process, a computational fluid dynamics model of the 

process, coupled with chemical kinetic information, 

was developed. This used the existing CVI system 

geometry and conditions at ORNL. 

Results 

Porvair has successfully reduced the thickness of 

the bipolar plates through a high particulate content 

giving high green strength (strength before 

infiltration with carbon). Determination of the 

through-thickness density gradient of the infiltrated 

Porvair material reveals that little carbon is deposited 

within the material and that the overcoating and 

sealing of the surface happens early during 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

infiltration (Figure 1). This is in contrast to the 

original ORNL pre-form material that consists 

entirely of fiber and carbonized phenolic, and has 

more than twice the uninfiltrated void volume. Thus, 

after infiltration, especially at higher temperatures 

where the ORNL material is overcoated and sealed 

relatively rapidly, the ORNL component has a large 

density gradient, whereas the infiltrated Porvair preform has a high-density outer coating and fairly 

uniform internal density. Lower temperature and 

longer infiltration times do not modify this behavior 

for the Porvair material, but do result in higher 

density, more uniform ORNL plates. All infiltrated 

plates are hermetic. 

Figure 1.	 Fracture Surface of a Sealed Bipolar Plate 

Produced with Porvair Pre-Form Material 

Showing the Particulate Filled Interior and 

the CVI Carbon Coating on the Surface 

Figure 2.	 Plot of Measured Strength Versus the Ratio 

of Hole Size to Sample Width Illustrating 

Ultimate Strength and Notch-Insenstivity 

 FY 2003 Progress Report 

The strength and fracture toughness of the 

bipolar plate material were evaluated using the 

variable hole tensile test. The results of the tensile 

curves (Figure 2) reveal that the material is relatively 

notch insensitive. The strengths indicated by the 

zero intercepts (Figure 2) range from 25 to 28 MPa. 

Measurements of contact resistance show a weak 

dependence on surface roughness. Table 1 shows the 

results where only the polished samples indicate a 

measurably lower contact resistance, with the 

exception of the uninfiltrated material which had 

fewer interfaces that could contribute to ohmic 

losses. High bulk conductivity is also indicated. 

The computational fluid dynamics modeling 

revealed flow patterns within the CVI reactor. This 

included differences in the flow above and below the 

bipolar plate. This information was used to modify 

the inlet geometry so that the flow was significantly 

more uniform, and therefore deposition rates on the 

top and bottom of the plates were more uniform. 

Figure 3 illustrates the effect of improving the flow 

geometry. 

Conclusions 

•	 Increasing the particulate content of the pre-form 

allows a reduction in bipolar plate thickness, more 

uniform density, and easier/more rapid sealing via 

CVI. 

•	 Mechanical property measurements indicate the 

bipolar plate material is notch-insensitive, and 

therefore relatively tough, and has good strength. 

•	 Electrical measurements indicate low contact 

resistance and high bulk conductivity, with a weak 

dependence on surface roughness. 

Figure 3.	 Computed Flow Pattern of Reactive Gases 

Around a Bipolar Plate in the ORNL CVI 

Reactor 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 1. Two- and Four-Point Probe Electrical Measurements 

Infiltration Sourface 

Roughness

Rz μm 

Resistance 

2 Probe DC 

ohms 

Conductivity

4 Probe V/I

Treatment σ S/cm 

4 hours at 1500°C 8.83 1.86 365 

24 hours at 1350°C 12.9 1.37 417 

Uninfiltrated 13.5 0.86 369 

4 hours at 1500°C 10.2 2.16 386 

24 hours at 1350°C 14.3 1.57 383 

24 hours at 1350°C 2.9 0.84 408 

•	 Computational fluid dynamics applied to the CVI 

process at ORNL indicated means for increasing 

plate infiltration uniformity. 

FY 2003 Publications/Presentations 

1. T. M. Besmann, J. J. Henry, Jr., J. Klett, D. Haack, 

and K. Butcher, "Optimization of a Carbon 

Composite Bipolar Plate For PEM Fuel Cells," 

Proc. Materials Research Society, Vol. 756 

Special Recognitions & Awards/Patents 

Issued 

1. Year 2002 National Federal Laboratory 

Consortium “Excellence in Technology Transfer 

Award.” 

2. Year 2002 Southeast Region of the Federal 

Laboratory Consortium “Excellence in 

Technology Transfer Award.” 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Cost-Effective Surface Modification for Metallic Bipolar Plates 

M.P. Brady (Primary Contact), K.L. More, P.F. Tortorelli, L.R. Walker 

MS 6115, Oak Ridge National Laboratory 

P.O. Box 2008, Oak Ridge, TN 37831-6115 

Phone: (865) 574-5153; Fax: (865) 241-0215; E-mail: bradymp@ornl.gov 

Collaborating Coauthors: K. Weisbrod, M. Wilson, and F. Garzon, Los Alamos National Laboratory; 

H. Wang, National Renewable Energy Laboratory; I. Paulauskas and R.A. Buchanan, University of 

Tennessee, Knoxville 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

ORNL Technical Advisor: David Stinton 

Phone: (865) 574-4556; Fax: (865) 241-0411; E-mail: stintondp@ornl.gov 

Objectives 

•	 Develop a low cost metallic bipolar plate alloy that will form an electrically conductive and corrosion 

resistant nitride surface layer during thermal nitriding to enable use in a proton exchange membrane 

(PEM) fuel cell environment. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost. 

•	 P. Durability 

Approach 

•	 Conduct a study of the nitridation behavior of a series of model Ni/Fe-X base alloys (X = nitride 

forming elements such as Cr, Nb, Ti, V) that can potentially meet DOE bipolar plate cost goals. 

•	 Identify the most promising combination of X additions, ternary and higher order alloying elements, 

and nitriding conditions that result in the formation of an adherent, protective nitride surface layer. 

•	 Evaluate the corrosion, electrical properties, and fuel cell behavior of the thermally nitrided alloys. 

•	 Characterize the nitride layer microstructure and composition by x-ray diffraction, electron probe 

microanalysis, scanning electron microscopy, and transmission electron microscopy. Use this 

information in a feedback loop to modify alloy chemistry and nitridation processing conditions to 

optimize the protectiveness of the nitride surface layer. 

Accomplishments 

•	 Nitridation of a model Ni-50Cr alloy was optimized to form a dense, protective CrN/Cr2N surface 

layer. 

•	 The nitrided model Ni-50Cr alloy exhibited very low levels of metal-ion dissolution and negligible 

increase in contact resistance in a 1000-hour single-cell, fuel cell test using 50 cm2 active area anode 

and cathode plates and in a 4100-hour bipolar coupon corrosion test. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 A United States patent disclosure was submitted in April 2003 for nitrided Ni/Fe-Cr and related base 

alloys thermally nitrided to form a protective CrN/Cr2N surface layer. 

•	 Collaboration was established with DANA Corporation, Tennessee Technological University, and the 

University of Minnesota to evaluate sealing and manufacturability issues of nitrided Ni-Cr alloys and 

to demonstrate technological viability of the approach by a 5-cell stack test. 

Future Directions 

•	 Continue in-cell evaluation of nitrided Ni-50Cr to fully characterize and optimize the protectiveness of 

the CrN/Cr2N surface layer. This testing will include single-cell and stack testing with Los Alamos 

National Laboratory (LANL) and fuel cell manufacturers. 

•	 Modify alloy composition/nitriding conditions to form a corrosion-resistant CrN/Cr2N surface layer on 

Ni/Fe-Cr base alloys that are comparable to conventional stainless steels in terms of manufacturability 

and cost in order to meet DOE bipolar plate cost goals. Establish partnerships with alloy producers 

and fuel cell manufacturers. 

Introduction 

The bipolar plate is one of the most expensive 

components in PEM fuel cells. Thin metallic bipolar 

plates offer the potential for significantly lower cost 

than currently-used machined graphite bipolar plates 

and reduced weight/volume and better performance 

than developmental polymer/ carbon fiber and 

graphite composite bipolar plates. However, 

inadequate corrosion resistance can lead to high 

electrical resistance and/or contamination of the 

polymer membrane, both of which can significantly 

degrade performance. Metal nitrides offer electrical 

conductivities up to an order of magnitude greater 

than that of graphite and are highly corrosion 

resistant. Unfortunately, most conventional coating 

methods (for metal nitrides) are too expensive for 

PEM fuel cell stack commercialization or tend to 

leave pin-hole defects, which result in accelerated 

local corrosion and unacceptable performance. 

Approach 

The goal of this effort is to develop a bipolar 

plate alloy that will form an electrically conductive 

and corrosion resistant nitride surface layer during 

thermal (gas) nitriding. There are three advantages 

to this approach. First, because the nitriding is 

performed at elevated temperatures, pin-hole defects 

are not expected because thermodynamic and kinetic 

factors favor complete conversion of the metal 

surface to nitride. Rather, the key issues are nitride 

layer cracking, adherence, and morphology (discrete 

internal subsurface precipitates vs. continuous 

external scales), which can potentially be controlled 

through proper selection of alloy composition and 

nitridation conditions. Second, the alloy can be 

formed into final shape by inexpensive metal 

forming techniques such as stamping prior to thermal 

nitridation. Third, thermal nitridation is an 

inexpensive, well-established industrial technique. 

Results 

A nitrided Ni-50Cr model alloy coupon was 

exposed for 4100 hours (h) under simulated PEM 

fuel cell anode and cathode bipolar plate conditions 

using the corrosion test cell developed at LANL [1]. 

The test environment was a pH 3 solution of H2SO4 

containing 2 ppm F-

 at 80°C. Hydrogen and air at 1 

atmosphere were supplied to the anode and cathode 

faces, respectively, of the flat (no flow field features) 

test coupon. Platinum screens passed 1 A/cm2 

electrical current to the ELAT® electrode/carbon 

backing paper/bipolar test coupon assembly, and the 

electrical potential was recorded in-situ to monitor 

resistive surface phase (e.g. oxide) growth. In the 

corrosion test cell, the nitrided Ni-50Cr bipolar 

coupon exhibited a voltage change of only 2 mV/ 

1000 h at the anode and 2.7 mV/1000 h at the 

cathode over the course of the 4100 h exposure. The 

anode face of the coupon effectively experienced 

~ -0.31 V vs standard hydrogen electrode (SHE) and 

the cathode face +0.56 V. Ni levels of only 0.85, 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1. Interfacial contact resistance data a) asnitrided b) after 4100 h in corrosion test cell. 

Note that the data for the bipolar coupon 

from the corrosion test cell include both 

anode and cathode faces; the as-nitrided 

comparative data from Figure 1a was 

therefore doubled. 

0.56, and 2.4 ppm were measured in the anode-face 

exposed solutions and 0.034, 0.019, and 0.027 ppm 

Ni in the cathode-face exposed solutions, 

respectively, for 0-1500, 1500-3400, and 3400-4100 

hours of exposure. Cr was not detected. Interfacial 

contact resistance (ICR) data as a function of 

compaction pressure are shown in Figure 1. The Ni50Cr alloy (no nitridation treatment) had a lower 

contact resistance than 316L stainless steel, shown 

for comparative purposes. Subsequent nitridation of 

Ni-50Cr significantly lowered contact resistance 

(Figure 1a). ICR measurements of the 4100 h 

exposed bipolar test coupon (Figure 1b) showed no 

increase in ICR relative to as-nitrided Ni-50Cr. Back 

scattered electron (BSE) images of a nitrided Ni50Cr control coupon, the 4100 h cathodeenvironment exposed face, and the 4100 h anodeFigure 2. Back Scattered Electron Cross-Sections of 

Nitrided Ni-50Cr a) as-Nitrided b) 4100 h Air 

(cathode face) Exposure in Corrosion Test 

Cell, c) 4100 h H2 (anode face) Exposure in 

Corrosion Test Cell 

environment exposed face, are shown in Figure 2. 

The external nitride scale consisted of three layers: a 

~1 micron thick semi-continuous outer layer of CrN 

(not visible in the figure); an intermediate, 3-5 

microns thick continuous layer of Cr2N; and an inner 

layer of the ternary Ni-Cr-N π phase. The 

microstructure of the nitride on the cathode-exposed 

face (Figure 2b) and the anode-exposed face (Figure 

2c) appeared essentially the same as the archival, asnitrided material, with no evidence of significant 

attack or surface oxide formation (based on 

transmission electron microscopy cross-sections). 

A single-cell fuel cell test was subsequently 

conducted using 50 cm2 active area anode and 

cathode plates of nitrided Ni-50Cr with a simple 

serpentine flow-field groove pattern (Figure 3). The 

membrane electrode assembly (MEA) was Nafion® 

112 with anode and cathode loadings of ~ 0.20 mg 

Pt/cm2 . The gas diffusion layers (backings) were 

uncatalyzed ELAT® . Double-sided ELAT® was used 

on the anode sides and single-sided on the cathodes. 

The cells were operated at 3 atmospheres (absolute) 

and at 80°C. Purified hydrogen was introduced to 

the cell at 0.3 standard liters per minute (SLPM) and 

compressed room air at 1.8 SLPM. The fuel cell was 

operated continuously at 0.7 V 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 3. Nitrided Ni-50Cr Cathode Plate from SingleCell Fuel Cell Test 

.An inadvertent cutoff in the supply of hydrogen 

to the cell during the test resulted in membrane 

damage and performance degradation such that the 

test was halted after 500 h, and the damaged MEA 

was replaced. A second MEA was prepared with 

anode/cathode loadings of 0.23/0.37 mg Pt/cm2 on a 

thicker membrane, Nafion® 1135. It was operated 

for 500 h, for a total of ~1,000 h of in-cell testing of 

the nitrided plates. Cell resistance, an indicator of 

membrane contamination, did not increase a 

discernable amount over the second 500 h 

(resistances were measured with the initial MEA but 

were untrustworthy due to the damaged MEA). The 

baseline interfacial resistance contributions between 

the nitrided plates and the adjacent gold-coated 

current collector plates were 5 mΩ-cm2 at the 

cathode plate and 1 mΩ-cm2 at the anode (the totalcell resistances were on the order of 130 mΩ-cm2

). 

X-ray fluorescence indicated only trace levels of 

Ni and Cr in the MEAs after the single-cell fuel cell 

test, in the range of only 0.01 to 0.3 x 10-6 g/cm2 

. 

This level of contamination is extremely low and 

consistent with the stable, inert, and protective 

behavior of the CrN/Cr2N surface. Some stagnant 

liquid was observed in one of the alignment pin ports 

on disassembly of the cell and was subsequently 

found to be Cr-rich. However, little Cr or other 

contamination was observed in the membrane in the 

area surrounding this alignment pin. A local casting 

flaw and/or compositional inhomogeneity (e.g., 

inclusion) in the alloy is suspected to have led to 

 FY 2003 Progress Report 

poor nitridation at this spot, making it vulnerable to 

attack. 

Conclusions 

The results of the 4100 h corrosion test and the 

1000 h single-cell fuel cell test demonstrate the 

potential of thermally grown CrN/Cr2N surface 

layers on Cr-bearing alloys to: 

1	 prevent significant metal-ion membrane 

contamination, 

2	 maintain low contact resistance, and 

3	 effectively cover and protect flow-field groove 

features under PEM fuel cell bipolar plate 

operating conditions. 

Future work will focus on the formation of 

corrosion-resistant CrN/Cr2N surface layers on Ni/ 

Fe-Cr base alloys that are comparable to 

conventional stainless steels in order to meet DOE 

bipolar plate cost goals. 

References 

1. K. Weisbrod, U.S. Patent 6,454,922 "Corrosion 

test cell for bipolar plates" September 24, 2002. 

FY 2002 Publications/Presentations 

1. M.P. Brady, K. Weisbrod, I. Paulauskas, R.A. 

Buchanan, K.L. More, H. Wang, M. Wilson, F. 

Garzon, L.R. Walker, "Protection of Metallic 

Bipolar Plates in PEM Fuel Cells", submitted for 

journal publication June 2003. 

2. M.P. Brady, I. Paulauskas, R.A. Buchanan, K. 

Weisbrod, H. Wang, L.R. Walker, L.S. Miller, 

"Evaluation of Thermally Nitrided Metallic 

Bipolar Plates for PEM Fuel Cells", to be 

published in Proceedings of the 2nd European 

PEFC Forum, Lucerne, Switzerland, June 30-July 

4, 2003. 

3. M.P. Brady, K. Weisbrod, C. Zawodzinski, I. 

Paulauskas, R.A. Buchanan, and L.R. Walker, 

"Assessment of Thermal Nitridation to Protect 

Metal Bipolar Plates in Polymer Electrolyte 

4 
Combustion and Emission Control for Advanced CIDI Engines FY 2003 Progress Report 

Membrane Fuel Cells", Electrochemical and 

Solid-State Letters, 5, 11 2002. 

4. M.P. Brady, K. Weisbrod, C. Zawodzinski, I. 

Paulauskas, R.A. Buchanan, L.R. Walker, K.L. 

More, D.F. Wilson, and P.F. Tortorelli, "Thermal 

Nitridation to Protect Metal Bipolar Plates in 

PEM Fuel Cells", presented at the Fall 2002 

Meeting of The Materials Research Society, 

December 2002. 

5. I. Paulauskas, M.P. Brady, R.A. Buchanan, 

"Thermally Nitrided Alloys As Materials For 

Bipolar Plates In PEM Fuel Cells", poster 

presented at the 2002 Gordon Research 

Conference of Fuel Cells, Roger Williams 

University, RI, July 28-August 2, 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. "Metallic Bipolar Plate Alloys Amenable to 

Inexpensive Surface Modification for Corrosion 

Resistance and Electrical Conductivity", M.P. 

Brady, J.H. Schneibel, B.A. Pint, and P.J. 

Maziasz, United States Patent Disclosure, April 

2003. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

High-Performance, Matching, PEM Fuel Cell Components and Integrated Pilot 

Manufacturing Processes 

Mark K. Debe (Primary Contact), Judith B. Hartmann 

3M Company 

3M Center, Building 0201-01-N-19 

St. Paul MN 55144-1000 

Phone: (651) 736-9563; Fax: (651) 575-1187; E-mail: mkdebe1@mmm.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

ANL Technical Advisor: Thomas Benjamin 

Phone: (630) 252-1632; Fax: (630) 252-4176; E-mail: benjamin@cmt.anl.gov 

Subcontractor: General Motors Corporation, Honeoye Falls, NY 

Objectives 

•	 Develop a set of high-performance, matched proton exchange membrane (PEM) fuel cell components 

and pilot manufacturing processes to facilitate high-volume, high-yield stack production. 

•	 Demonstrate the matched component performance in a 1-kW fuel cell stack. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 Q. Electrode Performance 

Approach 

Phase 1 

•	 Utilize the 3M-patented, nanostructured thin film catalyst support system and catalyst deposition 

process to easily generate new compositions and structures of (a) binary and ternary catalysts for 

higher cathode performance and (b) binary anode catalysts and electrode structures for higher 

reformate tolerance with a non-precious metal replacement for Ru. 

•	 Develop carbon electrode backing/gas diffusion layer (EB/GDL) media optimized for performance 

with the catalyst system and flow field. 

•	 Optimize the fuel cell flow field design for optimized water management and air bleed utilization with 

the catalyst and EB/GDL components. 

•	 Define pilot manufacturing scale-up of the processes for fabrication of catalysts, catalyst-coated 

membrane (CCM) assemblies, and EB/GDL. 

Phase 2 

•	 Optimize pilot-scale manufacturing of roll-good fabricated (made by a semi-continuous process and 

stored on a roll) catalyst support films and catalyst deposition. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Specify membrane electrode assembly (MEA) component parameters and conduct final pilot-scale 

runs to generate process statistics. 

•	 Fabricate, test, and provide a 1-kW stack to subcontractor for evaluation using optimized flow field 

and matched MEAs fabricated by pilot processes. 

Accomplishments 

•	 Completed multiple pilot-scale roll-good fabrication runs and statistical evaluation of nanostructured 

catalyst support films with multiple lots of cathode (PtAB) and anode (PtM) catalyst depositions on the 

substrates. 

•	 Completed multiple pilot-scale fabrication runs and statistical evaluation of multiple lots of roll-good 

fabricated CCM assemblies, using multiple lots of PEMs and catalyst roll-goods. 

•	 Completed fuel cell testing and statistical analyses of roll-good fabricated EB/GDL materials and 

CCMs having matched properties for optimum performance. 

•	 Fabricated and tested two air-cooled and one liquid-cooled stack designs (> 1 kW) with unique 

compression, manifolding, and cooling features for evaluating 200-cm2

 MEAs. 

•	 Completed successful liquid-cooled stack testing of MEAs made with roll-good fabricated, 

nanostructured, thin film catalysts and matching components at subcontractor and 3M facilities. 

Obtained 1.9 kWe + 2.25 kW heat at 62% air utilization under “Vehicle Test Conditions” with ~0.34 

mg Pt/cm2

/MEA total. Results meet DOE 2005 target of 0.6 g Pt/peak kW. 

Future Directions 

•	 Contract period of performance ended April 30, 2003. 

•	 New work on high-performance, lower-cost MEAs, which utilizes the accomplishments of this 

contract, is being conducted under DE-FC04-02AL67621, "Advanced MEAs for Enhanced Operating 

Conditions." 

Introduction 

The MEA is the core component set of a PEM 

fuel cell stack. An MEA consists of five basic 

components: anode and cathode catalysts, ion 

exchange polymer membrane, and anode and 

cathode electrode backing/gas diffusion layers (EB/ 

GDL). The functions of these basic components are 

intimately related, and their properties must be 

matched for optimum performance. For large-scale 

volume fabrication at the costs and quality targets 

required by transportation applications, very high 

yields and in-line process control of integrated 

processes based on cost-effective materials are 

required. To realize the full performance of the 

MEAs in a stack, the stack design must be optimized 

so as not to compromise the single-cell performance 

of the MEA. This requires understanding how to 

design the coolant and gas manifolds and 

compression control scheme and match the flow 

fields to the EB/GDL to obtain uniform reactant, 

temperature and current density distributions. This 

contract was directed towards demonstrating highperformance, matching PEM fuel cell components 

manufacturable by integrated pilot processes in a 1­

kW sized stack. 

Approach 

The approach to the development of highperformance MEAs involved the development of 

components that were individually optimized and 

then matched for best overall performance at a 

particular set of operating conditions. It included the 

development of new anode and cathode catalysts 

directed at increasing performance and stability and 

reducing precious metal loading, using the 3M 

nanostructured, thin film catalyst support system and 

2 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

catalyst deposition process, which easily generates 

new compositions and structures via a dry, roll-goods 

process. The approach also included development of 

roll-goods EB/GDL media optimized for 

performance with the catalyst system and flow field 

and of a flow field design for optimized water 

management and air and fuel utilization. Evaluation 

of each component involved a variety of 

characterization techniques and single-cell fuel cell 

performance measurements under a broad range of 

controlled conditions. Pilot-scale, roll-goods 

manufacturing processes were optimized for 

fabrication of catalyst support films and catalyst 

depositions, CCM assemblies, and EB/GDL media. 

Process statistics were gathered in pilot-scale runs to 

assess the potential for high-volume manufacturing. 

Stack development was carried out to optimize 

uniformity of the stack reactant flows, compression, 

and temperature distributions over the MEA. Finally, 

performance of the matched components was 

demonstrated in short stacks (>1 kW), which were 

assembled at 3M and evaluated at the subcontractor's 

facilities and at 3M. 

Results 

In the FY 2002 Annual Progress Report for this 

contract (Ref. 1), results were presented for Pt binary 

and ternary cathode catalyst constructions that 

outperformed pure Pt. In particular, MEAs made 

with a ternary cathode designated as PtAB-2 and a Pt 

anode were highlighted. The single cell performance 

with lab-scale fabricated roll-good MEAs 

corresponded to the DOE 2005 target of 0.6 g/kW at 

0.8 V and 0.3 g/peak kW of precious metal. During 

Phase 2, the nanostructured thin film catalyst support 

system and the PtAB catalyst deposition process 

were successfully scaled up on pilot line equipment, 

and the same fundamental performance 

enhancements of the ternary were maintained. A 

new binary anode catalyst, “PtM,” having a nonprecious metal replacement for Ru had shown 

promise in Phase 1, and its scale-up was started in 

Phase 2 along with testing of MEAs made with PtM/ 

PtAB. However, it did not perform as well with the 

PtAB cathode catalyst as PtRu. Also, changing from 

the lab to the pilot-scale process affected its 

performance. Because optimizing the PtM 

construction and process would have required more 

time than was available on the contract, the PtRu 

anode was selected for scale-up. Both the PtRu and 

the PtAB nanostructured catalysts were successfully 

scaled up in a pilot production facility. Multiple lots 

were fabricated by roll-good processes on pilot 

production equipment and used in pilot scale-up 

experiments for the CCM assembly process. 

Characterization of the down-web and cross-web 

catalyst composition and loading verified a high level 

of uniformity. 

The CCM process experiments, in which the 

anode and cathode catalyst layers were transferred 

from the customized nanostructured substrate to the 

PEM, were run on pilot-scale, roll-goods equipment 

using multiple lots and types of catalyst and PEM 

(3M fabricated) roll-goods. This included catalyst 

lots that had been coated on reused substrate as a way 

to reduce costs. Extensive characterization of the 

roll-good fabricated CCMs to validate properties 

such as precious metal loading and to investigate 

variability indicated that the processes had been 

successfully scaled up and also that the reuse of the 

substrate was successful. The CCMs used in the 

stack tests discussed below were fabricated in the 

final pilot-scale runs. 

The EB/GDL component was developed and the 

processes scaled up in Phase 1, and preliminary 

results were reported in Ref. 1. During Phase 2, 

statistical analyses of the process variability for key 

response variables were completed, and a nested 

design of experiments was designed and completed 

for fuel cell response variables. The fuel cell 

response was less sensitive than the EB/GDL off-line 

physical property responses, which indicated that 

good process control for those key responses is 

sufficient for low variability in the EB/GDL fuel cell 

performance. Overall, the assessment indicated good 

potential for meeting anticipated process capability 

requirements in high-volume production. 

Cost projections were made using a detailed 

proprietary cost model for the MEA components and 

roll-goods processes. Different production scenarios 

were evaluated beginning with the processes and 

facilities currently used and then calculating 

improvements in areas identified with significant 

cost reduction potential. The final scenario utilized 

hypothetical values of process, labor, and material 

costs that might be realized when a high-volume 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

market size is reached. Under the final scenario 

using the detailed cost model, the MEA cost is not 

inconsistent with currently projected high-volume, 

long-term automotive pricing requirements. 

The performance of the matched components 

was successfully demonstrated in stacks developed at 

3M with consultation from the subcontractor. The 

stack design goal was to optimize the uniformity of 

the compression and the reactant and coolant flows 

for the MEA well enough to realize the same 

performance as obtained in single-cell testing. This 

was achieved using a 3M proprietary flow field 

design (discussed in Ref. 1), a unique modular 

compression control and gasket scheme, and 

computational fluid dynamic and thermal modeling 

designed gas and coolant flow manifolds. Bipolar 

plate development was not part of the scope, so goldplated Al was used based on fabrication ease for 

small quantities, electrical conductivity, and 

corrosion resistance. Three 1.4-kW (nominal) 

designs (two air-cooled and one liquid-cooled) were 

fabricated and tested at 3M. One air-cooled design 

was targeted at reformate/air operation, with the 

other air-cooled design and the liquid-cooled design 

targeted for H2/air. The liquid-cooled stack, “Beta1,” was then fully evaluated by the subcontractor at 

the General Motors Fuel Cell Activities facility under 

various protocols designed to demonstrate different 

aspects of the stack and MEA characteristics, 

including automotive test conditions. The stack 

contained fourteen 200-cm2 MEAs made with the 

pilot-scale roll-good processes. The nanostructured 

Pt/PtAB CCMs had ~0.34 mg Pt/cm2

/MEA total. 

Under automotive (vehicle simulation and 

compressor load following) test conditions, the stack 

achieved a mean cell voltage within 11 mV of the 

subcontractor’s target of 680 mV at 0.8 A/cm2 under 

pressurization conditions at 80oC and stoichiometric 

flow ratios of 3.0 anode and 1.6 cathode with subsaturated anode and dry cathode reactant streams. 

The required anode and cathode pressure drops 

across the stack were demonstrated. Cell-to-cell 

uniformity was excellent (23 mV spread, 6 mV 

standard deviation @ 1 A/cm2). In other tests, fuel 

and air utilization was also shown to be very good: 

the stability at very low stoichiometric flow ratios 

greatly exceeded expectations, achieving 95% 

hydrogen utilization and 77% air utilization at 

ambient pressure. The vehicle polarization test 

 FY 2003 Progress Report 

results exceeded design expectations, producing 1.9 

kWe peak actual with 62% air utilization versus the 

1.4 kWe with 45% air utilization expected. The stack 

was subsequently operated for 400 hours with no 

substantial change in performance. The values of 

0.34 mg Pt/cm2

 and 1.9 kW represent 0.50 g Pt/peak 

kWe, which meets the DOE 2005 target of 0.6 g Pt/ 

peak kW. Results from a subset of the tests 

conducted at the subcontractor’s facilities are shown 

in Figures 1-4. 

Figure 1 compares the “Beta-1” stack output 

under ambient and pressurized constant flow 

conditions. The stack results match well with singlecell test results (not shown) using a 3M protocol. 

The up and down scans are both included, so 28 

curves are superimposed for each pressure condition, 

illustrating the tight uniformity of the response, 

including hysteresis, of the 14 MEAs, which were 

Figure 1.	 Comparison of ambient and pressurized 

operation of the 3M "Beta-1" stack at the 

subcontractor's facilities under a 3M test 

protocol for comparison with single-cell tests. 

The roll-good fabricated MEAs have 0.34 mg 

precious metal/cm2

/MEA. Test 1A: 75oC stack, 

70/70oC dew points, 25/72 standard liters per 

minute (SLM) H2/air, galvanodynamic 

scanning, 1 min. per point. Test 1B: 85oC 

stack, 70/70oC dew points, 30/90 SLM H2/air, 

galvanodynamic scanning, 1 min./point. Both 

up-scan and down-scan curves are shown for 

the 14 MEAs in both the ambient and 

pressurized conditions. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

taken at 1-foot intervals along the CCM and MEA 

roll-goods. 

Figure 2 shows the “Baseline High-Pressure 

Polarization Curve” under the subcontractor’s 

protocol. At 1 A/cm2

, the standard deviation from 

the average cell voltage among the 14 MEAs is only 

6 mV. 

In Figure 3, the stack response under the 

“Vehicle Polarization Test Conditions” is shown. 

The stack inlet pressures and dew points 

(proprietary) are varied with current density. The 

stack and MEAs yielded good cell-to-cell uniformity 

over a majority of the current density range. At 1.2 

A/cm2

, the spread in voltage among the 14 cells was 

only 42 mV for a relatively low cathode 

stoichiometry of 1.6. The voltage spread appears to 

be largest, 49 mV, at 0.4 A/cm2

, but, excluding cells 

1 and 2, it reduces to only 22 mV. At the maximum 

tested current density, a peak power of 1.9 kWe is 

produced with 2.25 kW of heat. 

Figure 4 compares the stack/MEA response 

under Test 7 (see Figure 3) with Test 3B, the 

subcontractor’s compressor-load following protocol. 

Figure 2.	 Test 4: "Baseline High-Pressure Polarization 

Curve," 80oC stack, 80/64oC anode/cathode 

dew points, 1.3/2.0 H2/air constant 

stoichiometry (CS), 24.7/24.7 psig inlet 

pressure, galvanodynamic scanning (GDS), 10 

min./point. 

 FY 2003 Progress Report 

The pressure-load profile was the same, but the stack 

temperature, reactant humidification, and flow 

stoichiometries differed. Even though Test 3B had a 

higher cathode flow stoichiometry (2.0) than Test 7 

(1.6), the humidification was somewhat greater than 

under Test 7, indicating that the MEAs and stack 

perform better under hotter and drier conditions. 

Figure 3.	 Test 7: "Vehicle Polarization Test Conditions," 

61-84oC stack, variable (proprietary) dew 

points, 3.0/1.6 H2/air stoichiometry, 2.9-24.7 

psig inlet pressure, galvanodynamic scans, 10 

min./point. 

Figure 4.	 Comparison of the stack/MEA response under 

Test 7 (see Figure 3) and Test 3B, the 

subcontractor's "Compressor-Load Following" 

protocol. Even though the cathode 

stoichiometry for Test 3B is higher than that of 

Test 7, the conditions are hotter and drier for 

Test 7, and this gives better performance in the 

mid-current range. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

The development and roll-goods fabrication of a 

set of high-performance, matched PEM fuel cell 

components was completed and successfully 

demonstrated in stack testing at the subcontractor's 

facilities. The results under H2/air correspond to 

0.50 g Pt/peak kWe, which meets the DOE 2005 

target of 0.6 g Pt/peak kW. The MEA components 

used in the stack testing were produced by roll-good, 

pilot-scale processes that have the potential for 

meeting projected high-volume automotive 

requirements. 

 FY 2003 Progress Report 

References 

1. Hydrogen, Fuel Cells, and Infrastructure 

Technologies FY 2002 Progress Report, page 379. 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

High-Temperature Membranes 

Thomas A. Zawodzinski (Primary Contact), Hayley Every, Chockalingam Karuppaiah, Berryinne 

Chou, Thomas Kalapos, Micahel Pelsozy and Ramachandran Subaraman 

Department of Chemical Engineering and Case Advanced Power Institute 

Case Western Reserve University (CWRU) 

Cleveland, OH 44106 

Phone: (216) 368-5547; Fax: (216) 368-3016; E-mail: taz5@po.cwru.edu 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop new membranes and membrane electrode assemblies (MEAs) for operation at temperatures 

substantially in excess of 120°C. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• O. Stack Material and Manufacturing Cost 

• P. Durability 

• Q. Electrode Performance 

• R. Thermal and Water Management 

Approach 

Simultaneously carry out R&D on: 

• Physical chemistry of polymer electrolytes 

• New polymeric electrolytes 

• New approaches to proton transport in polymer electrolytes 

Develop MEAs based on new polymer electrolytes 

Accomplishments 

New Membranes 

• Synthesized new hybrid organic/inorganic membranes 

• Synthesized new materials to implement strategies targeting 'water replacements' 

Catalyst Coated Membranes (CCMs)/Electrodes 

• Showed performance limitation associated with low humidity operation relying on water 

• Elucidated effect of imidazole adsorption on electrode reactions 

Industrial and Other Collaborative Interactions 

• Evolved team model for project 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Completed Roadmap for High Temperature Polymer Membranes 

•	 High-Temperature Polymer Membrane Working Group continues to expand with increased industrial 

interaction 

Future Directions 

Computational Studies 

•	 Perform more extensive work on novel systems designed to identify approaches to maintain water 

content at 120oC 

Membrane Development 

•	 Provide new materials from each partner 

•	 Implement battery of methods for screening membranes; new electrolytes to be tested in 4-month 

cycle starting in fall 

CCMs/Electrodes 

•	 Start developing MEAs from new materials (CWRU) 

•	 Expand initial tests on oxygen reduction reaction (ORR) at high temperature/low humidity and on 

adsorption of imidazole, with intent to provide solutions 

•	 Develop understanding of interactions at buried interfaces within electrodes 

•	 Provide means for scale-up of polymers, film-making and CCM production to modest scale 

Industry and Other Collaborations 

•	 Next round of new start funding: increased emphasis on 120oC solutions 

•	 Begin to distribute 'lessons learned' info via website 

Introduction 

The need to operate at temperatures exceeding 

100°C presents difficult new challenges for the 

electrolytes used in fuel cells. This difficulty stems 

from the decrease in water content of the polymer 

electrolytes in the desired temperature range. There 

is a need for detailed understanding of the impact of 

poor or zero hydration on membrane and electrode 

processes in the fuel cell. Water plays a key 

facilitating role in proton transport, and lower water 

content thus leads to lower conductivity. Lack of 

water also has important negative consequences for 

electrode behavior. 

Approach 

At this point, we do not know which of several 

approaches is most promising. Thus, our membrane 

development efforts include: (1) a full-fledged effort 

to explore approaches involving polymer synthesis 

and development, as well as implementation of new 

"carrier" media to replace the function of water in 

Nafion; and (2) a study of proton transfer dynamics 

to inform the synthetic efforts. We are using theory 

to explore specific possibilities for new acid group 

types or for acid-base interactions that could lead to 

progress in proton transfer media and to assess the 

possibility of holding useful water in electrolytes at 

high temperature. We are increasing our 

understanding of the energetics of proton transfer to 

inform synthetic efforts. We are working to 

incorporate new polymers in fuel cells by developing 

catalyst-coated membranes from new materials. 

Finally, we also have extended our range of polymer 

electrolyte development efforts by including several 

different universities and significant industrial input. 

Our goal is to engage the polymer community to the 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

maximum extent possible, harvesting the best new 

ideas for development. 

Results 

Physical Chemistry. We are extending our 

computational studies to provide insight into the 

following processes: (i) tailoring bases to mimic 

water using substituted imidazoles or other proton 

carriers; and (ii) continuous water transport pathways 

at low relative humidity. This work augments 

experimental studies on water uptake by polymers 

and additives of various types. 

New Membranes. Many new materials are 

presently being prepared and tested. These are: (i) 

polymers and inorganic materials with controlled 

pore size modified with acid groups lining pores or 

by inclusion of proton conducting subunits; (ii) 

polymer matrices filled with surface-modified 

inorganic particles; (iii) polymeric systems with 

intrinsically stronger acid groups; and (iv) polymer 

systems swollen or imbibed with tailored proton 

acceptors including imidazole and ionic liquids. 

These are useful both intrinsically and as test or 

model systems. Summarized below are approaches 

being explored by some of the partners in the High 

Temperature Membrane project: 

CWRU: inorganic/organic hybrid systems; new 

polymers; strong acid groups; electrode studies at 

high temperature; making MEAs; polymer scale-up 

and film processing; computational studies; and fuel 

cell testing (working on both temperature ranges). 

University of Texas/Dallas: inorganic scaffolds 

with added conducting polymers (primarily high 

temperature range) 

Arizona State University: molten salts 

(primarily high temperature range) 

NASA Jet Propulsion Laboratory: proton 

conducting salts (primarily high temperature range) 

Virginia Commonwealth University: strong acid 

groups; advanced MEA processing method (low 

temperature range) 

CCMs. In work this year, we focused on basic 

studies of the problems that arise in the high 

 FY 2003 Progress Report 

temperature regime. Specifically, we used 

impedance spectroscopy on fuel cells operating 

under conditions of subsaturation. We found 

additional features in the spectrum under these 

conditions. This is illustrated in Figure 1. We are 

presently working to understand the precise 

mechanistic reasons for existence of these features. 

Several approaches to high temperature 

conduction involve the use of imidazole or modified 

imidazoles. In Figure 2, a cyclic voltammogram 

shows the impact of imidazole on basic 

electrochemistry at Pt. It appears that the oxide 

Figure 1.	 Impedance Spectrum of Fuel Cell Under SubSaturation Conditions (Operating conditions: 

Current density: 0.1 A/cm2

; Pressure: ambient; 

Fuel: H2; Oxidant: oxygen; Gas utilization: 

10%; Cell temperature: 70°C to 100°C; Dew 

point: 70°C) 

Figure 2. Cyclic Voltammogram of Pt Electrode Exposed 

to Imidazole 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

formation region is strongly impacted by the 

presence of imidazole in solution. 

Industrial and Other Collaborative Interactions. 

We are engaged in a series of collaborative efforts 

with industry, national laboratories, and universities 

to facilitate efforts to achieve the targets for hightemperature polymer membranes. We have 

organized the High-Temperature Polymer Membrane 

Working Group, which has met four times to date. 

Bi-annual meetings allow us to assess progress and to 

communicate issues and needs to the hightemperature membrane community. 

Conclusions 

The development of new polymer electrolytes 

for operation at elevated temperature is under way. 

However, this is a long-term project. Replacement of 

water is the most difficult problem, but adequate 

stability and cathode activity are not trivial objectives 

to achieve. We have developed several different 

approaches to address this problem. Fundamental 

work is guiding the process via useful insights into 

the conduction process to guide synthetic efforts. 

The first polymers geared for temperatures in excess 

of 100°C are emerging, and testing is showing that, 

although promising, there are definite shortcomings. 

Work on making viable new materials continues. 

 FY 2003 Progress Report 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Electrodes for Polymer Electrolyte Membrane Operation on Hydrogen/Air and 

Reformate/Air 

Francisco Uribe (Primary Contact), Wayne Smith, Mahlon Wilson, Judith Valerio, Tommy Rockward, 

Fernando Garzon, Eric Brosha, Andrew Saab, Guido Bender, Peter Adcock, Jian Xie, Kirsten 

Norman, George Havrilla 

Los Alamos National Laboratory 

PO Box 1663, MS D429 

Los Alamos, NM 87545 

Phone: (505) 667-3964; Fax: (505) 665-4292; E-mail: uribe@lanl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811, E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Improve tolerance to carbon monoxide (CO) and study the effect of other fuel and air impurities. 

•	 Improve the efficiency of the fuel cell electrodes while lowering the dependence on Pt loadings. 

•	 Improve overall polymer electrolyte membrane (PEM) fuel cell operating efficiency. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 Q. Electrode Performance 

Approach 

•	 Investigate the use of reconfigured anodes to improve fuel cell performance in the presence of trace 

levels of CO impurities. 

•	 Evaluate new anode catalysts for CO tolerance. 

•	 Investigate porosity and fuel cell performance as functions of the ionomer content in the catalyst layer. 

•	 Evaluate new cathode catalyst materials for higher operating efficiencies at lower precious metal 

loadings. 

•	 Investigate the effect of potential ambient air impurities on cathode performance. 

Accomplishments 

•	 Demonstrated increased tolerance to 500 ppm CO/reformate using the reconfigured anode. 

•	 Demonstrated 1000 hrs of operation of the 1 wt% Pt-10 wt% Ru anode catalyst running on H2 /air with 

50 ppm CO and 4% air bleed. 

•	 Demonstrated the performance degradation of a Pt-Cr cathode catalyst after 500 hours of operation. 

•	 Demonstrated how the catalyst layer porosity and fuel cell performance correlate with catalyst layer 

Nafion content. 

•	 Established the negative effects of SO2 and NO2 on cathode performance. 

1 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Investigate alternative catalyst materials for use in reconfigured anodes. 

•	 Continue the evaluation of new potential CO tolerant catalysts. 

•	 Screen new potential cathode catalyst materials, particularly with low Pt content. 

•	 Continue to develop improved membrane electrode assembly (MEA) fabrication protocols. 

•	 Investigate methods to mitigate the effects of SO2 and NO2 on fuel cell performance. 

•	 Investigate the effect of other potential ambient air impurities on fuel cell performance. 

•	 Investigate strategies for recovering the performance of fuel cells whose catalysts have been poisoned 

by H2S and SO2. 

Introduction 

The reforming of hydrocarbon fuels is one of the 

leading processes under consideration for producing 

hydrogen to power PEM fuel cells. However, the 

hydrogen stream generated by the reforming process 

can contain volatile chemical compounds that 

significantly diminish fuel cell performance. Two 

approaches to solving this problem are to improve 

the efficiency of the reformation process to lower the 

levels of harmful impurities, or to modify the fuel 

cell itself to be more tolerant toward those 

compounds. This study has taken the latter approach, 

where ways were investigated to improve the anode 

performance in the presence of anticipated reformate 

impurities. 

Fuel cell operation depends not only on 

hydrogen oxidation at the anode but also on oxygen 

reduction at the cathode. The oxygen reduction 

reaction plays a very significant role in limiting the 

operating efficiency of the fuel cell and is very 

dependent on high precious metal loadings in the 

catalyst layer. Improving the efficiency of the 

oxygen reduction reaction while lowering the 

precious metal loading is critical to 

commercialization of fuel cell technology for 

transportation applications. Also, recent awareness 

that impurities in the air stream can affect fuel cell 

performance has led to a more detailed investigation 

of some potentially harmful compounds commonly 

found in air. 

Approach 

The impurity in the reformate stream expected to 

have the largest adverse affect on fuel cell 

performance is carbon monoxide (CO). This gas is 

more strongly adsorbed on the surface of the catalyst 

than hydrogen, effectively blocking the sites where 

hydrogen oxidation would normally occur. One 

method to prevent this from happening is to remove 

the CO by oxidizing it to carbon dioxide, which does 

not adsorb on the catalyst, before it can reach and 

react with the anode surface. This can be 

accomplished by using the reconfigured anode 

developed by Los Alamos National Laboratory 

(LANL). The reconfigured anode has an outer, nonprecious metal catalyst layer added to the standard 

MEA. Bleeding a low level of oxygen into the fuel 

stream results in preferential oxidation of CO at this 

outer layer. A second approach to solving the CO 

problem is to use an anode catalyst that is 

intrinsically more CO tolerant. For example, 

platinum/ruthenium alloys have been shown to be 

more CO tolerant than platinum alone and have the 

added advantage of containing a lower percentage of 

the expensive platinum metal component. Many new 

potential catalysts are submitted to LANL on a 

regular basis from both commercial and noncommercial sources. These materials are fabricated 

into MEAs using an established protocol, and then 

tested in fuel cells under standard operating 

conditions. 

A third approach to identifying improved fuel 

cell anodes is to develop a better understanding of the 

kinetics and mechanisms associated with reactions of 

suspected impurities in the reformate stream with 

various catalyst materials. This information can 

potentially lead to alternative mitigation schemes. 

The mechanism for CO poisoning of platinum-based 

anode catalysts is fairly well understood; for other 

potential poisons and catalyst combinations, that may 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

not necessarily be the case. During this past review 

period, we have focused on catalyst interactions with 

hydrogen sulfide and ammonia, two very likely byproducts in reformed fuels initially containing sulfur 

and nitrogen compounds. 

A similar list of activities was undertaken to 

improve fuel cell cathode performance and can be 

summarized in the following outline: 

•	 Develop new MEA fabrication methods to 

improve catalyst utilization. 

•	 Work with catalyst suppliers to develop/test new 

catalyst formulations. 

•	 Study the effect of catalyst layer structure on performance. 

•	 Study the effects of suspected impurities present 

in air (sulfur dioxide, nitrogen oxides, particulates) on cathode performance. 

Results 

Anode catalysts consisting of Pt-Ru alloys have 

been shown to be more tolerant to CO in the fuel 

stream than platinum alone. However, the 

commercially available materials are still expensive 

due to their high Pt contents. R. Adzic and coworkers from Brookhaven National Laboratory 

submitted a new catalyst for evaluation, with much 

lower platinum loading. This material contained 

only 1% platinum and 10% ruthenium, on a carbon 

support. A 1000-hour performance test was carried 

out using this catalyst in a fuel cell anode with a 

loading of 17 μg Pt/cm2

, approximately 1/10 that of a 

normal loading. The results are shown in Figure 1. 

The voltage losses after 1000 hours of operation at 

fixed current were only 40 mV when the cell was 

operated on clean H2, and 60 mV when operated with 

H2 containing 50 ppm CO and 4% air. This is an 

extremely promising result that could have a major 

impact on lowering fuel cell costs and bringing the 

technology closer to commercialization. 

On the cathode side, the effects of two common 

air impurities were investigated: sulfur dioxide 

(SO2) and nitrogen dioxide (NO2). Figure 2 shows 

the performances of fuel cells whose cathodes are 

exposed to 1 ppm and 5 ppm of SO2, respectively. 

Both levels of impurity degraded the fuel cell 

performance, and, as expected, the effect with the 

higher concentration was faster and more acute. In 

 FY 2003 Progress Report 

Figure 1. Low Pt Content Anode Durability Test at 

Constant Current 

Figure 2. Effect of Sulfur Dioxide on Fuel Cell 

Performance 

both cases, the cathode performance degradations 

were irreversible; the fuel cell did not recover after 

the SO2 was shut off and it was allowed to operate on 

clean air for many hours. Further characterization by 

3 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

cyclic voltammetric measurements showed the SO2 

(or a related species) was strongly adsorbed on the Pt 

catalyst surface. 

Nitrogen oxide has a similar negative effect on 

cathode performance, as shown in Figure 3. 

Performance degradation was less severe than with 

sulfur dioxide, but still significant. The degradation 

upon exposure to 5 ppm of NO2 for about 15 hours 

was reversible as the cell recovered its original 

performance when operated again with clean air. 

Long-term exposure to 0.4 ppm NO2 produced a 

slower negative effect on fuel cell performance that 

did not recover on operation with clean air. This data 

is still preliminary, and there is still no conclusive 

evidence to suggest the mechanism by which this 

impurity degrades performance. However, it is clear 

that the quality of the air stream entering the fuel cell 

is as important as the quality of the fuel stream and 

Figure 3. Effect of Nitrogen Dioxide on Fuel Cell 

Performance 

 FY 2003 Progress Report 

must be of reasonably high purity to guarantee 

performance optimization and durability. 

Further characterization of the catalyst layers of 

the MEA was also conducted with an aim toward 

optimizing fuel cell performance. For example, a 

measure of the porosity of the catalyst layer formed 

from recast Nafion showed that maximum porosity 

corresponded with optimum performance at a Nafion 

content of approximately 30%. It was also 

discovered that varying the fabrication materials and 

method could alter the surface morphology of the 

catalyst layer. Under certain conditions, a thin 

ionomer film formed on the outer surface of the 

catalyst layer. This film inhibited transport of 

reactant gases to the active catalyst sites and the 

removal of water formed at the cathode. The 

decrease in mass transport resulted in a drop in 

performance at high current densities. 

Conclusions 

•	 We have shown that a level of 50 ppm CO in the 

fuel stream could be tolerated with a Pt/Ru catalyst at relatively low loading (17 μg Pt/cm2

) 

when combined with air bleed. This catalyst was 

also shown to be quite stable under normal operating conditions, exhibiting a minimal drop in 

performance over 1000 hours. 

•	 Some common air impurities, SO2 and NO2, 

were also found to have a deleterious effect on 

fuel cell performance when admitted to the cathode air stream. These compounds will have to be 

removed prior to use in a fuel cell system to 

ensure continued performance and durability. 

•	 The preparation method and materials affect the 

morphology of the catalyst layer in an MEA. 

The optimal performance observed at a Nafion 

loading of approximately 30% in the MEA correlates with a maximum in catalyst layer porosity. 

Under certain preparation conditions, a thin skin 

that inhibits molecular transport forms on the 

outer catalyst layer. This skin affects the fuel cell 

performance in the high current region of the 

operating curve. 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

FY 2003 Presentations 

1. K. Sasaki, Y. Mo, J. X. Wang, F. A. Uribe and R. 

R. Adzic. "Pt Submonolayer Electrocatalysts for 

H2 Oxidation and O2 Reduction". 203rd Meeting 

of The Electrochemical Society Meeting, Paris, 

France. April 2003. Abstr. 2679. 

2. K. Sasaki, Y. Mo, J. X. Wang, M. 

Balasubramanian, F. A. Uribe, J. McBreen, R. R. 

Adzic. "Pt Submonolayers on Metal 

Nanoparticles - Novel Electrocatalysts for H2 

Oxidation and O2 Reduction". Accepted in 

Electrochimica Acta (2003). 

3. J. Xie, F. H. Garzon, T. Zawodzinski and W. 

Smith. "The Ionomer Segregation in Composite 

Membrane Electrode Assemblies and the Effect 

on the Performance of PEM Fuel Cells". 203rd 

Meeting of The Electrochemical Society Meeting, 

Paris, France. April 2003. Abstr. 1185. 

4. P. A. Adcock, E. L. Brosha, F. H. Garzon, and F. 

A. Uribe. "Characterization of Potential Catalysts 

for Carbon Monoxide Removal from Reformate 

Fuel for PEM Fuel Cells". Mat. Res. Soc. Symp. 

Proc. Vol. 756 (2003) 365. 

5. G. Bender, T. A. Zawodzinski, and A. P. Saab. 

"Fabrication of High Precision PEFC Membrane 

Electrode Assemblies", in print at Journal of 

Power Sources. 

6. G. Bender, M. S. Wilson and T. A. Zawodzinski. 

"Further Refinements in the Segmented Cell 

Approach to Diagnosing Performance in Polymer 

Electrolyte Fuel Cells", in print at Journal of 

Power Sources. 

 FY 2003 Progress Report 

7. F. Uribe. "Coping with Fuel Impurities in PEM 

Fuel Cells". Advances in Materials for Proton 

Exchange Membrane Fuel Cell Systems. Division 

of Polymer Chemistry, ACS. Asilomar, CA, 

February 2003. 

8. W. Smith. "Fuel Cell Research and Development 

at Los Alamos National Lab". Fuel Cell Seminar. 

Palm Springs, CA, November 2002. 

9. P.A. Adcock, S. Pacheco, E. L. Brosha, T. 

Zawodzinski, and F. Uribe. "Maximization of CO 

Tolerance of PEMFC Systems Using 

Reconfigured Anodes". 202nd Meeting of The 

Electrochemical Society Meeting, Salt Lake City, 

Utah. October 2002. Abstr. 854. 

10.G. Bender and J. Ramsay. "Flow Field Design 

Development Using the Segmented Cell 

Approach". 202nd Meeting of The 

Electrochemical Society Meeting, Salt Lake City, 

Utah. October 2002. Abstr. 813. 

11.G. Bender and T. A. Zawodzinski. "Spatial 

Distribution of the CO Transient Response of a 

PEFC". Third International Symposium On 

Proton Conducting Membrane Fuel Cells, 202nd 

Meeting of The Electrochemical Society Meeting, 

Salt Lake City, Utah. October 2002. 

12.F. Uribe and T. A. Zawodzinski. "A Study of 

Polymer Electrolyte Fuel Cell Performance at 

High Voltages. Dependence on Cathode Catalyst 

Layer Composition and on Voltage Conditioning". 

Electrochimica Acta, 47(2002) 3799. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

New Electrocatalysts for Fuel Cells 

Philip N. Ross, Jr. (Primary Contact), Nenad Markovic 

Lawrence Berkeley National Laboratory 

Materials Sciences Division 

1 Cyclotron Rd., MS 2-100 

Berkeley, CA 94720 

Phone: (510) 486-6226; Fax: (510) 486-5530; E-mail: pnross@lbl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811, E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Conduct research on the kinetics and mechanism of electrode reactions in low temperature fuel cells. 

•	 Develop new electrocatalysts using a materials-by-design approach. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 Q. Electrode Performance 

Approach 

•	 Study the kinetics of fuel cell electrode reactions on well-characterized model electrodes and high 

surface area fuel cell electrocatalysts using modern electroanalytical methods. 

•	 Study the mechanisms of the reactions using state-of-the art in-situ spectroscopes. 

•	 Use ultrahigh vacuum (UHV) methods of surface preparation and surface analyses to form tailored 

surfaces. 

•	 Synthesize nanoclusters to have the tailored surface. 

•	 Characterize the microstructure of the nanoclusters by high-resolution electron microscopy. 

•	 Transfer technology to catalyst developers/vendors. 

Accomplishments 

•	 Proof-of-principle experiments demonstrated that a Au-Pd alloy with <50 wt. % Pd can replace Pt as 

the hydrogen electrode catalyst without any loss in performance. 

•	 Proof-of-principle experiments demonstrated that "Pt skin" structures with a non-precious metal core 

can be stable under proton exchange membrane fuel cell (PEMFC) air cathode operating conditions. 

Future Directions 

Cathode side: 

•	 Create "skin" nanostructures of Pt on non-noble substrates and determine activity and stability as a 

novel low-Pt air cathode electrocatalyst. Select the most promising substrate for synthesis as high 

surface area catalyst. 

•	 Develop and optimize a new class of non-Pt model catalysts. Synthesize and test new non-Pt high 

surface area catalysts at fuel cell conditions. 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Anode side: 

•	 Synthesize and characterize Pd-Au bimetallic nanoparticles and conduct preliminary testing as anodes 

in PEMFC hydrogen-air cells. 

•	 Determine CO-tolerance of tailored electrodes consisting of thin films (1-10 monolayers) of Pd on the 

close-packed single crystal surfaces of Ta, Re, and W. 

Introduction 

It is known from the theory of surface 

segregation in bimetallic alloys that in certain 

systems, preferential surface enrichment in one 

element is so strong that it leads to a "skin" structure, 

i.e. the outermost layer is a "skin" of one element. 

Theoretically, for nanoparticles, such a segregating 

alloy system could form particles having a "grape" 

microstructure, a skin of one element over a core of 

the other. In principle, one could use this 

thermodynamic property to replace the "buried" 

atoms in Pt nanoparticles with a non-precious metal, 

e.g. Fe or Co, resulting in 100% Pt dispersion (all Pt 

atoms are surface atoms) without the need to create 

extremely small particles, e.g. <2 nm. For example, 

if a standard pure Pt catalyst consists of particles 

having on average a dispersion of 20%, replacement 

of the buried atoms in those particles with a base 

metal would enable the Pt loading to be reduced by a 

factor of 5, all other factors being the same. This is 

the basic strategy we are currently pursuing to reduce 

Pt loading in PEMFC cathodes. 

Approach 

Pt3Ni and Pt3Co are classical examples of alloys 

of Pt having a skin surface structure, a pure Pt skin. 

In this case, enrichment occurs by interchange of Pt 

and Co atoms between the first two atomic layers, the 

subsequent layers having the bulk composition (75% 

Pt). The thermodynamic driving force in this case is 

for the larger atom to be at the surface, since in facecentered cubic metals the surface is generally relaxed 

outward and the second layer contracted. The Pt3Ni 

and Pt3Co systems do not represent cases of the 

extreme segregation we need for replacing buried Pt 

atoms, but they do serve as a useful test case for the 

concept of a skin structure, and there appears to be a 

beneficial electronic effect for the Pt skin. 

Importantly, the Pt skin structure in Pt3Co(Ni) was 

stable when used as an oxygen reduction electrode 

under PEMFC conditions. The current approach is to 

extend the concept to Pt-refractory metal alloys, such 

as Pt-Re, Pt-W, or Pt-Ta. In these systems, the 

segregation is more extreme, driven by both the 

strain energy (Re and W are smaller atoms than Pt) 

and the surface tension; hence, the skin structure can 

be achieved with a lower bulk Pt concentration, 

replacing more buried Pt atoms with a non-Pt atom. 

Results — Model Cathode Catalysts 

Pt3Re solid electrodes were prepared using 

conventional metallurgy and pre-treated in a surface 

analytical UHV chamber equipped with various 

instruments for surface preparation and analysis. As 

with Pt3Co(Ni), for each alloy, either a pure Pt skin 

or a 75 at. % Pt surface could be prepared and tested 

as an oxygen reduction catalyst. The resulting 

activity for oxygen reduction as a function of 

composition is shown in Figure 1. The Pt skin 

structure on all three alloys is more active than the 

pure Pt reference surface, suggesting there is an 

Figure 1.	 Steady-state current densities (per unit 

geometric area) at 0.85 V (vs. reversible 

hydrogen electrode—1 bar H2, 333 K) for six 

different alloy electrodes vs. pure Pt: Pt skin on 

Pt3Ni, Pt3Co, and Pt3Re (the annealed 

surfaces); and the 75% Pt surfaces on Pt3Ni and 

Pt3Co (the sputtered surfaces) 

2 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

electronic effect that is generally beneficial for 

oxygen reduction kinetics. Importantly, the results 

represented in Figure 1 were obtained under the 

extreme conditions of use as an oxygen reduction 

electrode, e.g. continuous cycling between 0.1 – 1.0 

V under 1 bar O2 in acid electrolyte at 60o

C 

produced no change in the cyclic voltammetry curves 

for the surfaces.

 Epitaxial thin films of Pd on Pt(111) and 

Re(0001) single crystals were deposited either in 

UHV by a vapor deposition method or in-situ by 

purely electrochemical methods. The morphology 

was studied by a combination of ex-situ UHV surface 

analytical tools (low-energy electron diffraction, 

low-energy ion scattering—LEIS) and in-situ soft xray spectroscopy and Fourier transform infrared 

spectroscopy. Photoelectron spectroscopy (PES) 

results depicted in Figure 2a show that in the surface 

electronic density of states of the valence band, the 

position of the d-band center relative to the Fermi 

level is slightly lower for the pseudomorphic 

monolayer of Pd on Pt(111) than on bare Pt(111). 

The monolayer thickness was determined by LEIS 

(Figure 2b). Interestingly, such a small change in the 

surface electronic structure has a dramatic effect on 

the kinetics of the oxygen reduction reaction (ORR). 

In 0.1 M KOH, the general form of current vs. ΘPd 

relationship for the ORR has a volcano shape (Figure 

2c), with the maximum catalytic activity exhibited by 

a surface modified with 1 monolayer (ML) of Pd. 

When the Pd deposit exceeds 1 ML, the catalytic 

activity is decreased linearly, with the Pd multilayer 

less active than unmodified Pt(111). This is 

strikingly similar to the “volcano relation” we 

reported here last year for the hydrogen oxidation 

reaction (HOR) on the same surfaces. For either the 

ORR or the HOR, there is no clear explanation for 

the volcano relation. On the side where ΘPd > 1, the 

higher activity of the Pd monolayer versus the 

multilayer cannot be attributed to the effect of strain 

on the reactivity of metal surfaces proposed by 

Norskov and co-workers (Phys. Rev. Lett. 81(1998) 

2819), since the strain is too small (+0.65% increase 

in the interatomic spacing). On the side where ΘPd < 

1, the increase in activity from the addition of an 

intrinsically less active metal is surprising and 

unexplained. 

 FY 2003 Progress Report 

However, for the Pd film deposited on Re(0001), 

we were able to find a clear and compelling 

Figure 2.	 (a.) High-resolution UV (hυ = 90 eV) 

photoelectron spectra in the valence band 

region for a Pd monolayer film on Pt(111) and 

the clean Pt(111) surface; (b.) LEIS spectra for 

the same surfaces showing the Pd layer is one 

atomic layer thick; (c.) Kinetics of ORR as a 

function of Pd coverage of Pt(111) 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

correlation between the electronic interaction of the 

Pd overlayer with the Re substrate and the resultant 

catalytic properties. The strong electronic interaction 

causes a significant narrowing of the d-band for the 

surface metal atoms (Figure 3a difference curve) 

with two relatively sharp peaks strikingly similar to 

the d-band of Ag(111). The d-band center, as defined 

by Norskov, is located ca. 1 eV below that of a Pd 

multilayer and/or that of the Pd deposited on Pt(111). 

Figure 3.	 (a.) High-resolution UV (hυ = 90 eV) 

photoelectron spectra in the valence band 

region for a Pd monolayer film on Re(0001) 

surface and the clean Re(0001) surface; (b.) 

Comparison of the polarization curves for ORR 

on the two different Pd monolayer films 

showing the dramatic effect of the electronic 

interaction with the substrate on the 

electrocatalytic properties of the Pd film 

First principles density functional theory calculations 

by Norskov and co-workers for Pd/Re(0001) (Phys. 

Rev. B 60 (1999) 6146) predicted a shift of 0.72 eV 

due to filling of the d-band by electrons from the Re 

substrate. This d-band filling, in turn, has the 

expected effect on oxygen reduction kinetics, 

lowering chemisorption energy for O2– and thus the 

kinetics of the ORR, as shown by the kinetic results 

in Figure 3b. While the results with the model Pd/ 

Re(0001) system are not of practical interest, the 

clear correlation to electronic properties of the 

surface, which can be accurately calculated for 

nearly any surface one can conjure up, is extremely 

significant and encouraging. 

Conclusions 

Proof-of-principle experiments indicate that 

synthesis of Pt as a "skin" on bimetallic nanoparticles 

could enable Pt loadings in the PEMFC air cathode 

to be lowered by as much as a factor of 5 from 

present (optimized) levels, e.g. from 1 g per kW to 

0.2 g per kW. Comparable experiments with Pd thin 

films indicate an even greater reduction in Pt group 

metal (PGM) loading is possible for the hydrogen 

electrode, comparable to the PGM content of the 

catalytic converter in current typical internal 

combustion engine vehicles. 

Publications 

1. Paulus U.A., Wokaun A., Scherer, G.G., Schmidt 

T.J., Stamenkovic V., Radmilovic V., Markovic 

N.M., and Ross P.N., “Oxygen reduction on 

carbon supported Pt-Ni and Pt-Co alloy catalysts”, 

J. Phys. Chem. B 106 (2002) 4181. 

2. Stamenkovic V., Schmidt T.J., Ross P.N., 

Markovic N.M., “Surface composition effects in 

electrocatalysis: Kinetics of oxygen reduction on 

well-defined PtNi and PtCo alloy surfaces.” 

Journal of Physical Chemistry B. 106 (2002) 

11970-11979. 

3. Tripkovic A.V., Popovic K.D., Grgur B.N., 

Blizanac B., Ross P.N., Markovic N.M., 

“Methanol electrooxidation on supported Pt and 

PtRu catalysts in acid and alkaline solutions.” 

Electrochim. Acta. 47 (2002) 3707-3714. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

4. Schmidt T.J., Stamenkovic V., Arenz M., 

Markovic N.M., Ross P.N., “Oxygen 

electrocatalysis in alkaline electrolyte: Pt(hkl), 

Au(hkl) and the effect of Pd-modification.” 

Electrochim. Acta. 47 (2002) 3765-3776. 

5. Paulus U.A., Wokaun A., Scherer G.G., Schmidt 

T.J., Stamenkovic V., Markovic N.M., Ross P.N., 

“Oxygen reduction on high surface area Pt-based 

alloy catalysts in comparison to well defined 

smooth bulk alloy electrodes.” Electrochim. Acta. 

47 (2002) 3787-3798. 

6. Schmidt T.J., Markovic N.M., Stamenkovic V., 

Ross P.N., “Surface characterization and 

electrochemical behavior of well-defined PtPd{111} single-crystal surfaces: A comparative 

study using Pt{111} and Pd-modified Pt{111} 

electrodes.” Langmuir 18 (2002) 6969-6975. 

7. Schmidt T.J., Ross P.N., Markovic N.M., 

“Temperature dependent surface electrochemistry 

on Pt single crystals in alkaline electrolytes Part 2. 

The hydrogen evolution/oxidation reaction.” J. 

Electroanal. Chem. 524 (2002) 252-260. 

 FY 2003 Progress Report 

8. Arenz M., Stamenkovic V., Schmidt T.J., Wandelt 

K., Ross P.N., Markovic N.M., “CO adsorption 

and kinetics on well-characterized Pd films on 

Pt(111) in alkaline solutions.” Surface Science 

506 (2002) 287-296. 

9. Schmidt T.J., Ross P.N., Markovic N.M., 

“Temperature-dependent surface electrochemistry 

on Pt single crystals in alkaline electrolyte: Part 1: 

CO oxidation.” Journal of Physical Chemistry B. 

105 (2001) 12082-12086. 

10.Schmidt T.J., Stamenkovic V., Attard G.A., 

Markovic N.M., Ross P.N., “On the behavior of 

Pt(111)-Bi in acid and alkaline electrolytes.” 

Langmuir 17 (2001) 7613-7619. 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low-Platinum Catalysts for Oxygen Reduction at Proton Exchange Membrane 

Fuel Cell Cathodes 

Karen Swider Lyons (Primary Contact), Peter J. Bouwman, Norma P. Ugarte 

Naval Research Laboratory 

Code 6171, Surface Chemistry Branch 

Washington, DC 20375-5342 

Phone: (202) 404-3314; Fax: (202) 767-3321; E-mail: karen.lyons@nrl.navy.mil 

Wojtek Dmowski 

Department of Materials Science and Engineering 

University of Tennessee 

Knoxville, TN 37996-1508 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Decrease the platinum content of the oxygen reduction catalysts in fuel cell cathodes to meet the DOE 

2010 precious-metal-loading goals of 0.2 g/rated kW and electrode costs of $5/kW. 

•	 Achieve catalyst loadings of 0.02 mg Pt/cm2

 and stability greater than 5000 hours. 

•	 Optimize catalyst performance for low overpotentials. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

Approach 

•	 Disperse platinum on selected hydrous-oxide and hydrous-phosphate supports to enhance the proton 

transport to and catalytic activity of the platinum sites. 

•	 Evaluate the electrochemical performance of the low-platinum catalysts in standardized half-cell and 

fuel-cell measurements. 

•	 Perform stability studies of the catalysts in aggressive chemical solutions, in the presence of gaseous 

poisons, and in operating fuel cells. 

•	 Identify the structure-property relationships of the active materials by studying nanoscale features with 

various characterization tools, including pair density function analysis of X-ray diffraction. 

•	 Collaborate with industry and university contacts for independent evaluation of the catalysts. 

Accomplishments 

•	 Identified stable platinum/hydrous iron phosphate catalysts that have approximately 10H less platinum 

than the platinum/Vulcan carbon catalysts. 

•	 Observed lack of adsorption of carbon monoxide on Pt-FePOx catalysts in half-cell measurements. 

1 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Developed new, stable platinum/hydrous tin-oxide catalysts that exhibit excellent electrochemical 

performance at 10H lower platinum loadings compared to a standard platinum/Vulcan carbon catalyst. 

•	 Improved electrochemical testing methods (half cell and fuel cell) by internal developments and 

collaborations with industry. 

•	 Operated fuel cells having cathode catalysts of either platinum iron phosphate or platinum tin oxide. 

•	 Characterized nanoscale structure and platinum oxidation state of active phosphate and oxide catalysts. 

Future Directions 

•	 Continue to identify optimum platinum loadings of catalysts for maximum performance. 

•	 Develop methods to make high surface-area, nanoscale particles of the phosphate and oxide catalysts. 

•	 Test tolerance of the catalysts to poisons such as carbon monoxide and sulfur dioxide in the air streams 

of proton exchange membrane fuel cells (PEMFCs). 

•	 Improve methods for the preparation of fuel cell cathodes having the new oxide and phosphate 

catalysts via research at the Naval Research Laboratory (NRL) and collaboration with industry. 

•	 Test new catalysts in PEMFCs at NRL and with collaborators, and evaluate long-term stability. 

Introduction 

The cost of the fuel cells and imports of noble 

metals can be drastically reduced by using little or no 

Pt in fuel cell electrodes, thereby improving the 

commercialization potential of fuel cells. 

Researchers recognized years ago that the Pt content 

of PEMFC electrodes could be reduced by dispersing 

nanoscale Pt particles on a porous, electronically 

conductive media (Vulcan carbon) and adding a 

proton conducting media (a perfluorosulfonic 

membrane, Nafion®)(1). When surrounded by 

Vulcan carbon and Nafion, the Pt serves more 

effectively as an electrocatalyst for hydrogen 

oxidation and oxygen reduction because there are 

ample transport paths for protons and electrons. 

Whereas the catalytic activity of the Pt is critical, the 

electrode reactions are mediated by the rate of the 

transport of the gases, protons, electrons and water to 

and from the Pt surfaces. 

We are investigating three types of catalyst that 

may be able to serve as low-cost, stable electrodes in 

fuel cells: Pt-FePOx, Pt-NbPOx, and Pt-SnOx. 

Selected hydrous phosphate and oxides can serve as 

catalytic supports for Pt because of their innate 

activity and their microporous or open-framework 

structures that enhance proton conduction (2). 

Hydrous iron phosphates are known as corrosion 

barriers, paint additives and friction coatings; 

anhydrous phosphate-based catalysts can be used for 

direct conversion of methane into oxygenates and 

oxidative dehydrogenation (3); and lithiated FePO4 

is also being tested as a positive electrode in Li-ion 

batteries (4). Anhydrous Pt-SnOx materials have 

been previously investigated for use in PEMFC 

anodes by other researchers (5), but proved to be 

unstable under reducing conditions. 

Approach 

Hydrous phosphates and oxide catalysts are 

made in aqueous solutions from commercially 

available chemicals, filtered, air dried, and then 

heated from 150 to 200°C. By heating below 200°C, 

the materials retain >0.2 mole % water in their 

structure. The powdered materials are mixed with 50 

to 80 weight % Vulcan carbon to improve their 

electronic conductivity and for fabrication into 

electrodes. 

The Pt-doped phosphate and oxide materials are 

evaluated for their performance in PEMFCs using a 

modified recipe for a rotating disk electrode (RDE) 

for platinum electrocatalysts (6). They are also 

formed into membrane electrode assemblies for 

testing in PEMFCs using the procedures developed 

and optimized by Los Alamos National Laboratory 

(7). The stability of the catalysts is evaluated by 

heating the powdered catalysts (without carbon) in 

1.0 M sulfuric acid at 90°C for 1 to 12 h and then 

testing the electrochemical performance of the 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

recovered powders. A key criterion is that the acid 

has no evidence of metal dissolution. 

The physical properties of the catalysts are 

characterized using a variety of approaches, 

including surface area measurements, thermal 

analysis, transmission electron microscopy, X-ray 

photoelectron spectroscopy, and X-ray absorption 

spectroscopy. The materials are generally 

amorphous to conventional X-ray diffraction, so their 

structure is characterized by the pair-density-function 

analysis of high-energy X-ray diffraction patterns. 

The pair-density-function analysis has been 

particularly useful for this group of catalysts because 

it is able to resolve the local and medium-range 

structure of the materials from 0.2 to 1.5 nm, or the 

size region that has the greatest impact on the 

ensuing catalytic results. 

Results 

Nanoscale Pt-FePOx particles dispersed on 

Vulcan carbon have excellent electrocatalytic activity 

for oxygen reduction, as shown in the cyclic 

voltammetry plot in Figure 1. The activity is 

exemplified by the precipitous drop in the activity 

Figure 1.	 Cyclic voltammetry of a rotating disk electrode 

of 10% Pt-FePOx mixed with Vulcan carbon 

under Ar, air and oxygen. The RDE is prepared 

using the method in reference 7. The data 

shown is in 0.1 M HClO4 at 60°C at a rotation 

rate of 1600 rpm and at a scan rate of 5 mV/s 

using a Pd/H reference electrode that is 

corrected to RHE. The Pt loading of the RDE 

is approximately 0.1 mg Pt/cm2 

. 

 FY 2003 Progress Report 

between 1.0 and 0.7 V vs. a real hydrogen electrode 

(RHE), giving a half-wave potential of 0.91 V, as 

shown in the Tafel plot in Figure 2. By comparison, 

a standard 20% Pt/Vulcan carbon catalyst has a halfwave potential of 0.89 V. The active Pt-FePOx 

catalysts have ~0.3 nm micropores, and the Pt is 

dispersed throughout the phosphate tetrahedra and is 

lodged in interstitial sites throughout the structure, 

creating disorder and opening micropores. X-ray 

photoelectron and absorption spectroscopies indicate 

that the Pt is oxidized, most likely in a 2+ or 4+ state. An 

advantage of Pt

x+ catalyst sites is that they are 

poisoned less easily than Pt-metal sites. In fact, Pt2+/ 

Pt4+ is not poisoned by sulfur, but rather catalytically 

oxidizes it to benign sulfate species (8). Because the 

Pt is an oxidized form in these phosphate catalysts, 

they appear to be unpoisoned by carbon monoxide. 

Typically, carbon monoxide adsorbs on the surface of 

platinum and blocks it from further catalysis, but 

these phosphate catalysts show no evidence of 

carbon monoxide adsorption and/or poisoning when 

tested in a half cell. These Pt-FePOx materials have 

been successfully fabricated into membrane 

electrode assemblies and tested in a PEMFC at NRL. 

The ultimate test of these materials’ viability will be 

their long-term performance in a PEMFC, as trace 

iron will degrade Nafion (9). 

Figure 2.	 Tafel plots of Pt-FePOx on Vulcan carbon vs. a 

20% Pt/Vulcan carbon standard as calculated 

from cyclic voltammetry experiments carried 

out using the conditions described in the 

caption for Figure 1. The Pt loading is 0.1 mg 

Pt/cm2 in both RDEs. Crosses indicate the 

half-wave potentials of the catalysts. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

The Pt-NbPOx materials are attractive because of 

their high stability in acid, and they perform well for 

oxygen reduction when doped with Pt. However, the 

materials have relatively low open circuit potentials 

(OCPs) that are 0.8 V vs. RHE, compared to the 

expected 1.0 V for Pt/Vulcan carbon. These low 

OCPs are a detriment to PEMFCs, as they cut down on 

the cell voltage and therefore the power. Because of 

this drawback, these catalysts have not yet been tested 

in PEMFCs, but efforts are underway to increase the 

OCP via doping with other transition metals. 

The Pt-SnOx materials also have excellent 

electrochemical performance. The performance of 

the catalysts in a PEMFC is shown in Figure 3. In 

this experiment, the Pt loading of the cathode is 0.02 

mg Pt/cm2 of Pt-SnOx/Vulcan carbon, and the anode 

is 0.2 mg Pt/cm2

 of 20% Pt/Vulcan carbon. When 

normalized to current, these Pt-SnOx catalysts 

outperform the Pt/Vulcan carbon standard by a factor 

of 3.5, per weight Pt. Further improvements are 

anticipated as the Pt loading of the SnOx is optimized 

and the particle size is reduced. The Pt-SnOx 

Figure 3.	 Comparison of PEMFCs having cathodes of 

0.023 mg Pt/cm2

 of Pt-SnOx/Vulcan carbon and 

0.22 mg Pt/cm2

 of 20 wt% Pt/Vulcan carbon at 

60°C, under humidified H2/O2 at atmospheric 

pressure, and using Nafion 112 membranes. 

Both anodes have loadings of 0.2 mg Pt/cm2 of 

20-wt% Pt/Vulcan carbon. The standard 

PEMFC has a power of 0.18 W/cm2 at a current 

density of 0.34 A/cm2, while the Pt-SnOx 

PEMFC has a maximum power 0.09 W/cm2 at 

a current density of 0.26 A/cm2, despite having 

10× lower Pt at the cathode. 

 FY 2003 Progress Report 

catalysts are stable to heating in sulfuric acid; 

however, we also observe that the catalysts are not 

stable at fuel cell anodes. Like the phosphate 

materials above, these SnOx-based materials are 

microporous, as shown in Figure 4. 

Conclusions 

•	 Hydrous metal oxides and phosphates doped 

with platinum may be viable candidates as highactivity, inexpensive oxygen reduction catalysts 

for PEMFC cathodes. 

•	 The microporous structures of the catalysts appear 

to influence the performance of the catalysts. 

•	 The catalysts are stable under aggressive acid 

treatment, and therefore are likely to have longterm stability under the operating conditions of a 

PEMFC cathode. 

•	 The catalysts can be successfully fabricated as 

stable cathodes for PEMFCs. 

•	 These phosphate and oxide catalysts may prove 

to be more stable than Pt metal over long-term 

tests because their platinum is in an oxidized 

state (Pt2+/Pt4+) and therefore is less prone to 

poisoning. 

Figure 4.	 Schematic of the microporous structure of Ptdoped hydrous SnOx. The nanoscale pores are 

conducive to proton conduction. 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

References 

1. I. D. Raistrick, US Patent 4876115 (1989). 

2. P. Colomban, Ed., "Proton conductors: solid, 

membranes and gels - materials and devices," 

Cambridge University Press, Cambridge (1992). 

3. K. Otsuka, Y. Wang, Appl. Catal. A, 222, 145-161 

(2001). 

4. A. K. Padhi, K. S. Nanjundaswamy, J. B. 

Goodenough, J. Electrochem. Soc., 144, 1188­

1194 (1997). 

5. M. Watanabe, S. Venkatesan, H. A. Laitinen, J. 

Electrochem. Soc., 130, 59-64 (1983). 

6. Private communication, H. Gasteiger and S. 

Kocha, General Motors. 

7. M. S. Wilson, J. A. Valerio, S. Gottesfeld, 

Electrochim. Acta, 40, 355-362 (1995). 

8. K. E. Swider, D. R. Rolison, Langmuir, 15, 3302­

3306 (1999). 

9. A. Pozio, R. F. Silva, M. De Francesco, L. Giorgi, 

Electrochim. Acta, 48, 1543-1549, (2003). 

FY 2003 Publications/Presentations 

1. N. P. Ugarte, K. E. Swider-Lyons, "Low-Platinum 

Tin-Oxide Electrocatalysts for PEM Fuel Cell 

Cathodes," in the Proceedings of the Symposium 

on Polymer Fuel Cells, Electrochemical Society 

Proceedings Series, October 2002, in press. 

2. N. P. Ugarte, K. E. Swider-Lyons, "Low-Platinum 

Metal-Oxide Electrocatalysts for PEM Fuel Cell 

Cathodes," Third International Symposium on 

Proton Conducting Membrane Fuel Cells, 202nd 

Meeting of the Electrochemical Society, Salt Lake 

City, Utah, 20-25 October 2002. 

3. P. J. Bouwman, J. A. Stanley, G. B. Cotten, K. E. 

Swider-Lyons, W. Dmowski, T. Egami, "LowPlatinum, Oxide-Based Electrocatalysts for 

Oxygen Reduction in PEM Fuel Cells," Gordon 

Research Conference on Electrochemistry, 

Ventura, California, 12-16 January 2003.
 

4. K. E. Swider-Lyons, P. J. Bouwman, N. P. Ugarte, 

W. Dmowski, "Amorphous Hydrous Metal Oxides 

as Electrocatalysts for Fuel Cell Cathodes," 

American Chemical Society Symposium on 

Advances in Materials for Proton Exchange 

Membrane Fuel Cells, Monterey, California, 23­

26 February 2003. 

5. W. Dmowski and K. E. Swider-Lyons, "Real 

Structure of Real Materials from Pair-density 

Function Analysis of X-ray and Neutron 

Scattering," American Chemical Society 

Symposium on Advances in Materials for Proton 

Exchange Membrane Fuel Cells, Monterey, 

California, 23-26 February 2003. 

6. K.E. Swider-Lyons, P. J. Bouwman, N. P. Ugarte, 

W. Dmowski, "Low-Platinum Phosphate and 

Oxide Electrocatalysts for Fuel Cells," Gordon 

Research Conference on Fuel Cells, RI, 27-31 

July 2003. 

7. W. Dmowski, T. Egami, K. E. Swider-Lyons, D. 

R. Rolison, "Atomic structure of Disordered 

Hydrous RuO2, Pt-Ru and Pt-FePO4," 

Symposium on Advanced Materials for Fuel Cells 

and Batteries, 204th Meeting of The 

Electrochemical Society, Orlando, Florida, 12-17 

October 2003. 

8. P. J. Bouwman, W. Dmowski, K. E. SwiderLyons, "Hydrous Pt-FePOx Catalysts for Oxygen 

Reduction in Proton Exchange Membrane Fuel 

Cells," Symposium on Advanced Materials for 

Fuel Cells and Batteries, 204th Meeting of The 

Electrochemical Society, Orlando, Florida, 12-17 

October 2003. 

9. K. E. Swider Lyons, P. J. Bouwman, N. P. Ugarte, 

W. Dmowski, "Low Platinum, Oxide-based 

Electrocatalysts for Oxygen Reduction in Proton 

Exchange Membrane Fuel Cells," ASM 

International Symposium on Fuel Cells: 

Materials, Processing and Manufacturing 

Technologies, Pittsburgh, Pennsylvania, 13-16 

October 2003. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Special Recognitions & Awards/Patents 

Issued 

1. Patent disclosure: K. S. Lyons, P. J. Bouwman, 

"Hydrous phosphate catalysts with low platinum," 

Navy Case No. 84,631, 26 March 2003. 

2. Patent disclosure: K. S. Lyons, N. P. Ugarte, 

"Platinum-impregnated hydrous tin oxide 

catalysts," Navy Case No. 84,632, 26 March 2003. 

6 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low Platinum Loading Catalysts for Fuel Cells 

Radoslav Adzic (Primary Contact), Kotaro Sasaki, Yibo Mo, Jia Wang, Miomir Vukmirovic 

Brookhaven National Laboratory, Bldg. 555 

Upton, NY 11973-5000 

Phone: (631) 344-4522; Fax: (631) 344-5815; E-mail: adzic@bnl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Further improve the new catalyst consisting of a submonolayer of Pt on carbon-supported Ru 

nanoparticles (1%Pt/10%Ru/C) to come close to the DOE’s 2010 target of 100 μg/cm2 noble metal 

loading. 

•	 Further elucidate the inhibition mechanism of CO on H2 oxidation on Pt. 

•	 Reduce Ru loadings in Pt-Ru electrocatalysts. 

•	 Explore monolayer-level-supported Pt electrocatalysts for O2 reduction. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 Q. Electrode Performance 

Approach 

•	 Synthesize and characterize the electrocatalyst having a submonolayer of Pt on Ru nanoparticles and 

determine its CO tolerance. 

•	 Test the new electrocatalyst in a membrane electrode assembly (MEA) at the Los Alamos National 

Laboratory. 

•	 Use an in situ surface x-ray diffraction technique to follow the adsorption of CO on Pt during H2 

oxidation. 

•	 Synthesize and test a non-noble metal alloy and early transition metal nanoparticles as support for Pt to 

reduce Ru loading. 

•	 Prepare Pt monolayer/multilayer deposits on Au (111) and Au nanoparticles using our new method for 

depositing Pt monolayers and test these surfaces as O2 reduction electrocatalysts. 

Accomplishments 

•	 The CO tolerance of the 1%Pt /10%Ru/C catalyst for oxidizing H2 containing 1000 ppm CO at 2500 

rpm was more than doubled compared with the last year’s value. MEA stability tests at Los Alamos 

National Laboratory, conducted by Francisco Uribe and coworkers, showed a small loss in activity 

after 1000 hours of operation with combined H2 and H2 + 50 ppm CO + 4% air-bleed fuels. This 

catalyst has 1/10th (17 μg/cm2) of the Pt loading of standard catalysts. For Pt, the loading of the new 

catalyst is below the DOE’s target (150 μg/cm2

) for precious metals for 2004. For Ru, it is at the 

present level of state-of-the-art catalysts. 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• The ( 	 √19 x √19)13CO phase was determined for the first time by x-ray diffraction technique on 

Pt(111): a fast (2 x 2) ↔ (√19 x √19) phase transition was found. The oxidation of H2 with 2% CO is 

inhibited by the formation of an ordered CO (2 x 2) adlayer. 

•	 Pt on C-supported Au nanoparticles can be an efficient catalyst for reducing O2. A Pt mass specific 

activity 2.5 times higher than that of Pt10%/C was achieved. Its stability needs to be investigated. 

•	 Pt on C-supported W nanoparticles may be a promising catalyst for H2 oxidation. 

Future Directions 

•	 Optimize a Pt/Ru electrocatalyst, and conduct final tests at LANL and industrial laboratories. 

•	 Investigate the possibilities of reducing Ru loading by non-noble metals, such as W. 

•	 Explore Au-non-noble metal alloy nanoparticles as supports for a Pt monolayer for O2 reduction. 

•	 Investigate several low d-band vacancy metals as support for a Pt monolayer for O2 reduction. 

Introduction 

We investigated a new catalyst consisting of a 

submonolayer of Pt on carbon-supported Ru 

nanoparticles (1%Pt/10%Ru/C) with the goal of 

improving its properties and further understanding 

the origins of its activity. Its catalytic activity was 

determined using a rotating thin-film disk electrode. 

The long-term stability and CO tolerance of this 

catalyst was tested in a fuel cell electrode (membrane 

electrode assembly) at Los Alamos National 

Laboratory. Several preliminary experiments were 

aimed at reducing the Ru loading. We also obtained 

new insights into the mechanism of poisoning the 

catalytic activity of a Pt(111) surface by CO. 

The possibility of making an active catalyst for 

O2 reduction consisting of Pt monolayers on metal 

nanoparticles on carbon support was explored. The 

initial results for Pt on Au indicate that very active 

catalysts can be obtained by this approach. 

Approach 

A new method for preparing Pt/Ru catalysts 

involving spontaneous deposition of Pt on Ru 

nanoparticles was further studied with the goal of 

optimizing it to increase the activity of the catalysts. 

In contrast to the Pt-Ru alloys catalysts, all the Pt 

atoms in this new one are available for the catalytic 

reaction. Therefore, the interaction of the Pt atoms 

with Ru, and the state of the Ru surface, are of 

utmost importance for the catalyst’s activity. Ru-Ni 

and Ru-Co nanoparticles were deposited on carbon 

using an impregnation method, while a Pt 

submonolayer was deposited on these nanoparticles 

spontaneously. The activity for H2 oxidation and the 

CO tolerance were determined. The tests also were 

conducted with Pt clusters obtained by electroless 

deposition on polycrystalline W and carbonsupported W nanoparticles. Tungsten nanoparticles 

were obtained using BNL’s new method of 

sonication solvolysis of W salts. 

We employed an in situ x-ray diffraction 

technique using synchrotron radiation to follow the 

formation of ordered CO adlayers on Pt(111) during 

H2 oxidation, monitoring the process as a function of 

time. The inhibition of H2 oxidation was clearly 

related to the adlayers’ structure. 

Obtaining Pt monolayer catalysts for O2 

reduction is important for several reasons, including 

the possibility of reducing Pt loading, and of 

improving the activity of the catalysts. The initial 

results, obtained with a Pt monolayer deposited on 

Au using our new method of galvanic replacement of 

an adsorbed Cu monolayer, show the high activity of 

such surfaces. 

Results 

A thin-film rotating disk electrode (RDE) was 

used to determine catalytic activities and CO 

tolerance. Figure 1 shows the results of an accelerated 

test of CO tolerance of the PtRu20 catalyst based on 

measuring the current at 0.05 V as a function of time 

for the oxidation of H2 containing 1000 ppm CO at 

2 
 

 

 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

60oC. For comparison, we include the results showing 

a smaller CO tolerance for two commercial catalysts, 

along with the results for PtRu20 from the last review. 

A considerable improvement has been achieved; the 

CO tolerance of the PtRu20 catalyst increased in this 

test from < 3 h to > 6 h. 

Figure 2 shows the life test in MEA with an 

earlier version of the catalyst synthesized a year and 

a half ago. Clean H2 and H2 with 50 ppm CO and 

4% air bleed were used as fuel. The losses after 

1000 hours are 40 mV when the cell operates on 

clean H2, and 60 mV with the H2+50 ppm CO+4% 

air mixture. The cell was run with the latter fuel 

composition for a third of the total time. The test 

still is in progress. This result clearly shows that Pt 

submonolayers on Ru nanoparticles are stable 

during the fuel cell’s operation and that this system 

represents a real catalyst. In addition to the high 

activity for H2 oxidation and a weak CO bonding, 

the strong segregation of Pt and Ru is a key factor 

that determines this catalyst’s stability. The data 

provide a powerful illustration of the possibility of 

nanoparticle surface modification by Pt monolayers 

as a method of obtaining low noble-metal loading 

of catalysts. 

Figure 1.	 The CO tolerance of the improved PtRu20 

catalyst (top curve) compared with an earlier 

sample and two commercial catalysts. The 

current at 0.05 V is plotted as a function of 

time for the oxidation of H2 containing 1000 

ppm CO at 60oC; 2500 rpm. The catalyst 

loadings are given in the graph. RHE = 

reversible hydrogen electrode. 

 FY 2003 Progress Report 

The (√19 x √19)13CO phase was determined for 

the first time on Pt(111) by in situ x-ray diffraction 

technique. We found that the (2 x 2) ↔ (√19 x √19) 

phase transition occurs in several seconds. The 

oxidation of H2 with 2% CO is inhibited by 

formation of the ordered CO (2 x 2) adlayer. 

Incomplete removal of CO disorders the phase, but 

the inhibition of H2 oxidation remains unchanged. 

To reduce the Ru loadings, RuNi and RuCo 

nanoparticles were deposited on XC-72 by wet 

impregnation, followed by spontaneous deposition of 

Pt. The activity of these catalysts for H2 oxidation is 

somewhat lower than that of PtRu20, while their CO 

tolerance is similar. Pt/Wpoly and Pt/W/C catalysts 

have a considerable activity for H2 oxidation but 

poor CO tolerance. 

Figure 3 displays rotating ring-disk electrode 

(RRDE) measurements of O2 reduction on the Pt 

monolayer on an Au(111) surface, showing its very 

high activity (E1/2 = 0.830 V) and practically no 

H2O2 generation. Two Tafel slopes, usually 

observed with Pt electrodes, can be obtained from 

kinetic currents determined by the Koutecky-Levich 

plots. O2 reduction on the Pt adlayer (9 μg Pt/cm2) 

on Au/C has E1/2 = 0.820 V. X-ray absorption 

Figure 2.	 The long-term test in a cell conducted at 

LANL by F. Uribe and coworkers. Anode: 

0.19 mg total metal/cm2 (10%Ru, 1%Pt) 17 

μg Pt/cm2

; Cathode: 0.23 mg Pt (20% Pt/C, 

ETEK)/cm2

; Electrode areas=50 cm2; T= 

80oC; Pressures A/C = 30/30 psig. Total run 

time = 1000 hours at constant current (710 

hours of operation with clean H2 and 290 

hours with H2 + 50 ppm CO + 4 % air bleed). 

3 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 RRDE measurements of O2 reduction on a 

Pt1ML/Au(111) surface. The insert shows the 

Tafel plot with kinetic currents obtained from 

the Koutecky-Levich plots. 

spectroscopy measurements and voltammetry 

curves indicate that PtOH formation on Pt/Au/C and 

Pt/Au(111) shifts to more positive potentials than 

those of Pt/C and Pt(111) surfaces, respectively. 

This property may be very important for the 

function of these catalysts since PtOH inhibits O2 

reduction. The long-term stability of the Pt/Au 

catalyst is questionable since this system is antisegregated. These results, however, illustrate the 

important possibility that a Pt monolayer on metal 

nanoparticles can be an active catalyst for O2 

reduction. 

Figure 4 is a histogram of the Pt-mass-specific 

activities of several bimetallic catalysts that we have 

tested so far. It shows that all the adlayer Pt deposits 

on Au nanoparticles have a higher Pt mass-specific 

activity than a standard 10%Pt/C catalyst. A mixed 

Pt0.75Pd0.25 catalyst performs the best. 

Conclusions 

The performance of the 1%Pt10%Ru catalyst 

was considerably improved and a two-fold increase 

in CO tolerance achieved according to the 

Figure 4.	 Histogram of the Pt-mass-specific activities 

of several bimetallic catalysts at E=0.8 V; 

1600 rpm. 

accelerated test with a rotating disk electrode. The 

long-term testing of the earlier version of the 

catalyst in MEA at LANL has reached 1000 hours 

in the oxidation of H2 and H2 + 50 ppm of CO and 

4% of air with only a minor loss of performance. 

The test is still in progress. For Pt, the loading of 

the new catalyst is below the DOE’s target (150 μg/ 

cm2

) for precious metals for 2004. For Ru, it is at 

the present level of the state-of-the-art catalysts. As 

illustrated by the data for Pt on Au, Pt monolayers 

on metal nanoparticles can be active catalysts for 

O2 reduction. 

Publications 

1. H. Inoue, S.R. Brankovic, J.X. Wang, R.R. Adzic, 

Oxygen Reduction on Bare and Pt MonolayerModified Ru(0001), Ru(101-0) and Ru 

Nanostructured Surfaces, Electrochim. Acta, 47 

(2002) 3777. 

2. S.R. Brankovic, N.S. Marinkovic, J.X. Wang, 

R.R. Adzic, Carbon Monoxide Oxidation on Bare 

and Pt-modified Ru(101-0) Single Crystal 

Electrodes, J. Electroanal. Chem., 532 (2002) 57 

3. J.X. Wang, S.R. Brankovic, Y. Zhu, J.C. Hanson, 

and R.R. Adzic, Kinetic Characterization of H2 

Anode Catalysts Made by Spontaneous 

Deposition of Pt on Ru Nanoparticles, J. 

Electrochem. Soc. in press. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

4. K. Sasaki, Y. Mo, J.X. Wang, M. 

Balasubramanian, F. Uribe, J. McBreen, R.R. 

Adzic, Pt Submonolayers on Metal Nanoparticles 

- Novel Electrocatalysts for H2 Oxidation and O2
 

Reduction, Electrochim. Acta, in press.
 

Patents 

1. Patent application submitted. The U.S. Patent 

Office serial number 09/812246. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Direct Methanol Fuel Cells 

Piotr Zelenay (Primary Contact), Eric Brosha, John Davey, Christian Eickes, Robert Fields, 

Fernando Garzon, Manoj Neergat, Bryan Pivovar, Geraldine Purdy, John Ramsey, John Rowley, 

Mahlon Wilson, and Yimin Zhu 

Materials Science and Technology Division 

Los Alamos National Laboratory 

Los Alamos, New Mexico 97545 

Phone: (505) 667-0197; Fax: (505) 665-4292; E-mail: zelenay@lanl.gov 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop materials and components and optimize operating conditions of the direct methanol fuel cell 

(DMFC) for maximum power density and fuel conversion efficiency at a minimum cost. In particular: 

•	 Design and optimize membrane-electrode assemblies (MEAs) to enhance cell performance. 

•	 Advance electrocatalysis of methanol oxidation and oxygen reduction to increase power density and 

lower total precious metal loading. 

•	 Characterize and optimize non-Nafion polymers with reduced crossover and improved performance. 

•	 Model, develop and demonstrate practical viability of advanced cell components. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

•	 R. Thermal and Water Management 

Approach 

•	 Build, operate and test performance of DMFCs with different anode and cathode catalysts, membranes 

and MEAs. 

•	 Through experimentation, develop thorough understanding of the key factors impacting cell
 

performance and durability.
 

•	 Maximize efficiency, power and energy density of DMFCs by creative designing of stack components 

and experimental verification of the hardware performance. 

Accomplishments 

Cathode Research 

•	 Carbon-supported Pt catalysts optimized for performance at a loading of 0.6 mg cm-2 . 

•	 Respectable performance demonstrated at an air stoichiometric ratio between 2 and 3. 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Electrocatalysis 

•	 Alternative carbon-supported cathode catalyst demonstrated for over 200 hours with power density 

~15% better than that of a reference Pt catalyst. 

•	 Key factors affecting the performance of Pt-Ru anode catalysts determined by a combination of 

electrochemical ("in fuel cell"), x-ray diffraction (XRD), thermogravimetric analysis (TGA) and COstripping techniques. 

Performance Durability 

•	 Effect of Pt oxide formation on short-term DMFC performance determined; a method of regaining 

cathode activity developed and successfully implemented in life testing. 

•	 Ruthenium crossover through Nafion® membrane and its effect on the cathode activity demonstrated 

for the first time; other reasons for long-term MEA degradation identified. 

Membrane Research 

•	 Significant selectivity improvement over non-fluorinated bi-phenol sulfone (BPSH) polymers 

achieved with two fluorinated poly(arylene ether sulfone) polymers: 6F [hexafluorinated (biphenol A) 

sulfonated poly(arylene ether sulfone)] and 6F-CN [hexafluorinated / nitrile-functional sulfonated 

poly(arylene ether sulfone)]. 

•	 Low-resistance 6F-CN MEAs prepared and successfully tested in a DMFC for several hundred hours 

with tolerable performance degradation. 

Stack R&D 

•	 Three generations of 11-W stacks for a 20-W DMFC system for portable power designed, built and 

tested. 

•	 Four latest-generation stacks delivered to Ball Aerospace for system integration. 

•	 Design of all components for the 500-W auxiliary power unit (APU) DMFC stack completed; 

excellent performance demonstrated with a six-cell short stack operating at zero cathode backpressure 

and air stoichiometry ratio below three. 

Future Directions 

•	 Investigate the mechanism and design methods for controlling degradation of the Nafion® and nonNafion MEAs. 

•	 Optimize performance and improve durability of systems based on novel alternative membranes, such 

as 6F and 6F-CN. 

•	 Perform theoretical and practical study of the impact of catalyst layer structure on the rate of methanol 

oxidation and oxygen reduction. 

•	 Investigate novel carbon-supported catalysts for low-loading DMFC operation. 

•	 Improve DMFC performance by understanding and optimizing hydrophilic/hydrophobic properties of 

the cathode. 

•	 Demonstrate for at least 100 hours sustained operation of a large-surface area stack with air
 

stoichiometry ratio below two.
 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

Direct methanol fuel cell research at Los Alamos 

National Laboratory (LANL) has focused on 

developing materials and designing optimum 

operating conditions for DMFCs to be used in 

portable power applications (commercial electronics, 

battery replacement for the military) and 

transportation (on-board APUs). The main objective 

of LANL's research effort in the DMFC area has 

been to demonstrate that methanol-based systems can 

meet power-density, energy-conversion efficiency 

and cost targets. 

Results 

In our FY 2003 research, we continued our effort 

to optimize carbon-supported catalysts for the main 

purpose of reducing the precious metal loading in 

DMFCs. Five cathode Pt/C catalysts with Pt content 

ranging from 30 wt% to 80 wt% were tested at a 

target catalyst loading of 0.6 mgPt cm-2 . 

Experiments revealed that 56% Pt/C and 60% Pt/C 

are not only the most active for oxygen reduction, but 

are also more immune to methanol crossover effects. 

DMFC performance recorded with the 80% Pt/C was 

not as good as that of 56% Pt/C and 60% Pt/C, yet 

was much above that of the 40% Pt/C and 30% Pt/C. 

Last year, we introduced a new binary cathode 

catalyst, Pt-X/C (patent application pending), with 

higher activity towards oxygen and improved 

methanol tolerance compared to the Pt/C reference 

catalyst. In FY 2003, we demonstrated superior 

performance of that catalyst in a 200-hour life test. 

The Pt-X performance at the end of the life test, 15% 

better than that of a reference Pt/C catalyst, would 

have been even better had it not been for its relatively 

poor long-term stability. Future research will focus 

on improving the stability of this catalyst, which 

could lead to as much as 50% improvement in the 

cell performance. An attempt will also be made to 

obtain the Pt-X catalyst in an unsupported form, 

more suitable for portable DMFC use. 

Progress in cathode and cell-component research 

has led to significant lowering of the airflow required 

to maintain good cell performance. In FY 2003, we 

demonstrated single cells and prototype stacks that, 

in addition to showing good performance and high 

efficiency, can operate on ambient air and with an air 

stoichiometry ratio of ~2.3. This low stoichiometry 

exceeds the airflow reduction milestone of the 

DMFC project at LANL. 

The current year marks a very significant 

increase in the DMFC durability research at LANL. 

We developed a setup for the parallel durability 

testing of several MEAs as well as techniques for 

detecting performance losses of different MEA 

components. We have extensively used carbon 

monoxide probing for determining the number of 

active catalyst sites and atomic composition of the 

anode and cathode surfaces at various times of the 

life test. All durability research was carried out 

under practical cell operating conditions, at low flow 

and pressure of the cathode air and high cell 

operating voltage. As indicated by the life-test data 

in Figure 1, most of the short-term DMFC 

performance losses occur in the first 24 hours of the 

life test. This loss has been attributed to the surface 

oxidation of the platinum catalyst at its operating 

potential of 0.80-0.85 V. It can be regained by 

reducing the catalyst surface, for example, by 

stopping the cathode airflow for a few seconds 

(Figure 2). 

In addition to short-term performance loss 

caused by oxidation of the Pt surface, DMFCs also 

suffer from long-term (generally irreversible) 

performance degradation. This performance loss is 

most likely due to changes in the hydrophobic/ 

hydrophilic properties of the cathode, loss of the 

Figure 1.	 A 350-hour Parallel Life Test of Six Cells 

Operated at a Constant Current Density of 

0.08 A cm-2 at 75°C 

3 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

ionomer from the electrodes (cathode in particular), 

and lowering of the cathode activity as a result of 

ruthenium crossover and its re-deposition at the Pt 

surface. Ruthenium crossover was first 

demonstrated at LANL in FY 2003 by using the 

carbon monoxide probe technique. This research 

will continue in FY 2004, focusing on the methods of 

stabilizing Ru in the DMFC anode. 

In the past year, we developed alternatives to 

standard Nafion® MEAs that for the first time 

promise considerable improvement in DMFC 

membrane technology. This research, carried out in 

close collaboration with Virginia Polytechnic 

Institute, led to the demonstration of two new 

polymers from the poly (arylene ether sulfone) 

family: 6F and 6F-CN. Changes in the 

physicochemical properties of the non-fluorinated 

BPSH polymer brought about by the presence of 

-CF3 (lower water uptake and better adhesion) 

helped to significantly reduce the interfacial 

Figure 2. Effect of Cell Voltage (Cathode Potential) 

Pulsing on the DMFC Operation at 80°C 

 FY 2003 Progress Report 

resistance between the membrane and the electrodes 

while preserving good selectivity. Consequently, the 

initial DMFC performance of the two new 

membranes was found to be better than that of 

Nafion® 117 under the same test conditions (Figure 

3). Unlike non-fluorinated BPSH membranes, which 

suffer from irreversibly reduced performance after 

only 100 hours, 6F-CN-35 showed no degradation in 

the first 200 hours of life testing and only a slight 

performance drop after 700 hours. 6F-CN-35 

exhibited no increase in high-frequency resistance 

over the time of the life test, suggesting a good and 

stable membrane/electrode interface. This result 

represents a significant achievement in alternative 

DMFC membrane research. 

In parallel with the fundamental research in 

catalysis, membranes and MEAs, which has 

remained the focal point of the direct methanol fuel 

cell program at LANL, we also made substantial 

progress in the design and prototyping of DMFC 

stacks for portable and auxiliary power applications. 

Three generations of highly efficient and lightweight 

11-W stacks were developed for the operation at a 

design voltage of 0.55/cell. Four units from the last 

generation were supplied to our system partner, Ball 

Aerospace & Technologies Corporation, for 

integration into two 20-W system prototypes for the 

military (a DARPA-sponsored project). 

Figure 3.	 DMFC Polarization Plots Obtained with Four 

Different membranes: Nafion® 117, 6F-40, 

6F-CN-35 and BPSH-35 (Plots recorded at 

80°C and an ambient cathode air pressure of 

0.76 atm in Los Alamos) 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

All key components for the 500-W APU stack Conclusions 

were designed and tested in a six-cell stack, which 

preceded the construction of the actual stack The main conclusions from the DMFC research 

deliverable scheduled in a few months. The short performed at LANL in the past year can be 

stack was assembled using 100-cm2 active area cells. summarized as follows: 

All six cells in the short stack exhibited uniform and 

good performance when operated at ambient cathode 

pressure and an air stoichiometry ratio of 3.0. The 

maximum power generated by the stack under these 

conditions was measured at 140 W (Figure 4), with 

negligible penalty on a scale-up from the single cell 

to the stack. As a result, the number of cells in the 

full stack required to generate the design power of 

500 W is estimated at approximately 50, significantly 

lower than the originally planned 100. 

Figure 4.	 Development of 500-W DMFC Stack for 

Auxiliary Power System: Polarization and 

Power Plots for Six-Cell Stack at 80°C 

•	 The use of carbon-supported Pt catalyst with a Ptto-C ratio of 50 - 60 wt% significantly reduces the 

catalyst loading at only a moderate performance 

penalty. Careful optimization of the cathode 

structure allows for continuous cell/stack operation at an air stoichiometric ratio as low as two. 

•	 DMFC cell/stack suffers from short- and longterm performance loss. The short-term loss is 

predominantly caused by the oxidation of the 

cathode Pt. This loss can be reversed by intermittent reduction of the catalyst. Long-term performance degradation results from irreversible 

changes to the structure of the electrode and the 

hydrophobic/hydrophilic properties of the cathode, as well as from Ru crossover. Mitigating 

the long-term durability issues will require modifications to the MEA components and methods 

of cell fabrication. 

•	 Thanks to low impedance of the membrane-electrode interface and preserved high selectivity, 

two new membranes from the BPSH family, 6F 

and 6F-CN, exhibit superior DMFC performance 

to Nafion® 117. Based on the life test data for 

6F-CN-35, the membranes also promise good 

durability. 

•	 Significant practical potential of DMFC technology was demonstrated with the 11-W stack prototypes operating at low flow and ambient 

pressure of the air. The stack power density, 

already measured at 130 W kg-1, is expected to 

exceed 300 W kg-1 soon, both for low power (11­

W) and high power (500-W) stacks. 

FY 2003 Publications 

1. "Direct Methanol Fuel Cells: Progress in Cell 

Performance and Cathode Research," S. C. 

Thomas, X. Ren, S. Gottesfeld and P. Zelenay, 

Electrochim. Acta, 47, 3741-3748 (2002). 

5 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

2. "A Six-Cell 'Single-Cell' Stack for Stack 

Diagnostics and Membrane Electrode Assembly 

Evaluation," B. Pivovar, F. Le Scornet, C. 

Eickes, C. Zawodzinski, G. Purdy, M. Wilson, 

and P. Zelenay, in Proton Conducting Membrane 

Fuel Cells III, T. F. Fuller, S. Gottesfeld, M. 

Murthy, and J. W. Van Zee (Eds.), ECS 

Proceedings, Electrochemical Society, 

Pennington, New Jersey, in press. 

3. "The Effect of BPSH Post Treatment on DMFC 

Performance and Properties," M. Hickner, Y. 

Kim, J. McGrath, P. Zelenay and B. Pivovar, in 

Proton Conducting Membrane Fuel Cells III, T. 

F. Fuller, S. Gottesfeld, M. Murthy, and J. W. 

Van Zee (Eds.), ECS Proceedings, 

Electrochemical Society, Pennington, New 

Jersey, in press. 

4. "Optimization of Carbon-Supported Platinum 

Cathode Catalysts for DMFC Operation," Y. 

Zhu, E. Brosha and P. Zelenay, in Proton 

Conducting Membrane Fuel Cells III, T. F. 

Fuller, S. Gottesfeld, M. Murthy, and J. W. Van 

Zee (Eds.), ECS Proceedings, Electrochemical 

Society, Pennington, New Jersey, in press. 

5. "Electrochemical and XRD Characterization of 

Pt-Ru Blacks for DMFC Anodes," C. Eickes, E. 

Brosha, F. Garzon, G. Purdy, P. Zelenay, T. 

Morita and D. Thompsett, in Proton Conducting 

Membrane Fuel Cells III, T. F. Fuller, S. 

Gottesfeld, M. Murthy, and J. W. Van Zee (Eds.), 

ECS Proceedings, Electrochemical Society, 

Pennington, New Jersey, in press. 

6. "Processing Induced Morphological 

Development in Hydrated Sulfonated 

Poly(arylene ether sulfone) Copolymer 

Membranes," Y. S. Kim, L. Dong, M. Hickner, 

B. Pivovar, and J. McGrath, Polymer, accepted 

for publication June 13, 2003. 

FY 2003 Presentations 

1.	 W. L. Gore, Elkton, Maryland, June 20, 2002. 

Title: "Direct Methanol Fuel Cells"; P. Zelenay* 

(invited lecture). 

 FY 2003 Progress Report 

2.	 Gordon Research Conference on Fuel Cells, 

Bristol, Rhode Island, July 28 - August 2, 2002. 

Title: "DMFC Research at Los Alamos: 

Towards Better Performing Cells and Stacks" P. 

Zelenay* (invited/keynote lecture). 

3.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, UT, October 20-24, 2002. Title: 

"A Six-Cell 'Single-Cell' Stack for Stack 

Diagnostics and Membrane Electrode Assembly 

Evaluation," B. Pivovar*, F. Le Scornet, C. 

Eickes, C. Zawodzinski, G. Purdy, M. Wilson, 

and P. Zelenay. 

4.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, UT, October 20-24, 2002. Title: 

"The Role of Membrane Thickness and 

Interfaces on DMFC Properties," M. Hickner 

and B. Pivovar*. 

5.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, Utah, October 20-24, 2002. 

Title: "The Effect of BPSH Post Treatment on 

DMFC Performance and Properties"; M. 

Hickner*, B.S. Pivovar, Y. Kim, J. McGrath and 

P. Zelenay. 

6.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, Utah, October 20-24, 2002. 

Title: "Modeling the Direct Methanol Fuel Cell 

Anode"; C. Diniz*, R. Moore, P. 

Badrinarayanan and P. Zelenay. 

7.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, Utah, October 20-24, 2002. 

Title: "Understanding the Cathode of A Direct 

Methanol Fuel Cell"; P. Badrinarayanan*, R. 

Moore, C. Diniz, J. Cunningham and P. Zelenay. 

8.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, Utah, October 20-24, 2002. 

Title: "Optimization of Carbon-Supported 

Platinum Cathode Catalysts for DMFC 

Operation"; Y. Zhu*, E. Brosha and P. Zelenay. 

9.	 202nd Meeting of the Electrochemical Society, 

Salt Lake City, Utah, October 20-24, 2002. 

Title: "Electrochemical and XRD 

Characterization of Pt-Ru Blacks for DMFC 

Anodes"; C. Eickes*, E. Brosha, F. Garzon, G. 

Purdy, P. Zelenay, T. Morita and D. Thompsett. 

6 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

10. The International Battery Association and 5th 

Hawaii Battery Conference, Ernest B. Yeager 

Memorial Symposium, Waikoloa, Hawaii, 

January 7-10, 2003. Title: "Electrocatalysis in 

Direct Methanol Fuel Cells"; P. Zelenay (invited 

lecture). 

11. Workshop on "Advances in Materials for Proton 

Exchange Membrane Fuel Cell Systems," 

Asilomar, California, February 23-27, 2003. 

Title: "Direct Methanol Fuel Cell Research at 

Los Alamos: From Fundamentals to Stacks"; P. 

Zelenay (plenary lecture). 

12. Workshop on "Advances in Materials for Proton 

Exchange Membrane Fuel Cell Systems," 

Asilomar, California, February 23-26, 2003. 

Title: "The Influence of Polymer Structure on 

Fuel Cell Electrolyte Properties"; B. S. Pivovar 

(invited talk). 

13. Columbia University, Department of Chemical 

Engineering, New York, NY, April 22, 2003. 

Title: "Effect of Polymer Structure on Fuel Cell 

Properties"; B. S. Pivovar (invited talk). 

 FY 2003 Progress Report 

14. 203rd Meeting of the Electrochemical Society, 

Paris, France, April 27 - May 2, 2003. Title: 

"Methanol Crossover in Direct Methanol Fuel 

Cell Systems"; B. Pivovar*, G. Bender, P. Piela 

and P. Zelenay. 

15. 203rd Meeting of the Electrochemical Society, 

Paris, France, April 27 - May 2, 2003. Title: 

"State of the DMFC Cathode During Prolonged 

Cell Operation"; C. Eickes, P. Piela and P. 

Zelenay*. 

16. Seminar "Electrocatalysis in PEM Fuel Cells", 

Trondheim, Norway, May 5, 2003. Title: 

"Electrocatalysis in Direct Methanol Fuel 

Cells"; C. Eickes, P. Piela and P. Zelenay* 

(invited lecture). 

17. Annex XI Meeting of International Energy 

Agency Meeting, May 6 - 7, 2003, Trondheim -

Bergen, Norway. Title: "20 W DMFC System 

Development at LANL"; P. Zelenay*. 

7 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of Advanced Catalysts for Direct Methanol Fuel Cells 

S. R. Narayanan 

Jet Propulsion Laboratory (JPL) 

California Institute of Technology 

Pasadena, California 91109 

Phone: (818) 354-0013; Fax: (818) 393-6951; E-mail: s.r.narayanan@jpl.nasa.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Reduce catalyst cost for direct methanol fuel cells 

•	 Demonstrate the feasibility of reducing noble metal catalyst loading to less than 0.5 mg/cm2 

•	 Develop a low-cost manufacturing technique for membrane electrode assembly (MEA) fabrication 

•	 Identify potential non-noble metal catalytic systems 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

Approach 

•	 Prepare multi-component thin film catalyst layers by direct current and radio frequency magnetron 

sputtering 

•	 Identify a corrosion-resistant non-noble metal system 

•	 Exploit nanophase properties of sputtered thin films based on Ni/Zr, Co/Zr, and other valve metal 

combinations 

•	 Devise ways to control composition, microstructure, and electrochemical performance 

•	 Characterize catalyst layers in half-cells and full cells 

•	 Characterize catalyst layers by X-ray diffraction (XRD) and scanning electron microscopy (SEM) for 

structural and electronic properties 

Accomplishments 

•	 Prepared multicomponent combinatorial samples with unique non-equilibrium nanophase structure by 

sputter deposition 

•	 Identified novel corrosion-resistant non-noble nanophase thin film catalyst layers based on nickel and 

zirconium 

•	 Nickel/zirconium intermetallics with compositions less than 70% nickel found to be corrosion resistant 

under fuel cell conditions 

•	 Nickel/zirconium layers have been found to protect base metal surfaces such as nickel in sulfuric acid 

•	 Quaternary composition consisting of Pt-Ru-Ni-Zr enhances noble metal utilization in catalysts for 

methanol oxidation 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Continue to study composition, morphology and electrochemical performance of Ni/Zr coatings 

•	 Evaluate quaternary compositions of Ni-Zr-Pt-Ru to lower the amount of Pt-Ru and to tune electronic 

interactions 

•	 Evaluate Co-Zr sputtered layers for methanol oxidation activity; Co has higher catalytic activity 

compared to Ni for many organic transformations 

•	 Exploit morphological modification using ion-beam techniques for improving activity 

•	 Correlate electronic properties of materials from extended X-ray absorption fine structure (EXAFS) 

and X-ray photoelectron spectroscopy (XPS) with catalytic properties 

Introduction 

Fuel cells offer the possibility of reduced 

emissions and high efficiency for transportation 

applications. Of the various fuel cells being 

considered, the direct methanol fuel cell (DMFC) is 

very attractive due to the key advantages of system 

simplicity and good transient response compared to 

reformate-air fuel cell systems. However, DMFCs 

currently require unsupported noble metal catalysts 

at high loadings of 2.5-4.0 mg/cm2

, leading to a high 

catalyst cost of $100-150/kW. Also, to keep the 

overall fuel cell cost low, the preferred method of 

catalyst application must be designed for 

manufacturing. Thus, cost presents a major obstacle 

to commercialization of DMFCs for transportation 

applications. Enhancement of the overall fuel cell 

efficiency is also necessary to meet the weight and 

volume requirements for transportation applications. 

The present research effort aims at addressing these 

key issues of cost and efficiency. The overall 

objective of the effort is to develop new low-cost 

electrocatalyst materials and new methods of 

preparing fuel cell electrodes that will reduce the 

amount of noble metal used and lead to overall cost 

reduction and improved performance of direct 

methanol fuel cells. 

Approach 

of organics, they are not stable in acidic media. 

Therefore, the possibility of creating multicomponent alloys containing some mixture of Ni, 

Co, Zr, Pt, and Ru that are catalytically active and 

stable in the fuel cell environment has been 

investigated. The first studies conducted were on cosputtered Ni-Zr films. Structure, corrosion resistance 

in acid, and electrochemical activity for methanol 

oxidation were then studied. A series of quaternary 

Ni-Zr-Pt-Ru samples were also fabricated and tested 

to examine the possibility of lower Pt/Ru loadings in 

the catalyst. 

Results 

Investigations at JPL on sputter-deposited 

nanocrystalline Ni-Zr have shown that these 

bimetallic phases exhibit excellent corrosion 

resistance in 1 M sulfuric acid. Figure 1 contains 

results of X-ray diffraction from a series of 

combinatorially deposited Ni-Zr alloys with Ni/Zr 

atomic ratios ranging from 45/55 to 75/25. These 

data suggest that a single-phase nanocrystalline solid 

solution is obtained. Scherrer peak-broadening 

analysis indicates that the average grain size in these 

films is less than 2 nm. Based on the literature, such 

an amorphous/nanocrystalline type of structure is 

anticipated to be more corrosion resistant than 

similar materials with a polycrystalline 

microstructure. 

Using sputter-deposition, mixed compounds and 

multi-component alloys of virtually any composition 

can be readily deposited [1]. Specifically, nonequilibrium phases have unique properties compared 

to phase-separated intermetallics. Although nonnoble metals such as nickel and cobalt are excellent 

for catalysis of hydrogenation and dehydrogenation 

Figure 2 shows an image of a series of samples 

consisting of Ni-Zr of varying composition deposited 

on carbon foil and immersed in a 1 M H2SO4 

solution for 24 hours. The photograph is visible 

evidence that films with Ni/Zr atomic ratios less than 

70/30 remain intact and shiny, while those films with 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 X-ray diffraction from a series of Ni/Zr films as 

deposited onto a Si wafer substrate. The data 

are consistent with that expected from a 

nanocrystalline Ni/Zr solid solution. 

Figure 2.	 Image of Ni/Zr films sputtered onto carbon foil 

and immersed in 1 M H2SO4 solution for 24 

hours. The films with Ni/Zr atomic ratios less 

than 70/30 are still visible, while those films 

with higher Ni contents appear to have 

dissolved. 

higher Ni content dissolve and leave behind a 

substrate with no coating. 

Figure 3 (top) shows plots of open circuit 

potential (Voc) of various Ni/Zr film electrodes as a 

Figure 3.	 (top) Plot showing Voc vs. time for Ni/Zr on C 

foil. Those with a Ni/Zr ratio lower than 70/20 

had a higher potential vs. MSE compared to 

that observed from pure Ni, indicating chemical 

stability. (bottom) Potentiostatic current vs. 

time plots for a 40/60 Ni/Zr film under 

potentials ranging from 0.05 to 0.74 V vs. 

NHE. No measurable currents were detected. 

function of time in de-aerated solutions of 1 M 

sulfuric acid. The open circuit potential values 

attained with all the compositions is much greater 

than 0.6 V vs. the mercury/mercurous sulfate 

reference electrode (MSE), suggesting that the 

surface is not evolving hydrogen and is extremely 

passive in contact with sulfuric acid. Also, data in 

Figure 3 (bottom) shows that there is essentially no 

cell current induced upon cell biasing with potentials 

ranging from 0.05 to 0.75 V vs. normal hydrogen 

electrode (NHE), confirming the corrosion resistance 

and absence of any significant faradaic process under 

applied anodic potentials. A film consisting of 40/60 

Ni/Zr was used in a fuel cell anode as an under-layer 

for a sputtered Pt/Ru DMFC anode layer. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

In this test, the anode structure consisted of a 

Torayâ carbon paper substrate, a 150-nm thick layer 

of Ni/Zr, and a 200 nm thick layer of Pt/Ru (50/50). 

This anode was combined with a Nafionâ membrane 

and a Pt-black cathode to form a membraneelectrode assembly that was tested as a direct 

methanol fuel cell. Figure 4 shows the performance 

of the fuel cell. The fuel cell performance was stable 

over several days of testing with no evidence of 

degradation, showing that the Ni/Zr was robust in the 

acidic fuel cell environment. 

The results in Figure 4 also indicate that the Ni/ 

Zr was sufficiently electrically conductive - an 

important criteria that needs to be satisfied by a 

corrosion-resistant layer to be considered for this 

type of application. 

It is also possible for this new class of materials 

to be used to minimize the Pt/Ru loading by creating 

quaternary alloy systems that contain very small 

amounts of noble metal and are primarily composed 

of non-noble metals. One such possible system is cosputtered Pt/Ru/Ni/Zr. 

Results of polarization experiments in solutions 

of methanol/1 M sulfuric acid are shown in Figure 5. 

These results indicate that a catalyst layer that 

contains just 17% Pt exhibits the same current as that 

with 50 atomic % Pt, confirming the possibility of 

 FY 2003 Progress Report 

significantly lowering the noble metal content using 

non-noble metal additives such as Ni and Zr. 

Investigation of the electrochemical oxidation 

activity of these films, consisting of Pt-Ru-Ni-Zr, at 

elevated temperatures show that activity levels 

exceed those expected from plain sputtered PtRu 

(without Ni/Zr). The mechanisms driving this effect 

will be investigated in FY 2004. 

Conclusions 

•	 Thin film corrosion-resistant and electrocatalyst 

layers consisting of non-noble metal 

combinations have been prepared by sputter 

deposition. 

•	 As-deposited Ni-Zr films were found to be 

nanocrystalline in nature, with average grain 

sizes less than 2 nm in diameter. 

•	 Ni/Zr films with nickel content greater than 40% 

were found to be corrosion-resistant in sulfuric 

acid and in the fuel cell environment. 

•	 A direct methanol fuel cell comprising of a 

sputtered Pt/Ru (50/50) anode catalyst layer with 

an underlayer of 150 nm thick Ni-Zr was found 

to be stable over multiple days of testing. 

Figure 4.	 Multiple current-voltage sweeps of a DMFC 

made using a Ni-Zr support layer on the anode. 

Though the Pt-Ru layer was not optimized for 

best performance, this test showed that a Ni/Zr 

support layer was compatible with a full fuel 

cell environment. 

Figure 5.	 Potentiostatic data showing half-cell current vs. 

time for a Pt50Ru50 film and a 

Ni16Zr36Pt17Ru31 film sputtered on carbon foil. 

When held at 0.7 V vs. NHE in 1 M methanol, 

1 M sulfuric acid at about 25oC, the observed 

current levels are very similar. 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

•	 Quaternary alloy mixtures of Pt-Ru-Ni-Zr have 

been found to have properties similar to Pt-Ru 

films with over three times the Pt content. This 

new class of alloy catalyst that consists of a large 

amount of non-noble metal with very small 

amounts of Pt seems to be extremely promising. 

References 

1. DOE Labs Annual Report 2001. 

FY 2003 Publications/Presentations 

1. S. R. Narayanan, J. Whitacre and C.K. Witham, 

"Advanced Catalysts for Direct Methanol Fuel 

Cells", Presentation at the DOE Lab Annual 

Merit Review, May 2003, Berkeley, CA. 

2. "Nanocrystalline Corrosion-Resistant Layers Via 

Sputter Deposition." Manuscript in preparation, 

to be submitted to Journal of Power Sources in 

September 2003. 

 FY 2003 Progress Report 

3. "Minimizing Pt Loading in Methanol Fuel Cells 

Using A Quaternary Pt-Ru-Ni-Zr Catalysis 

Layer." Manuscript in preparation, to be 

submitted to Journal of Electrochemistry in 

September 2003. 

Special Recognitions & Awards/Patents 

Issued 

1. New Technology Report # 40415 titled 

"Corrosion resistant materials for fuel cells based 

on nanophase Nickel-Zirconium alloys", S.R. 

Narayanan, Jay Whitacre and T. I. Valdez, May 

2003. 

2. New Technology Report #20250: Sputterdeposited fuel cell electrodes and membranes 

with high performance and low-cost: A new 

technique for commercialization of fuel cells", 

B. Jeffries-Nakamura, W. Chun, S.R. Narayanan, 

R. Ruiz, August 1997. 

5 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Novel Approach to Non-Precious Metal Catalysts (New FY 2004 Project) 

Dr. Radoslav T. Atanasoski (Primary Contact) 

3M Company 

Fuel Cell Components Program 

Building 201-02-S-05 

St. Paul, MN 55144-1000 

Phone: (651) 733-9441; Fax: (651) 575-1187; E-mail: rtatanasoski@mmm.com 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: Donna.Ho@ee.doe.gov 

Objectives 

•	 Reduce the dependence of proton exchange membrane (PEM) fuel cell catalysts on precious metals. 

•	 Achieve performance comparable to precious metal catalysts used in currently commercialized 

membrane electrode assemblies (MEAs) at a cost 50% less compared to a target of 0.2 g Pt/peak kW. 

•	 Target demonstrated durability of greater than 2,000 hours with less than 10% power degradation. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

Approach 

The objectives of this project are to reduce the 

dependence of PEM fuel cell catalysts on precious 

metals in order to reduce the cost of the fuel cell 

stack as well as the overall system cost without loss 

of current performance or durability. The target is to 

develop catalysts that perform at least as well as the 

conventional precious metal catalysts currently in use 

in commercialized MEAs and that cost 50% less 

compared to a target of 0.2 g Pt/peak kW. The target 

for catalyst durability is greater than 2,000 hours 

with less than 10% power degradation. 

The proposed work is directed at meeting these 

objectives while taking into account that the total 

costs of the catalysts include the processing costs for 

their synthesis and integration into an MEA. Several 

innovative technology approaches will be combined 

for synthesizing new non-precious metals and their 

support particles by process methods that also 

simultaneously disperse and coat the catalysts onto 

high-volume compatible substrates for low-cost 

integration into MEAs. The proposed candidate nonprecious metal catalysts are based on the latest 

advances in fundamental understanding of the most 

promising areas of cathode catalyst development in 

the world. Sound scientific evidence from published 

data has been used to identify a new class of 

potentially active multi-element chemical centers for 

oxygen reduction. Two process methods, new for 

this purpose, will be investigated for synthesizing 

these new materials and applying them onto a 3M 

proprietary, high surface area, catalytic support 

system, compatible with high-volume roll-good 

processing of MEAs. The approach takes advantage 

of recent advances in 3M cathode catalyst 

development, which have significantly reduced the 

precious metal content of Pt-based ternary catalysts. 

The proposed work is divided into two principal 

tasks. The first task is focused on development of the 

required new material properties. This will be 

accomplished through extensive catalyst fabrication 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies

and performance screening to obtain correlations of 

the material composition and structure characteristics 

with the desired electrochemical properties on the 

one hand and the various process parameters on the 

other. The second task is focused on scale-up of the 

materials and processes to demonstrate the feasibility 

for high-volume production and generate large area 

MEAs for PEM fuel cell stack testing. The proposed 

work covers a 3-year period. 

 FY 2003 Progress Report 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Novel Non-Precious Metals for PEMFC: Catalyst Selection Through Molecular 

Modeling and Durability Studies (New FY 2004 Project) 

Dr. Branko N. Popov (Primary Contact) 

Department of Chemical Engineering 

Swearingen Engineering Center 

University of South Carolina (USC) 

Columbia, SC 29208 

Phone: (803) 777-7314; Fax: (803) 777-8265; E-mail: popov@engr.sc.edu 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: Donna.Ho@ee.doe.gov 

Objectives 

•	 Construct and test membrane electrode assemblies (MEAs) with different non-precious 

metallic nanoclusters. 

•	 Demonstrate the potential of non-precious metal catalysts to perform at least as well as the 

conventional Pt catalysts currently in use in MEAs and cost at least 50% less while meeting a target of 

0.2 g (Pt loading)/peak kW. 

•	 Optimize the catalyst composition for durability of >2000 hours operation with less than 10% power 

degradation. 

•	 Perform slab band surface calculation of H2O and OH adsorption on novel catalysts. Based on this, we 

will identify promising catalysts and optimize their compositions. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

Approach 

The goal of the proposed work is to construct and 

test membrane electrode assemblies (MEAs) with 

different non-precious metallic nanoclusters. The 

objective is to demonstrate the potential of nonprecious metal catalysts to perform at least as well as 

the conventional Pt catalysts currently in use in 

MEAs and cost at least 50% less while meeting a 

target of 0.2 g (Pt loading)/peak kW. Apart from 

activity, optimization of catalyst composition will be 

based on durability of >2000 hours operation with 

less than 10% power degradation. Performance 

(activity and stability) of the following three different 

types of metallic nanoclusters will be extensively 

studied: (i) metal carbon nanoclusters; (ii) nonprecious chalcogen compounds and (iii) binary 

transition metal microcycles. The approach takes 

advantage of recent accomplishments in USC 

cathode catalyst development which have drastically 

reduced the thickness of the catalyst layer and the 

precious metal content of Pt-based binary catalysts. 

Theoretical studies will be conducted to 

determine the electronic, geometric, and 

thermodynamic factors that determine catalytic 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

and electrocatalytic behavior as observed from 

the experimental characterization. Theoretical 

studies will comprise a series of high level ab 

initio investigations on representative clusters as 

well as on extended systems focusing on 

fundamental interactions relevant to adsorption 

and reaction processes. 

The proposed work is divided into five tasks. 

The first task is focused on molecular modeling of 

novel catalysts. The work will include Vienna ab 

Initio Simulation Program (VSAB) slab band 

calculation to model surface adsorption of H2O and 

O2 reduction intermediates for the purpose of 

estimating their reversible potentials of formation. 

The second task is focused on synthesis of novel 

catalysts, which will include: (i) synthesis of metal 

carbon nanoclusters; (ii) synthesis of non-precious 

chalcogen compounds and (iii) synthesis of binary 

transition metal microcycles. The third task targets 

the material characterization of the catalysts. The 

 FY 2003 Progress Report 

fourth task focuses on electrochemical 

characterization, including electrochemical 

characterization of thin film membrane assemblies 

and optimization studies of nanostructured electrode/ 

electrolyte interface. The fifth task will optimize the 

stability of the catalysts. The objective of this task is 

to evaluate the long-term performance of the 

composite electrodes. Tafel and linear polarization 

(LP) technique and conventional three-electrode 

setup will be used to estimate the corrosion rates of 

the electrocatalysts in sulfuric acid. To test the longterm performance of the electrocatalyst under real 

environmental conditions, a single test cell will be 

used coupled with the test station. The infrared 

polarization test will be performed as a function of 

time (300 hours) at constant potential of 0.8 V. 

This work will be done in collaboration between 

University of South Carolina (USC); Case Western 

Reserve University (CWRU), Cleveland, Ohio; and 

Northeastern University, Boston, Massachusetts. 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Thermal and Water Management System for PEM Fuel Cells 

(New FY 2004 Project) 

Mark K. Gee 

Honeywell International Inc. 

2525 W. 190th Street 

Torrance, CA 90504 

Phone: (310) 512-3606; Fax: (310) 512-4998; E-mail: mark.gee@honeywell.com 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811: E-mail: Donna.Ho@ee.doe.gov 

Objectives 

Develop an integrated thermal and water management (TWM) system that efficiently uses the fuel cell 

waste heat and water to minimize overall system weight and volume without compromising overall system 

efficiency 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 C. Thermal Management 

•	 F. Heat Utilization 

•	 R. Thermal and Water Management 

Approach 

For automotive applications, it is essential to 

develop a low-cost, high-performance thermal and 

water management (TWM) system for proton 

exchange membrane (PEM) fuel cells. The objective 

of this project is to develop an integrated TWM 

system that efficiently uses the fuel cell waste heat 

and water to minimize overall system weight and 

volume without compromising overall system 

efficiency. Water consumption and production will 

be balanced to eliminate the need for makeup water. 

Waste heat generated by the PEM fuel cell 

cannot be easily removed from the system because it 

is supplied with a relatively low temperature. This 

requires heat exchangers with high effectiveness to 

achieve compact systems. Compact, lightweight heat 

exchangers of this type, having advanced heat 

transfer extended surfaces, have been developed for 

aerospace applications, where a premium is placed 

on size, weight, and performance. This heat transfer 

technology will be transitioned to Honeywell's 

automotive division, where high-volume 

manufacturing processes will be utilized to reduce 

costs of the equipment. 

Some of the advanced technologies to be 

evaluated for accomplishing the objectives of the 

project include: 

•	 An enthalpy wheel developed by Emprise 

Corporation, a member of the Honeywell team, 

utilizing latent heat transfer methods to greatly 

improve recovery of water and fuel cell waste 

heat. 

•	 A membrane-based water management system 

developed by Isotronics, a member of the 

Honeywell team, that can be used to transfer 

water vapor from the hot and humid exhaust 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies

stream from the fuel cell to the cooler and drier 

stream entering the fuel cell as reactant. 

•	 A cathode recycle approach to avoid water 

condensation and revaporization. 

•	 Microchannel thermal heat transfer equipment, 

an evolving technology that may lead to savings 

of 30 percent volume in the thermal management 

system over current technologies. 

 FY 2003 Progress Report 

The analytical and test results of this study could 

have a dramatic impact on water and thermal 

management systems for PEM fuel cells for 

automotive applications. The project will be 

conducted over a three-year period in two phases. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of Polybenzimidazole-based, High-Temperature Membrane 

and Electrode Assemblies for Stationary and Automotive Applications 

(New FY 2004 Project) 

Rhonda Staudt 

Plug Power, Inc. 

968 Albany Shaker Road 

Latham, NY 12110 

Phone: (518) 782-7700, x1215; Fax: (518) 782-7961; E-mail: rhonda_staudt@plugpower.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0987; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Objectives 

•	 Select the appropriate polymer chemistry for polybenzimidazole (PBI) proton exchange membrane 

materials optimized to fuel cell requirements. 

•	 Demonstrate the long-term performance of the PBI membrane, including mechanical, electrochemical, 

and operating properties, in cells and stacks. 

•	 Provide a cost analysis of a low-cost membrane manufacturing process with projected costs consistent 

with meeting the specified high-volume targets. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Transportation Systems Barriers 

•	 C. Thermal Management 

•	 E. Durability 

•	 F. Heat Utilization 

Component Barriers 

•	 P. Durability 

•	 Q. Electrode Performance 

•	 R. Thermal Management 

Approach 

The goal of this project is to optimize a hightemperature PBI membrane to meet the performance, 

durability, and cost targets required for stationary and 

automotive fuel cell applications. The ultimate result 

will be a low-cost PBI membrane material and a 

corresponding manufacturing process that will meet 

the DOE targets for a membrane that operates at 

greater than 120°C at pressures up to 3 atm with a 

projected design lifetime in excess of 40,000 hours. 

The corresponding membrane electrode assembly 

(MEA) cost targets are <$10/kW for 500,000 

automotive fuel cell stacks per year and <$1,500/kW 

for 1,000 stationary fuel cell stacks per year. In this 

project, the Plug Power team will conduct extensive 

testing and verification of candidate PBI materials 

under automotive and stationary operating 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

conditions, followed by selection of the best 

chemical composition and manufacturing process 

that will yield a highly reliable, low-cost membrane. 

The proposed work covers a three-year period 

and is divided into three principal parallel and 

integrated technology focuses. The first focus 

addresses screening of candidate polymers and 

membrane fabrication processes. Film properties 

will be measured, and their relationship with polymer 

structure will be determined; the parameters that 

control film fabrication and manufacturing scale-up 

will be defined. 

In the second focus, MEAs will be screened for 

numerous performance characteristics, followed by 

in-depth parametric studies for both short- and longterm applications. Scaled-up MEAs with active 

areas of at least 250 cm2

 will be assembled into and 

evaluated in short stacks. 

The third focus is the development and 

demonstration of hardware optimized for PBI-based 

MEAs. Specifically, membrane/electrode interfaces, 

flow fields and acid management strategies will be 

investigated. Cathode performance improvements 

will be sought by optimizing standard electrode 

architectures and by investigating unique solutions 

such as nanotechnologies. The coupling of hardware 

and MEA performance will be a significant aspect of 

this work. A key deliverable will be a model to 

quantify the manufacturing cost of the selected PBI 

membrane. 

The Plug Power team includes two university 

partners, Rensselaer Polytechnic Institute (RPI) in 

Troy, New York, and Albany NanoTech (ANT) at the 

State University of New York (SUNY) in Albany. 

The third partner is Celanese Ventures (GmbH), a 

polybenzimidazole (PBI) manufacturer. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development, Characterization, and Evaluation of Transition Metal/Chalcogen 

Based Cathode Catalysts for PEM Fuel Cells (New FY 2004 Project) 

Noordin Nanji 

Ballard Power Systems Corporation 

15001 Commercial Drive N. 

Dearborn, MI 48120 

Phone: (604) 412-7929; Fax: (604) 453-3600; E-mail: noordin.nanji@ballard.com 

DOE Technology Development Manager: Donna Ho 

Phone: (202) 586-8000; Fax: (202) 586-9811; E-mail: Donna.Ho@ee.doe.gov 

Objectives 

Develop a non-precious metal cathode catalyst for proton exchange membrane (PEM) fuel cells which is 

as active and as durable as current platinum group metal (PGM) based catalysts at a significantly reduced 

cost. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• O. Stack Material and Manufacturing Cost 

Approach 

The objective of this project is to develop a nonprecious metal cathode catalyst for PEM fuel cells 

which is as active and as durable as current PGM 

based catalysts at a significantly reduced cost. The 

catalytic surfaces of interest are based upon nonprecious transition metals such as Co, Ni, Cr and Fe 

in structures with non-stoichiometric amounts of 

chalcogens (S and Se) to produce the active sites in 

an oxygen containing environment. 

The partnership Ballard Power Systems has with 

several universities, including the University of 

British Columbia and Case Western Reserve 

University, links together for the first time 

fundamental research on electrocatalysis and 

evaluation of catalysts in real fuel cell stacks. This 

project brings together scientific knowledge and 

innovation with commercial considerations and 

technological verification, giving an opportunity to 

deliver an application-ready material. 

This work will study well defined surfaces to 

determine not only the magnitude of the activity but 

also the nature of the active site and the mechanism 

involved. The project will then proceed to develop a 

commercially viable, environmentally friendly 

process for the production of high surface area fuel 

cell catalysts for demonstration in fuel cell stacks. 

The major advantages of this project are not just 

cost related, as the development of catalysts that are 

more specific for oxygen reduction than platinum 

leads to catalysts that are more robust and less 

sensitive to air-borne contaminants. The lower cost 

of a major component of fuel cell technology will 

significantly advance the fuel cell technology 

towards the marketplace in commercial products 

such as vehicles and portable power applications. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

PEM Stack Durability (New FY 2004 Project) 

DJayson W. Bauman, Ph.D. 

Program Manager, Product Durability 

DuPont Fuel Cells 

Chestnut Run Plaza, Building 701 

Wilmington, DE 19805-0701 

Phone: (302) 999-2194; Fax: (302) 999-2395; E-mail: jayson.bauman@usa.dupont.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lightner@ee.doe.gov 

Objectives 

•	 Develop a detailed understanding of the membrane electrode assembly (MEA) failure process 

•	 Develop perfluorosulfonic acid (PFSA) membranes with extended lifetimes 

•	 Model membrane failure modes 

•	 Perform extended stack tests with the optimized membranes and characterize structure and 

degradation mechanisms
 

•	 Elucidate failure mechanisms and develop technologies to meet the design lifetime target of proton 

exchange membrane (PEM) fuel cells (40,000 hours operation with <10% degradation in performance 

for stationary applications in 2010) 

•	 Perform research, development and demonstration of membrane/catalyst systems that address 

transportation and/or stationary applications
 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 E. Durability 

•	 O. Stack Material and Manufacturing Cost 

Approach 

Proton exchange membrane fuel cell companies 

need a more durable, longer-lived, cost effective 

membrane technology. PEM systems based on 

PFSA membranes are better understood than their 

high temperature counterparts. This project focuses 

on risk reduction of previously identified PFSA 

membrane degradation mechanisms and validation of 

promising mitigation strategies. 

DuPont has enlisted the unique experience and 

capabilities of the University of Connecticut and the 

University of Southern Mississippi to realize our 

goals. Our combined extensive experience, 

understanding of degradation mechanisms and 

proprietary membrane stabilization technology will 

provide a significant improvement in PFSA 

membranes that will achieve the DOE 2010 stack 

durability target of 40,000 hours for stationary fuel 

cells. 

DuPont Fuel Cells, in partnership with United 

Technologies, will deliver a fuel cell system with a 

40,000 hour PEM stack at an affordable price at the 

conclusion of this three-year project. 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

MEA and Stack Durability for PEM Fuel Cells (New FY 2004 Project) 

Dr. Mike T. Hicks (Primary Contact) 

3M Company 

Fuel Cell Components Program 

Building 201-02-N-19 

St. Paul, MN 55144-1000 

Phone: (651) 736-8433; Fax: (651) 575-1187; E-mail: mike-hicks@mmm.com 

DOE Technology Development Manager: Kathi Epping 

Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov 

Subcontractors: 

Plug Power Inc., Latham, NY 

Case Western Reserve University, Cleveland, OH 

Objectives 

•	 Develop an understanding of membrane electrode assembly (MEA) failure mechanisms encountered 

under real world operating conditions. 

•	 Develop a high performance MEA and matched system operating conditions having enhanced 

durability (targeted for 40,000 hours operation with <10% performance degradation in stationary 

applications). 

•	 Characterize life expectancy and performance degradation of the MEA in extended testing (>2000 

hours) in a field-ready fuel cell system using reformate fuel. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

Approach 

Proton exchange membrane (PEM) fuel cells are 

poised to change the landscape of power generation 

over the next ten years. Applications for portable 

power, back-up power, automotive power, and 

stationary power generation are being developed 

around the world. Estimates for the size of the fuel 

cell industry range as high as $50 billion by 2010. 

For this to be realized, however, considerable 

technical challenges still remain. The most 

significant of these challenges are those of cost and 

system lifetime, where 40,000 hours of operation 

with less than 10% decay is desired. In order to 

address these issues, we have assembled a team 

consisting of 3M, a materials and MEA manufacturer 

in the PEM fuel cell industry; Plug Power, a fuel cell 

stack and system manufacturer; and Case Western 

Reserve University, an electrochemical research 

institute with extensive knowledge of fuel cell 

technology. 

In order to achieve the desired lifetime goals, the 

team will focus on (1) determining the root causes of 

MEA failure modes – membrane failure, catalyst 

activity losses, mass-transport losses, electrode 

losses (structural changes) and interfacial losses, and 

(2) using the information garnered from part one in 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

the development of new materials and system 

designs to improve durability. The project plan has 

several innovative approaches, namely: (a) use of 

new perfluorinated sulfonic acid ionomers; (b) 

development of ex-situ component aging tests 

designed to separate out effects of individual material 

degradation mechanisms and correlation with realtime and accelerated in-cell performance tests; (c) 

assembly and testing of MEAs using virgin and aged 

components to identify how those aged components 

affect cell performance; (d) use of novel 

experimental approaches for determining the loci of 

degradation within the cell; (e) use of computational 

modeling of non-uniformities within a cell to 

 FY 2003 Progress Report 

characterize how non-uniformities affect failure 

modes and to design out the non-uniformities; and (f) 

system and materials perspective to understand the 

interactions of the stack design and operation on 

MEA performance and durability. Throughout this 

work, it is our intent to develop technologies that can 

accelerate the introduction of PEM fuel cell 

technology into a wider variety of applications that 

demand longer lifetimes. To accomplish this, Plug 

Power will evaluate the approaches and technologies 

identified to ensure that they are economically 

feasible in terms MEA cost and durability vs. a cost 

of energy model. The proposed work covers a threeyear period. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Low-Cost, Durable Membrane and Membrane Electrode 

Assembly for Stationary and Mobile Fuel Cell Applications 

(New FY 2004 Project) 

Dr. Michel Foure 

Atofina Chemicals, Inc. 

900 First Avenue 

King of Prussia, PA 19406 

Phone: (610) 878-6790; Fax: (610) 878-6298; E-mail: michel.foure@atofina.com 

DOE Technology Development Manager: Valri Lightner 

Phone: (202) 586-0937; Fax: (202) 586-9811; E-mail: Valri.Lighther@ee.doe.gov 

Objectives 

•	 Develop low-cost, high-durability membranes and membrane electrode assemblies (MEAs) for 

polymer electrolyte membrane (PEM) fuel cells. 

•	 Improve the Kynar polyvinylidenefluoride (PVDF) based membrane, particularly regarding 

conductivity and water management. The result of this work will be an optimized composition of 

Atofina's polymer alloy yielding a high-conductivity/low-cost membrane at the laboratory scale. 

•	 Prepare suitable electrodes for the Kynar PVDF membrane. 

•	 Develop manufacturing processes for polyelectrolyte ionomer, membranes, and high-performance 

MEAs. 

•	 Run long-term endurance tests in fuel cells, evaluate possible degradation and degradation 

mechanisms and, in parallel, develop accelerated tests to provide faster feedback to the synthetic effort 

related to the membrane and the polyelectrolyte ionomer. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

Approach 

The objective of this project is to develop lowcost, high-durability membranes and membrane 

electrode assemblies (MEAs) for polymer electrolyte 

membrane (PEM) fuel cells. The team members, 

lead by Atofina, are Johnson Matthey Fuel Cells, 

UTC Fuel Cells, the Georgia Institute of Technology 

and the University of Hawaii. 

The technical approach is based on 

technology developed by Atofina exploiting the 

unique properties of its Kynar

polyvinylidenefluoride (PVDF). Kynar offers 

a unique combination of exceptional chemical 

and electrochemical stability, excellent 

mechanical properties, low flame and smoke 

properties, and recyclability at a low cost. 

Atofina turned to its own fluoropolymers 

technology to seek cost-effective solutions, 

which also could offer several other significant 

benefits in terms of improved mechanical 

properties and high-temperature performance. 

These membranes and MEAs have the potential 

to operate at higher temperatures than 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

conventional fluoroionomers (of the Nafion

type) and offer high durability. 

The mechanical characteristics of membranes 

prepared from Kynar PVDF are excellent. The 

films are sturdy; they show very good tear resistance 

and negligible creep at all temperatures tested (as 

high as 120°C). Johnson Matthey Fuel Cells 

reported permeability to hydrogen on the order of 1/3 

of that of Nafion, a very desirable property. The 

combination of excellent mechanical properties and 

low gas permeability offers the exciting prospect to 

make high-performance, thin membranes. In this 

respect, it is noteworthy that it is the resistance of the 

membrane/MEA which dictates proton conductivity 

– not the intrinsic conductivity (i.e., thinner 

membranes have a lower resistance than thicker 

membranes). 

The project’s technical work is divided into three 

major tasks. Task 1 is membrane development led by 

Atofina in collaboration with Georgia Tech, 

particularly on high-throughput membrane 

composition screening and characterization. The 

deliverables of Task 1 are a high-conductivity, lowcost membrane (lab scale). Task 2, MEA 

development, is led by Johnson Matthey Fuel Cells, 

with substantial input from Atofina for the 

polyelectrolyte ionomer. The deliverable of Task 2 is 

a high-performance, low-cost MEA produced on a 

pilot line featuring high durability. Task 3, cell and 

stack development and verification, is led by UTC 

Fuel Cells with the help of the University of Hawaii. 

 FY 2003 Progress Report 

The product of Task 3 will be a multiple-cell stack 

meeting DOE’s goals. The three tasks will be 

conducted in sequence with substantial overlap for 

feedback loops. The total duration of the project is 

anticipated to be 36 months. 

Atofina is the fourth largest chemical company 

in the world. It has a major focus on thermoplastics 

polymers, and it is the largest producer of PVDF. 

The project will be conducted in its state-of-the-art 

Research Center located in King of Prussia, 

Pennsylvania. Johnson Matthey Fuel Cell (JMFC) is 

a business unit of Johnson Matthey PLC, a specialty 

chemicals company and a leader in platinum and 

platinum catalysts. JMFC is a leading developer of 

fuel cell components, particularly catalysts and 

MEAs. The work will be carried out primarily in 

West Chester, Pennsylvania. UTC Fuel Cells 

(UTCFC) is a unit of the United Technologies 

Corporation and is a leader in the development, 

manufacturing, and operations of fuel cell power 

plants. Their part of the project will be conducted 

partly in South Windsor, Connecticut, and partly at 

the University of Hawaii. The University of Hawaii, 

in collaboration with the Hawaiian Electric 

Company, UTCFC and the Office of Naval Research, 

has established a first class facility for testing and 

evaluating full-size single-cell and multi-cell fuel cell 

stacks. Georgia Tech has very special expertise in 

the field of high-throughput and combinational 

techniques. Atofina will utilize these techniques to 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

screen and optimize large numbers of compositions in an efficient manner. 

3
 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Neutron Imaging Study Of the Water Transport Mechanism in a Working Fuel Cell 

Muhammad Arif (Primary Contact), David Jacobson, Rahul Satija 

National Institute of Standards and Technology (NIST) 

Gaithersburg, MD 20899 

Phone: (301) 975-6303; Fax: (301) 926-1604; E-mail: arif@nist.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

•	 Quantify water content in fuel cell. 

•	 Quantify water dynamics in fuel cell. 

•	 Optimize neutron imaging spatial and temporal resolutions. 

•	 Demonstrate neutron imaging as a tool for analyzing water management and performance of 

operational fuel cells.
 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 R. Thermal and Water Management 

•	 P. Durability 

Approach 

•	 Stage 1. Based on previously established design parameters and goals, the facility was designed and 

the components manufactured. Careful radiation safety analysis was performed to ensure the 

effectiveness of radiation protection at the facility. 

• Stage 2. 	 Parallel discussions were held with fuel cell developers to evaluate a realistic fuel cell system 

in-situ. This included the use of a fuel cell and a fuel cell controller to monitor the operation of a fuel 

cell during operation on the neutron beam line. 

•	 Stage 3. Assembled facility is extensively tested for radiation protection. 

•	 Stage 4. Fuel cell experiments are run to observe the flow field dynamics and water build-up and 

clogging in the gas diffusion layer (GDL). 

Accomplishments 

•	 Designed and built a neutron imaging facility. 

•	 Demonstrated real time neutron imaging method. 

•	 Examined operational fuel cells for fuel cell component developers. 

Future Directions 

•	 Evaluate coded source imaging as a method for high-resolution real time imaging. 

•	 Provide license-free distributable software for fuel cell developers to independently analyze fuel cell 

operation data. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Upgrade detector systems to allow both: 

- oreal time frame rate (30 fps) and 

- ohigh spatial resolution. 

•	 Conduct both non-proprietary and proprietary imaging experiments to improve knowledge of how 

water management systems function in fuel cells. 

•	 Develop neutron imaging methods to accurately measure water gradients across a fuel cell proton 

exchange membrane (PEM). 

•	 Determine diffusion coefficient and hydrophobic characteristics of the GDL. 

•	 Characterize the two-phase flow mechanism in the fuel cell flow field. 

•	 Conduct a time-dependent study of the membrane-catalyst-GDL interface integrity. 

Introduction 

In a fuel cell, water is formed as a byproduct of 

the reaction between hydrogen and oxygen. If the 

water does not drain quickly and efficiently, then fuel 

cells will not work properly. Water formation is also 

a signature of activity in a fuel cell, so the lack of 

water formation demonstrates a defective area of the 

fuel cell. 

Since fuel cells are not transparent to visible 

light, other forms of penetrating radiation (example: 

x-rays, neutrons) must be used to analyze the 

operation of the fuel cell. X-ray imaging is 

unsuitable because hydrogen is nearly invisible to the 

high-energy x-rays required to penetrate the metallic 

encasement of the fuel cell. Neutrons, which are 

massive, neutrally charged particles, can easily 

penetrate metals and still be extremely sensitive to 

water in quantities less than a microgram. The 

reason for this is best illustrated by a comparison of 

the relative cross sections shown in Figure 1. The 

large x-ray cross section of Al compares to a small 

neutron cross section. Conversely, the x-ray cross 

section for hydrogen is small compared to the 

neutron cross section. This makes neutrons ideal for 

sensing microgram quantities of water. 

Approach 

A new Neutron Imaging Facility (NIF) has been 

constructed at the BT6 high intensity thermal beam 

line at the NIST Center for Neutron Research 

(NCNR) nuclear reactor (Figure 2) to nondestructively characterize water transport mechanism 

in single or multi-stack PEM fuel cells. The facility 

features a very high uniform neutron flux and high 

spatial resolution over area (Figure 3). The high 

neutron flux will allow attaining a time resolution of 

less than 1 second and a spatial resolution as low as 

10-30 mm with an appropriate neutron detector. 

Experimental tests of the facility have been 

performed in collaboration with various fuel cell 

Figure 1.	 Comparison of X-Ray Cross Sections to 

Neutron Cross Sections (The neutron cross 

section for hydrogen is much larger than the 

higher Z elements. The converse is true for 

x-ray cross sections.) 

Figure 2. New Neutron Imaging Facility Online at NIST 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Neutron Beam Size and Intensity 

Distribution (Beam diameter in the uniform 

region is about 18 cm.) 

Figure 4.	 (Top) Photo of the Graphite Flow Channels; 

(Bottom) Processed Neutron Image of the 

Water Formed During Operation of the Cell 

developers. The results of these tests are currently 

being evaluated for the design of future tests. 

Currently, the facility provides hydrogen (currently 

1.2 liters/minute), air and nitrogen gasses for users of 

the facility. Users are required to provide a fuel cell 

controller to match the fuel cell used in the facility. 

We shall incorporate a generic single cell fuel cell 

controller to the setup in the very near future. 

Results 

An example neutron image is shown in Figure 4. 

In the image, the gas distribution system of a fuel cell 

shows up as the serpentine race tracks. The purpose 

of these channels is to distribute gas evenly to the 

membrane and to act as a drain for water coming out. 

In these images, the neutrons easily penetrate the fuel 

cell when dry. As the fuel cell runs, water builds up 

and appears as a darker shadow region. Computer 

analysis, shown as the colorized (bottom) image in 

Figure 4, allows the dry cell to be removed, revealing 

only the water formation in both the flow channels 

and the gas diffusion media. In Figure 4, large 

amounts of water appear as red, and dry regions 

appear as black. 

At the imaging station, the largest fuel cell that 

can be imaged is about 20 cm x 20 cm. A sample of 

larger length can be imaged section by section 

through translation of the sample. The fuel cells also 

can be single-stack or multi-stack. The facility will 

operate as a user facility where proposals submitted 

will be required to be reviewed for merit before 

allocating beam time. A generic fuel cell test station 

will be available for general use, but users will be 

free to bring their own if needed. 

Conclusions 

•	 A neutron imaging facility now exists at NIST. 

-1 •	 High neutron flux of about 108 sec cm-2 has 

been achieved. 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 High spatial resolution of 20 μm - 200 μm has 

been achieved. 

•	 In-situ analysis of fuel cell water management 

using neutron imaging is now possible. 

•	 Near real time analysis of fuel cell operation is 

now possible. 

FY 2003 Publications/Presentations 

1. Invited talk at 'Plug Power', Albany, NY, March 

2002. 'Investigation of fuel cell water transport 

using thermal neutron imaging techniques.' 

2. Presentation at DOE fuel cell conference, Denver, 

CO, May 2002. 'High flux thermal neutron 

imaging station for fuel cell research.' 

3. Invited talk at Argonne National Laboratory, 

Argonne, IL, June 2002. 'Neutron imaging 

technique to determine diffusion co-efficient of Li 

ions in Li ion conductors.' 

4. Invited talk at Dupont, Wilmington, DE, February 

2003. 'NDE of fuel cell via neutron imaging.' 

5. "In-situ neutron imaging techniques for evaluation 

of water management systems in operating PEM 

fuel cells", Submitted to "Journal of Power 

Sources." 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Low-Friction Coatings and Materials for Fuel Cell Air Compressors 

George R. Fenske (Primary Contact), Oyelayo Ajayi, John Woodford, and Ali Erdemir 

Argonne National Laboratory 

9700 S. Cass Ave. 

Argonne, Illinois 60439 

Phone: (630) 252-5190; Fax: (630) 252-4798; E-mail: gfenske@anl.gov 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop and evaluate the friction and wear performance of low-friction coatings and materials for fuel cell 

air compressor/expander systems. Specific goals are: 

•	 50 to 75% reduction in friction coefficient 

•	 One-order-of-magnitude reduction in wear 

•	 Transfer of the developed technology to DOE industrial partners 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Compressors/Expanders 

Approach 

•	 Identify critical compressor components requiring low friction. 

•	 Apply Argonne's near-frictionless carbon (NFC) coatings to the components where appropriate and 

evaluate. 

•	 Develop polymer composite materials containing boric acid solid lubricant and evaluate. 

•	 Develop tribological mechanism-based material selection methodology for various compressor/ 

expander components. 

Accomplishments 

•	 Identified the radial air bearings and thrust bearings of Meruit’s turbocompressor as components that 

require both low friction and low wear rate for satisfactory performance. 

•	 Thrust washer wear tests showed that Argonne’s NFC coating reduced friction by about four times and 

wear rate by two orders of magnitude. Both exceeded the project goals. 

•	 NFC coatings increased the scuffing resistance of a steel surface about 10 times. 

•	 NFC-coated air bearing hardware components are currently undergoing durability testing. 

•	 Completed initial friction and wear testing of Nylon-12 polymer with B2O3 addition. Significant 

reduction in wear was observed with the addition of B2O3, especially under high relative humidity. 

•	 Achieved 50% reduction in friction for application in Variex-variable displacement compressor/ 

expander using Hitco C/C composite and anodized Al contact pairs. 

•	 Designed and constructed a new high-speed friction and wear test rig for evaluating materials for 

Mechanology’s torroidal intersecting vane machine (TIVM). 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Evaluated high-speed frictional performance of several candidate materials and coatings for TIVM 

vanes. 

Future Directions 

•	 Develop a tribology-based material selection methodology for compressor and blower components. 

•	 Compile a database of pertinent candidate material and coating properties. 

•	 Conduct a detailed tribological performance evaluation of TIVM select candidate materials based on 

high-speed frictional behavior. 

•	 Optimize NFC coating for TIVM vane application. 

•	 Coat TIVM components with optimized NFC for rig testing at Mechanology. 

•	 Initiate efforts to address tribological issues in AD Little and UTC Fuel Cells, Inc. compressor/ 

expander programs. 

Introduction 

A critical need in fuel cell systems for vehicles is 

an efficient, compact, and cost-effective air 

management system to pressurize the fuel cell 

systems to about 3 atmospheres. Pressurization of 

fuel cells will result in higher power density and 

lower cost. Because no off-the-shelf compressor 

technologies are available to meet the stringent 

requirements of fuel cell air management, several 

compressor and blower systems are currently being 

developed for DOE by different contractors. The 

efficiency, reliability and durability of compressors 

depend on effective lubrication or friction and wear 

reduction in critical components such as bearings and 

seals. Conventional oil or grease lubrication of 

compressor components is not desirable because 

such lubricants can contaminate and poison the fuel 

cell stack. The objective of this project is to develop 

and evaluate low-friction coatings and/or materials 

for critical components of air compressor/expanders 

being developed by various contractors for DOE 

vehicular fuel cell systems. The work this year 

focused on evaluation of materials and coatings for 

Mechanology's TIVM, as well as the development of 

generalized material selection methodology for 

compressor components. 

Approach 

For various air compressor/expanders being 

developed, we will identify the key critical 

components that require low friction coefficient and 

wear resistance. Over the years, the tribology group 

at Argonne has developed low-friction and low-wear 

coatings and materials. Most notable is the discovery 

of an amorphous carbon coating with extremely low 

friction coefficients (<0.001 in dry nitrogen) and 

very low wear. Where appropriate, the NFC coating 

will be applied to the critical component(s). Other 

commercially available low-friction coatings will be 

evaluated for various applications. In some cases, 

alternative low-friction polymeric materials and 

other low-friction coatings will be evaluated. 

Results 

Mechanology TIVM. The primary sources of 

friction in the TIVM are the vane sliding interface, 

the housing compressor seal and expander bearings. 

Design analysis shows that overall system friction 

coefficient less than 0.3 is required to meet the DOE 

program target for efficiency. The most critical of 

the three TIVM friction sources is the vane sliding 

interface because of its high sliding speed of 60-75 

m/s. Selection of appropriate vane material is critical 

for successful operation of the TIVM compressor/ 

expander. As reported last year, preliminary 

frictional behavior as a function of sliding speed was 

evaluated for several material and coating (including 

NFC) combinations. Some material combinations 

with adequate friction behavior at high sliding speeds 

were identified. 

More detailed tribological evaluations were 

conducted for potential TIVM vane materials. The 

three-ball-on-disc high speed test rig was refurbished 

to make it more robust. The normal and tangential 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

forces are now measured by a three-axes load cell 

(Figure 1). This will allow more accurate 

measurement of friction coefficient as the variation 

in the normal force is taken into account. The test rig 

is also now equipped with an environmental coated 

chamber, allowing the variation of relative humidity. 

Friction and wear tests were conducted as a function 

of sliding speed for candidate vane materials and 

coatings at ambient room relative humidity (~30% 

RH) and at 100% relative humidity. Figure 2 shows 

the variation of the friction coefficient with sliding 

speed for various materials and coatings meeting the 

friction requirement of 0.3 under ambient room air. 

The lowest friction coefficient was obtained when 

both the disc and the ball surfaces were coated with 

NFC. Steel on polyetheretherketone (PEEK) shows 

Figure 1.	 Picture of Modified High Speed Friction and 

Wear Test Rig With 3-Axes Load Cell and 

Environmental Chamber for Humidity 

Control 

 FY 2003 Progress Report 

friction coefficients less than 0.15 for the speed range 

evaluated. Under 100% relative humidity, the 

friction coefficients for all the materials evaluated 

were lowered (Figure 3). This may be due to 

hydrodynamic lubrication by the presence of water at 

the sliding interface. At the very high sliding speed, 

the friction coefficients for all material pairs were 

approaching the same value. This is consistent with 

the possibility of hydrodynamic lubrication by water. 

Figure 4 shows the wear on balls of various materials 

sliding on PEEK and NFC-coated discs. Minimal 

wear was observed on the balls sliding on PEEK, 

except for brass (Figure 4, top). Due to higher 

hardness of the NFC coating, it produced more wear 

on the balls slid against it (Figure 4, bottom). 

Conclusions 

More detailed friction and wear evaluation of 

candidate materials and coatings for Mechanology 

TIVM vanes showed that humid air will not have 

adverse effects on the friction behavior of these 

materials, at least for a short duration of time. LongFigure 2.	 Variation of Friction Coefficient with Sliding 

Speed for TIVM Vane Candidate Material 

and Coating Combinations in Ambient Room 

Air (30% RH) 

Figure 3.	 Variation of Friction Coefficient with Sliding 

Speed for TIVM Vane Candidate Materials 

and Coatings under 100% Relative Humidity 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

term effect of humidity must be assessed as part of FY 2003 Publications/Presentations 

future efforts. 

1. O. O. Ajayi, A. Erdemir, and G. R. Fenske, "Low 

A	 Friction Coatings and Materials for Fuel Cell 

Compressor & Blowers," 2003 Merit Review and 

Peer Evaluation Meeting, May 19-22, 2003. 

Berkeley, California. 

B 

Figure 4.	 Wear Volume in Various Balls Slid Against 

(top) PEEK Disc and (bottom) NFC-Coated 

Steel Disc 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Bipolar Plate-Supported Solid Oxide Fuel Cell 

Deborah Myers (Primary Contact), J. David Carter, James Ralph, Terry Cruse, Romesh Kumar 

Argonne National Laboratory 

9700 S. Cass Avenue 

Argonne, IL 60439-4837 

Phone: (630) 252-426; Fax: (630) 252-4176; E-mail: Myers@cmt.anl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Develop an improved solid oxide fuel cell (SOFC) for auxiliary power units (APUs). 

•	 Improve mechanical properties (i.e., vibration and shock resistance). 

•	 Improve cell power output by eliminating the contact resistance between cell and interconnect layers. 

•	 Reduce materials costs. 

•	 Develop a low-cost fabrication method. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

•	 M. Fuel Processor System Integration And Efficiency 

•	 O. Stack Material And Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

Approach 

•	 Support a SOFC on a metallic bipolar plate rather than a ceramic layer. 

•	 Reduce the thickness of the anode layer. 

•	 Fabricate cell components using powder metallurgy processing. 

•	 Sinter cell components in one high-temperature processing step. 

Accomplishments 

•	 Achieved sintered laminate of flow fields, bipolar plate, anode, and electrolyte. 

•	 Demonstrated that the bipolar plate-supported SOFC has four times the strength of an anodesupported cell. 

•	 Achieved an open-circuit voltage of 1.14 V (>99% of theoretical value). 

•	 Achieved a single-cell power output >260 mW/cm2. 

Future Directions 

•	 Design and fabricate a short stack (2 cells) to achieve an open-circuit potential that is >90% of the 

theoretical value on hydrogen/air. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Test two-cell stack on simulated reformate/air. 

• Test startup time, cyclability, and durability. 

• Investigate improved materials for the metallic support, anode, and cathode. 

• Improve fabrication procedure. 

• Collaborate with universities, industry, and other national laboratories. 

Introduction 

Solid oxide fuel cells (SOFCs) are attractive 

power sources for vehicular auxiliary power 

applications because they exhibit high power 

densities and efficiencies, have simplified fuelreforming requirements, and are fuel-flexible. 

However, their high operating temperature and the 

brittle nature of their ceramic cell components have 

precluded their use. SOFCs have traditionally been 

operated at ~1000°C because the cell support was a 

thick doped-zirconia electrolyte layer. Recently, the 

operating temperature has been lowered to 650­

800°C by supporting the cell on a thick ceramicmetal (cermet) anode layer and decreasing the 

thickness of the electrolyte layer to <20 μm, thus 

decreasing its resistance. The lower operating 

temperatures have made SOFCs more viable for 

transportation applications, allowing better thermal 

integration with the fuel reformer (operating at 

~700°C), the use of metallic flow fields and 

interconnects, and shorter startup times. However, 

there are still barriers to the use of SOFCs for these 

applications, including (1) susceptibility to cracking 

due to vibration, impact, and thermal shock; (2) 

contact resistance between the cell components; and 

(3) high materials and manufacturing costs. The bulk 

of the materials costs of the anode-supported SOFC 

lies in the large amount of zirconia in the thick anode 

support and the cost of expensive alloys in the 

bipolar plate. The use of a cermet layer to support 

the cell also makes the cell fragile and susceptible to 

damage by thermal shock. 

Approach 

Argonne researchers are developing a design 

concept, called the TuffCell, to address the issues 

facing the use of SOFCs in APU applications. The 

objective of the Argonne effort is to improve 

mechanical properties, eliminate contact resistance 

between the cell and interconnect layers, reduce 

materials costs, and use low-cost fabrication 

methods. In the TuffCell concept, the brittle 

electrolyte and anode layers are co-sintered with the 

metallic gas flow fields and bipolar plate, forming an 

integrated repeat unit for stacking. The metallic 

bipolar plate serves as the cell's support, which 

increases the mechanical strength and thermal 

cyclability of the cell. The bulk of the bipolar plate 

can be made of inexpensive stainless steels, with thin 

passivating layers at the surfaces exposed to the 

corrosive fuel and oxidant atmospheres. Materials 

costs are reduced by using thin layers of electrolyte, 

anode, and metal alloys on an inexpensive metallic 

support. In contrast to state-of-the-art SOFC 

fabrication, which includes several high-temperature 

sintering steps, this method uses a single-step powder 

metallurgy process carried out in a programmed 

atmosphere. Eliminating multiple high-temperature 

processing steps reduces fabrication costs. 

Each component layer of the cell is formed using 

tape-casting or slurry-coating methods and laminated 

with other components to form a single stack unit. 

Laminates containing the electrolyte, anode, fuel flow 

field, bipolar plate, and air flow field are sintered 

together in a controlled-atmosphere tube furnace. The 

cathode is applied and sintered in situ during the initial 

heating of the cell or stack. Figure 1 shows a 

schematic and photo of the TuffCell stacking unit. 

Results 

Several cells varying in thickness have been 

fabricated using the TuffCell approach. Figure 2 is a 

scanning electron micrograph of a laminate cross 

section prior to application of the cathode. This 

particular laminate consists of a 10-μm electrolyte, 

120-300-μm anode, 600-μm flow fields, and a 200­

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies

μm bipolar plate. All of the layers were well bonded, 

and the electrolyte and bipolar plate were gasimpermeable. The flow fields have 70-80% porosity, 

and the overall thickness of the laminate is 1.5 mm. 

Figure 3 illustrates the improvement in fracture 

strength of a bipolar plate-supported SOFC over a 

pre-reduced conventional anode-supported SOFC. 

The first inflection in the metal-supported SOFC 

curve marks the fracture of the electrolyte. Further 

displacement shows the effects of metal ductility. 

The anode-supported cells fracture in a brittle failure, 

showing one-quarter of the strength of the bipolar 

plate-supported SOFC. 

Figure 4 shows the improvements in single-cell 

polarization and power density achieved since the FY 

2002 Annual Report. These improvements were 

realized by improving the microstructure of the 

nickel-yttria-stabilized zirconia cermet anode to 

enhance the electrical conductivity (August 2002), 

and by using a doped-cobaltite cathode with a dopedFigure 1. Schematic and photograph of the bipolar 

plate-supported SOFC stacking unit. 

Figure 2.	 Scanning electron micrograph of a sintered 

bipolar plate-supported SOFC laminate. The 

laminate contains a dense electrolyte and 

bipolar plate as well as a porous anode and 

flow fields. The flow fields are continuously 

connected below the plane of the figure, 

achieving a well-bonded monolithic unit. 

 FY 2003 Progress Report 

ceria interlayer (November 2002) rather than the 

doped-ferrite cathode used in the past. 

One of the bipolar plate-supported cells was 

cycled between room temperature and 800°C at 

10°C/min to determine the tolerance of the cells to 

temperature cycling. Figure 5 shows that there is no 

degradation in the electrochemical performance of 

the cell after two temperature cycles (the test was 

terminated after two cycles). 

Figure 3.	 Load vs. displacement results of a 4-point 

bend test comparing the strength of the 

metal-supported SOFC with the conventional 

anode-supported SOFC. 

Figure 4.	 Improvement in the single-cell polarization 

and power density of the bipolar platesupported SOFC. Cells were tested at 

800°C with hydrogen anode gas and oxygen 

cathode gas. 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 5.	 Single-cell polarization curves after cycling 

the cell temperature between 800°C and 

room temperature at 10°C/min. The cell was 

tested at 800°C with hydrogen anode gas and 

air cathode gas. 

Conclusions 

A new design and fabrication concept is being 

developed for the SOFC to address the shortcomings 

of current designs for portable applications. The 

design supports the cell on a metallic bipolar plate, and 

fabrication uses ceramic and powder-metal processing 

to construct a monolithic unit bonding the flow fields, 

bipolar plate, anode, and electrolyte in one hightemperature sintering step. Results of four-point 

bending tests showed that the sintered laminates have 

four times the load-to-failure capabilities of 

conventional anode-supported cells. This means that 

handling and stacking these cells should be easier, and 

the stacks should be more mechanically robust. 

Single-cell electrochemical tests at 800°C on 

hydrogen and air achieved a power density of >250 

mW/cm2 . With proper refinements to the design and 

electrode layer compositions, significant 

improvements in the power density are expected. 

Future work will also focus on increasing the 

individual cell size; building short stacks of cells; 

testing these stacks using hydrogen and simulated 

reformate; and determining start-up time, the ability 

to cycle the temperature, and cell durability. The 

ultimate goal of this research is to develop rugged, 

high power density, low-cost stack units made by a 

commercially viable manufacturing process. 

FY 2003 Publications/Presentations 

1. T. A. Cruse, J.-M. Bae, J. D. Carter, R. Kumar, 

and M. Krumpelt, "A Novel Approach to Making 

Metallic Interconnects for Planar Solid Oxide 

Fuel Cells," 2002 Fuel Cell Seminar, Palm 

Springs, CA (2002). 

2. J. D. Carter, J. M. Ralph, J.-M. Bae, T. A. Cruse, 

C. Rossignol, M. Krumpelt, and R. Kumar, 

"Improved Materials and Cell Design for 

Mechanically Robust Solid Oxide Fuel Cells," 

2002 Fuel Cell Seminar, Palm Springs, CA 

(2002). 

3. J. D. Carter, T. A. Cruse, J.-M. Bae, J. M. Ralph, 

D. J. Myers, M. Krumpelt, and R. Kumar, 

"Bipolar Plate-Supported Solid Oxide Fuel Cells 

for Auxiliary Power Units," Mater. Res. Soc. Fall 

2002 National Meeting, Boston, MA (2002). 

4. J. D. Carter, T. A. Cruse, J.-M. Bae, J. M. Ralph, 

C. Rossignol, D. J. Myers, R. Kumar, and M. 

Krumpelt, "Application of Cathode Materials to 

Co-Sintered Metal Supported SOFC," American 

Ceramic Society 105th Annual Meeting, 

Nashville, TN (2003). 

5. J. D. Carter, T. A. Cruse, J. M. Ralph, and D. J. 

Myers, "Powder Metallurgy and Solid Oxide Fuel 

Cells," 2003 International Conference on Powder 

Metallurgy and Particulate Materials, Las Vegas, 

NV (2003). 

Special Recognitions & Awards/Patents 

Issued 

1. J. D. Carter, J.-M. Bae, T. Cruse, J. M. Ralph, R. 

Kumar, and M. Krumpelt, "Solid Oxide Fuel Cell 

with Improved Mechanical and Electrical 

Properties" (2002). 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Assessment of Fuel Cell Auxiliary Power Systems for On-Road Transportation 

Applications 

Masha Stratonova, Stephen Lasher (Primary Contact), Eric Carlson 

TIAX LLC 

15 Acorn Park 

Cambridge, MA 02140 

Phone: (617) 498-6108; Fax: (617) 498-7054; E-mail: lasher.stephen@tiax.biz 

DOE Technology Development Manager: John Garbak 

Phone: (202) 586-1723; Fax: (202) 586-9811; E-mail: John.Garbak@ee.doe.gov 

Subcontractors: Dr. C.J. Brodrick and Dr. Harry A. Dwyer, Institute of Transportation Studies, 

University of California, Davis, CA; Mr. William Gouse, III, American Trucking Association, 

Alexandria, VA 

Objectives 

•	 Assess the viability of the use of proton exchange membrane fuel cells (PEMFCs) and solid oxide fuel 

cells (SOFCs) as auxiliary power units (APUs) for on-road vehicles. 

•	 Identify major technical issues and key risk areas and determine research and development (R&D) 

needs and possible DOE roles. 

•	 Project potential fuel cell APU benefits to the nation. 

•	 Assess how fuel cell APUs may accelerate market introduction of fuel cells for propulsion and hybrid 

transportation applications. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

Approach 

•	 Determine PEMFC and SOFC performance parameters. 

•	 Identify and select three promising near-term and future fuel cell APU applications. 

•	 Develop design concepts and evaluate benefits and cost impacts for the three selected APUs. 

•	 Perform an R&D gap analysis, determining gaps among fuel cell cost and technical performance/ 

market needs. 

Accomplishments 

•	 Identified direct hydrogen PEMFCs as the most attractive near-term fuel cell technology and dieselfueled partial oxidation (POX) fuel processor with planar anode-supported SOFCs as the most 

attractive longer-term fuel cell technology for on-road transportation APU applications. 

•	 Characterized fuel cell/APU applications including medium- and heavy-duty trucks and light-duty 

vehicles. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Solicited data and feedback for promising APU applications and completed inventory of data gaps 

(e.g. capacity, fuel capability, duty cycle). 

•	 Selected three APU applications for conceptual design and vehicle integration analysis including 

diesel-fueled POX/SOFC APUs for long-haul trucks and transit buses, and direct hydrogen PEMFC 

APUs for law enforcement vehicles. 

•	 Estimated APU versus idling engine efficiency and emissions at rated power and part load for the three 

selected applications. 

•	 Projected annual fuel and emissions savings using fuel cell APUs in three selected applications. 

Future Directions 

•	 Evaluate the benefits of a truck refrigeration unit (TRU) and perform a detailed analysis if appropriate. 

•	 Finalize vehicle integration layouts and cost analysis for three fuel cell APU systems. 

•	 Finalize comparisons of conceptual systems with competing technologies. 

•	 Determine R&D gaps among fuel cell cost and technical performance/market needs. 

Introduction 

Over the last five years, interest in the use of fuel 

cells for auxiliary power units (APUs) in vehicles has 

risen, particularly for truck idling and truck 

refrigeration unit (TRU) applications, driven by 

increasingly stringent idling and TRU regulations. 

Fuel cell powered APUs have the potential to reduce 

emissions, noise, vibration, fuel consumption, and 

size relative to conventional, internal combustion 

engine (ICE) APUs. In this work, the DOE has 

commissioned TIAX to assess the viability of the use 

of proton exchange membrane fuel cells and solid 

oxide fuel cells as APUs for on-road vehicles. 

Approach 

After determining the fuel cell APU performance 

parameters, we selected three promising fuel cell 

APU applications, developed conceptual designs, 

and assessed the potential benefits of the systems. 

We concentrated on PEMFC and SOFC technologies 

and applications likely to be attractive at the present 

time and extending to 2010. We addressed 

applications that use the existing fuel infrastructure 

(namely gasoline and petroleum diesel), alternative 

fuels (e.g. propane), and future fuels (hydrogen). We 

considered passenger cars, class 1 and 2 light-duty 

trucks and sport utility vehicles (SUVs), class 3-8 

trucks, recreational vehicles, transit buses, and 

specialized vehicle applications. Military 

applications are not part of the current scope of work. 

The project involves five tasks: project kick-off, 

identification and selection of APU systems, 

development of design concepts and evaluation of 

potential benefits, analysis of R&D gaps, and 

analysis update after delivery of the draft final report. 

Results 

The key factors that influence fuel cell APU 

technology selection are cost, weight (i.e. power 

density), efficiency, and system volume. Other 

important factors are technology maturity, fuel 

capability/flexibility (and associated complexity of a 

fuel reformer), startup time, and fuel cell stack life. 

A high-level ranking showed that direct hydrogen 

PEMFC was the most attractive near-term 

technology and diesel-fueled partial oxidation (POX) 

fuel processor with planar anode-supported SOFC 

was the most attractive longer-term technology for 

fuel cell APUs. 

Two types of screens were used to identify three 

applications for detailed analysis. The initial 

screening criteria focused on application 

characteristics: 

•	 Duty cycle - vehicle accessory duty cycle (i.e. 

load profile) should be suited to APU use (e.g. 

hotel loads during idle times) 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

•	 Market size - market potential must be adequate 

to support investment in APU technology 

•	 Vehicle cost - initial vehicle cost must be high 

enough that an APU would likely represent a relatively small portion (<15 %) of the total cost 

The second screening criteria focused on both 

the short- and long-term benefits related to: 

•	 Energy savings 

•	 Emissions savings 

•	 Cost savings 

•	 Acceleration of fuel cell technology commercialization 

Vehicle applications meeting both screening 

criteria were long-haul truck cabs, transit buses, and 

law enforcement vehicles. Both long-haul trucks and 

the transit bus applications are attractive longer-term 

SOFC APU applications because they have potential 

to reduce fuel use and emissions significantly at 

relatively modest additional capital cost. As 

designed, both the truck and bus APU applications 

process the on-board diesel fuel in a POX reformer to 

generate fuel for the SOFC. Law enforcement 

vehicles are an attractive near-term PEMFC APU 

application because they are often centrally refueled 

and maintained by a fleet operator, mitigating 

alternative fuel infrastructure problems. They have 

the potential to accelerate fuel cell introduction by 

employing direct hydrogen fueling and storage, as 

well as to reduce fuel use and emissions. Law 

enforcement vehicles are also attractive because of 

their relatively low cargo needs, leaving space 

available for compressed hydrogen fuel tanks. For 

the purposes of this analysis, we assume the law 

enforcement vehicle has a hydrogen ICE powertrain 

and a direct hydrogen PEMFC APU. 

Accessory duty cycle and fuel cell system 

efficiency are used in a modified drive cycle model 

to estimate fuel consumption, emissions, and fuel cell 

sizing for the APU. Figure 1 illustrates the 

conceptual framework of the modified ADVISOR 

drive cycle model. Representative vehicle duty 

cycle(s), fuel cell performance data, and enginespecific emissions and fuel consumption maps are 

input, and fuel and emissions estimates are output. 

Long-Haul Truck Cab. The accessory duty cycle 

for a long-haul truck sleeper cab was estimated using 

 FY 2003 Progress Report 

industry-supplied data. The fuel cell system energy 

conversion efficiency was determined at various 

loads and design capacities using detailed 

thermodynamic and fuel cell performance models. 

The SOFC stack part load efficiency was optimized 

by choosing the appropriate combination of cell 

voltage and fuel utilization at each point (TIAX, 

2002). The analysis shows that there is not a large 

difference in efficiency with rated capacity in the 

range of 5 to 9 kW, especially near full load (see 

Figure 2). Using the accessory duty cycle and fuel 

cell system efficiencies in the modified drive cycle 

model, a 4-kW APU system was found to minimize 

fuel consumption. Estimated annual fuel savings and 

Figure 1. Conceptual Framework of ADVISOR-based 

Vehicle System Model 

Figure 2. SOFC System Efficiency as a Function of 

Load 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

emissions benefits per truck are shown on Figure 3 

for a 4-kW SOFC APU. Savings will depend on 

engine idling speed, or rotations per minute (rpms), 

which in turn depends on the engine design. Savings 

will also depend on the duty cycle, which varies over 

a wide range. Approximately 15-20% of the market 

idles <2 hours/day, 60-70% idles 2-10 hours/day, and 

15-20% idles >10 hours/day. 

Transit Bus. The accessory duty for transit buses 

was estimated to be 11 kW to run the air conditioner 

(A/C) in warm weather operation and a 3-kW 

baseload to run other accessories all the time. We 

evaluated two cases, one where the APU supplies 

power for the baseload only (3 kW), and one where it 

supplies both the baseload and A/C load (14 kW). 

The fuel cell system energy conversion efficiency 

was similar to the truck cab application. Estimated 

fuel savings and emissions benefits per bus are 

shown on Figure 4 for a 14-kW SOFC APU. Fuel 

savings are negative (i.e. more fuel is consumed) for 

Figure 3. SOFC APU Annual Diesel Fuel and 

Emissions Savings - Long-Haul Truck Cab 

 FY 2003 Progress Report 

the transit bus APU application because it is never 

practical to turn off the main engine during normal 

stop and go operation. Since engine idling is 

required in the typical drive cycle, it is more efficient 

to use the engine to supply all accessory power. 

While the SOFC is more efficient than the ICE, 

idling the ICE with no load plus operating the APU is 

less efficient than idling the engine to supply 3-14 

kW of accessory power with no APU. Annual 

emissions are reduced only slightly. 

Law Enforcement Vehicle. The accessory duty 

cycle for law enforcement vehicles was developed 

from a survey of police fleet operators. An APU for 

this application would require up to 5 kW for lights, 

radio, etc. during idling situations (e.g. traffic 

surveillance). The fuel cell system energy 

conversion efficiency was determined at various 

loads using detailed thermodynamic and fuel cell 

performance models (see Figure 5). The PEMFC 

system pressure and stack cell voltage are assumed to 

Figure 4. SOFC APU Diesel Fuel and Emissions 

Savings - Transit Bus 

Figure 5. Direct Hydrogen PEMFC Efficiency as a 

Function of Load 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 6. Direct Hydrogen PEMFC APU Annual Fuel 

Savings - Law Enforcement Vehicle 

vary with load (pressure decreases and cell voltage 

increases at lower load). Estimated annual fuel 

savings per vehicle are shown in Figure 6 for a 5-kW 

PEMFC APU. Savings will depend on idling time, 

which varies significantly. Emissions savings were 

not evaluated because it is assumed that the engine 

utilizes clean-burning hydrogen (i.e. hydrogen ICE 

powertrain). 

Conclusions 

Introduction of APUs for long-haul truck and 

law enforcement vehicle applications can provide 

significant fuel and emissions savings proportional to 

the amount of abated idling time. Transit bus 

applications, however, are unlikely to result in 

significant benefits due to the necessity for engine 

idling even with an APU. In place of a detailed 

vehicle integration and cost analysis of the transit bus 

application, we will instead evaluate the benefits of a 

TRU and perform a detailed analysis if appropriate. 

References 

1. TIAX, “Grid-Independent, Residential Fuel-Cell 

Concept Design and Cost Estimate”, Final Report 

to DOE NETL in Subcontract to Parsons, 

Subcontract Number 73622-30005, October 18, 

2002 

FY 2003 Publications/Presentations 

1. Presentation to 21st Century Truck Industrial 

Working Group in conjunction with SAE 

Government & Industry meeting, Washington, 

DC, May 15, 2002 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Evaluation of Partial Oxidation Fuel Cell Reformer Emissions 

Stefan Unnasch (Primary Contact), Scott Fable
 

TIAX LLC
 

1601 S. De Anza Blvd., Suite 100
 

Cupertino, CA 95014
 

Phone: (408) 517-1563; Fax: (408) 517-1553; E-mail: unnasch.stefan@tiax.biz
 

DOE Technology Development Managers: 

Nancy Garland: Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov
 

Kathi Epping: Phone: (202) 586-7425; Fax: (202) 586-9811; E-mail: Kathi.Epping@ee.doe.gov
 

ANL Technical Advisor: 

Walter Podolski: Phone: (630) 252-7558; Fax: (630) 972-4430; E-mail: podolski@cmt.anl.gov
 

Objectives 

•	 Measure the emissions from a partial oxidation/autothermal reformer (POx/ATR) fuel processor for a 

proton exchange membrane fuel cell (PEMFC) system under both cold-start and normal operating 

conditions 

•	 Assess the feasibility of meeting emissions standards for automobiles and light-duty trucks through the 

use of a fuel cell vehicle with a flexible-fuel reformer 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 K. Emissions and Environmental Issues 

Approach 

•	 Define a representative test cycle consisting of both startup and normal operating conditions 

•	 Use the established test cycle to quantify emissions from a POx reformer before and after anode gas 

burner (AGB) treatment 

•	 Measure emissions with continuous emissions monitoring (CEM) measurements supplemented with 

laboratory analyses of speciated hydrocarbons and particulate matter (PM) 

•	 Use reasonable approximations and estimates to convert emissions data from a grams/unit fuel basis to 

a predicted grams/mile basis 

Accomplishments 

•	 Measured emissions from a gasoline-fed fuel processor (without fuel cell) over several operating 

conditions 

•	 Measured emissions from an ethanol-fed fuel processor with fuel cell over several operating
 

conditions (analysis pending)
 

•	 Speciated total hydrocarbon (THC) data before and after the AGB 

•	 Assessed the sensitivity of monitoring equipment over a range of operating conditions 

•	 Analyzed data to report emissions on a g/kg fuel basis 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Perform extensive emissions testing of a fuel cell/reformer system to include particulate, 

formaldehyde, and ammonia as well as NOx, hydrocarbons, and CO 

•	 Sample and analyze emissions from Nuvera Fuel Cells fuel processor-fuel cell system in 2003 

•	 Project on-road emissions from fuel cell vehicles with on-board reformers 

Introduction 

Fuel reformer operation is generally divided into 

two operating modes: startup and normal partial 

oxidation. During startup, the fuel processor burns 

fuel at near stoichiometric conditions until critical 

system temperatures and pressures stabilize to target 

values. Once the target conditions are reached, the 

reformer operates in normal mode in which the fuel 

processor burns fuel at very rich conditions. Since 

these modes are comprised of considerably different 

operating conditions, it follows that the emissions 

associated with each of these modes are also 

considerably different. 

The combustor is typically cold under startup 

conditions, generating emissions during this brief 

period (target times are under 30 seconds) that can be 

substantially higher than those produced during the 

remaining, much longer portion of the driving cycle. 

The pollutant emissions produced during startup 

operation include NOx, CO, formaldehyde, and 

organic compounds. These organic compounds, 

including hydrocarbons, alcohols, and aldehydes, are 

regulated in California and referred to as nonmethane organic gases (NMOG). Under normal, fuel 

rich operating conditions, virtually no NOx is 

formed, although the formation of ammonia is 

possible. Most hydrocarbons are converted to carbon 

dioxide (or methane and/or hydrogen if the reaction 

is incomplete); however, trace levels of hydrocarbons 

can pass through the fuel processor and fuel cell. 

The shift reactors and the preferential oxidation 

(PrOx) reactor reduce CO in the product gas, with 

further reduction in the fuel cell. Thus, of the criteria 

pollutants (NOx, CO, and hydrocarbons [NMOG]), 

NOx and CO levels are generally well below the 

most aggressive standards. NMOG concentrations, 

however, can exceed emissions goals if these are not 

efficiently eliminated in the catalytic burner. 

Approach 

In this study, a gasoline fuel processor and an 

ethanol fuel processor were operated under 

conditions simulating both startup and normal 

operation. Emissions were measured before and 

after the AGB in order to quantify the effectiveness 

of the burner catalyst in controlling emissions. The 

emissions sampling system includes CEM for O2, 

CO2, CO, NOx, and THC. Also, integrated gas 

samples are collected in evacuated canisters for 

hydrocarbon speciation analysis via gas 

chromatography (GC). This analysis yields the 

concentrations of the hydrocarbon species required 

for the California NMOG calculation. The PM 

concentration in the anode burner exhaust is 

measured through the placement of a filter in the 

exhaust stream. 

Emissions data will be used to project on-road 

emissions for fuel cell vehicles with reformers. 

Emissions data will be characterized in terms of 

startup or reforming modes. Although current fuel 

processor technologies are not configured to follow a 

typical vehicle load profile, hybrid vehicle power 

management strategies may facilitate using such fuel 

processors. For this project, the fuel processor is 

operated at several steady-state points while 

emissions are monitored for the steady-state 

conditions and transients between load changes. The 

data collected during startup, different loads, and 

transients serve as inputs to a vehicle emissions 

model. Using these data, this vehicle emissions 

model then predicts the emissions for each second in 

a driving cycle based on load. Startup emissions are 

considered along with the total driving emissions. 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Results 

During FY 2003, we performed two series of 

emissions tests: one gasoline ATR system tested 

without a fuel cell and one ethanol ATR system 

tested with a fuel cell. The emissions tests involved 

sampling criteria pollutants and CO2 from each of 

these systems at various operational load points, as 

described in the previous section. Concentrations of 

the aforementioned species are obtained using the 

emissions sampling system shown in Figure 1. 

Although emissions data have been collected for both 

the gasoline and ethanol systems, only the gasoline 

system data have been sufficiently analyzed to allow 

presentation of results at this time. 

Figure 1. Emissions Testing Setup for the Fuel 

Processor and Fuel Cell System 

 FY 2003 Progress Report 

In general, testing did not attempt to follow a 

vehicle driving cycle, but rather followed a series of 

steady-state conditions with load changes. Figure 2 

shows emissions levels at the AGB for the beginning 

of a gasoline reformer testing series. This series of 

operating load points was started at low load 

conditions after a hot start (about 6 kWe or 12% load) 

and brought to steady state at 12 kWe. THC 

emissions at the AGB outlet were below the monitor 

detection limit throughout the testing period. CO 

emissions were highest at the lower load points and 

dropped when the power was increased above 10 

kWe, or 20% full power. NOx emissions stabilized at 

about 20 ppm for operation above 10 kWe. 

In order to determine how current emissions 

performance would compare to existing vehicle 

standards, these emissions levels were converted to a 

gram per mile basis using the system power input and 

typical vehicle efficiencies. The results of this 

conversion are given in Figure 3 along with the 

corresponding California super ultra low emission 

vehicle (SULEV) passenger vehicle standards. For the 

series shown in Figure 2, CO and THC emissions are 

much lower than the SULEV standard. For the same 

test series, the NOx emissions are on the same order of 

magnitude as the SULEV standard, indicating that the 

reformer system may require additional optimization 

to meet the SULEV NOx standard. 

The PM concentrations for both tests correspond 

to emissions levels below California SULEV vehicle 

emissions standards. These PM concentrations were 

determined by passing the entire exhaust stream 

Figure 2. CEM Emissions Test Results at the AGB 

Outlet (partial) 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 3. Projected Vehicle Emissions at the AGB 

Outlet (unoptimized) 

Figure 4. PM Emissions Results at the AGB Outlet 

 FY 2003 Progress Report 

through the PM filter and averaging the integrated PM 

sample over the total flow that passed through the 

filter. Figure 4 shows PM concentrations at the AGB 

determined for steady-state gasoline ATR system 

operation and the corresponding SULEV standard. 

Conclusions 

The combustion of reformer products at the AGB 

did not represent an optimized fuel cell vehicle 

configuration. Even with these limitations, the 

following conclusions can be drawn from the data. 

• NO	 x emissions from an AGB averaged about 20 

ppm for the load points tested. These emissions 

levels would correspond to approximately 0.05 

g/mile of NOx for operation. In order to meet 

stringent emissions standards, further 

optimization will be required. Also, other power 

loads will need to be tested to ensure that 

emissions are acceptable for all operating modes. 

•	 In-use THC and CO emissions were under 0.2 

ppm and 3 ppm, respectively, which would 

correspond to on-road emissions well below the 

SULEV standards. More data on startup with an 

optimized fuel processor is required before 

startup on-road NMOG and CO emissions can be 

estimated. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Modeling and Control of a Solid Oxide Fuel Cell Auxiliary Power Unit 

Mohammad A. Khaleel (Primary Contact), Stewart J. Moorehead, Brian J. Koeppel, Ba Nghiep 

Nguyen 

Pacific Northwest National Laboratory 

P.O. Box 999, MS K2-18 

Richland, WA 99352 

Phone: (509) 375-2438; Fax: (509) 475-6605; E-mail: moe.khaleel@pnl.gov 

DOE Technology Development Manager: John A. Garbak 

Phone: (202) 586-1723; Fax: (202) 586-9811; E-mail: John.Garbak@ee.doe.gov 

Objectives 

• Task 1: 	 Develop a dynamic system model of a solid oxide fuel cell (SOFC) based auxiliary power unit 

(APU) and design a system controller to minimize diesel fuel consumption, maximize operating 

lifetime and satisfy electrical load requirements for Class VIII truck applications. 

• Task 2: 	 Develop analytical models and perform testing to determine the dynamic structural response 

and vibrational limits of SOFC-based APU systems in a Class VIII truck operational environment. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 C. Thermal Management 

•	 D. Fuel Cell Power System Benchmarking 

•	 H. Startup Time 

•	 P. Durability 

Approach 

Task 1 

•	 Create a dynamic, electro-chemical model of the SOFC stack. 

•	 Create dynamic balance of plant component, operational models using theoretical first principles and 

experimental data. 

•	 Create a system functionality model by combining component models. 

•	 Design controllers using the model to optimize fuel efficiency and lifespan. 

•	 Verify models through experimental testing and collaboration. Collect actual Class VIII truck
 

electrical load profiles with PACCAR and test APU systems with Delphi.
 

Task 2 

•	 Develop a lumped parameter model to determine the vibration amplitude of the SOFC stack due to 

base excitation of the APU. 

•	 Perform stress analysis on a detailed finite element model of a multiple-cell planar SOFC stack using 

the stack loading history. 

•	 Develop failure models for Positive-Electrolyte-Negative (PEN) cell fracture and seal interfacial 

separation to define APU vibrational limits and isolation requirements for stack durability. 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Collect data in collaboration with PACCAR for actual vibration loads of a truck-mounted APU. 

•	 Perform dynamic testing of an APU and components for fundamental material data and model 

validation. 

Accomplishments 

Task 1 

•	 Creation of APU system and component models: electro-chemical model of the SOFC stack, diesel 

fuel reformer, exhaust gas combustor and heat exchangers. 

•	 Completion of a dynamic model of a truck heating and air-conditioning system, including inrush 

current at startup and driver heat input. 

•	 Assembly of controllers to regulate cathode air temperature during heat-up phase to prevent thermal 

shock to SOFC and fuel flow rate control under varying electrical load. 

Task 2 

•	 Reviewed standards for shock and vibration testing and electronic equipment design for heavy trucks 

to establish a basis for the dynamic loading environment. 

•	 Created lumped parameter model in ANSYS to determine influence of APU components on stack 

dynamic response. 

•	 Detailed finite element model of SOFC stack to determine resonant frequencies and dynamic stresses 

due to harmonic excitation. 

•	 Identified method to define a vibrational limit spectrum to prevent stack failure. 

Future Directions 

Task 1 

•	 Create high level, optimized controllers to maximize fuel efficiency and device lifespan. 

•	 Improve dynamic models. Focus on the SOFC stack response to dynamic inputs (such as fuel flow 

rate changes and temperature changes) through collection of experimental data on single cell SOFCs. 

•	 Model un-measurable inner parameters of SOFC stack. 

•	 Improve power conversion electronics modeling through collaboration with University of Illinois, 

Chicago. 

•	 Collect actual electrical system load profiles in Class VIII trucks with PACCAR. 

•	 Test realism of control strategies for APU system in partnership with Delphi. 

Task 2 

•	 Complete failure model development for PEN fracture and interfacial separation. 

•	 Incorporate spectral solution methods. 

•	 Develop procedure to analyze shock and impact loading of the APU. 

•	 Perform parametric analysis for various SOFC and APU designs. 

•	 Collect actual truck shock and vibration data in collaboration with PACCAR. 

•	 Determine fundamental properties for cell materials under dynamic loading. 

•	 Perform experimental testing of SOFC and APU components in collaboration with Delphi. 

2 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

Long-haul trucks require electrical power to 

operate hotel loads (lights, heating/air conditioning 

and televisions) while parked for the operator to rest. 

Typically, these loads are powered by idling the 

engine or, less commonly, with a dedicated diesel 

generator based auxiliary power unit (APU). Fuel 

cell based APUs hold the promise of greater energy 

efficiency, lower operating costs, lower emissions, 

and quiet operation. A solid oxide fuel cell (SOFC) 

is expected to be the choice for transportation 

applications because 1) it has higher power density 

than other designs to minimize stack mass and 

volume and 2) it offers fuel flexibility due to its high 

operation temperatures and toleration of impurities. 

This project looks at modeling of SOFC APUs to 

understand how design choices impact efficiency and 

durability. This work is the first step towards full 

electrification of the truck when the engine is used 

solely for propulsion and today's belt driven pumps 

and fans are run off electricity from the APU. Task 1 

investigates operational models of APU components 

and the entire system to show how the devices 

interact, and different configurations are investigated 

for increased fuel efficiency. The operational models 

allow the creation of effective control strategies to 

optimize fuel efficiency and long lifespan. Task 2 

provides modeling tools to evaluate the dynamic 

thermal-mechanical stresses in the stack. The high 

temperature and dissimilar materials make SOFC 

structural robustness challenging when it must also 

withstand the rigorous dynamic loading of a heavy 

truck. The models will allow designers to define 

appropriate materials, cell design, physical layout, 

and isolation components to minimize vibrational 

loads to acceptable levels for increased durability in 

real applications. 

are created in a modular environment that allows 

them to easily be connected in different 

configurations. This allows different fuel and 

thermal management strategies to be tested. Work on 

the controller has begun, with independent control of 

individual components. This will be followed by 

higher level controllers, coordinating all components 

and increasing fuel efficiency. Finally, as the model 

matures, it will be possible to optimize control to 

minimize fuel consumption, maximize lifespan and 

meet electrical load requirements. 

Task 2: The commercial finite element code 

ANSYS was used to model the APU system response 

at three levels. For the first model, the APU was 

simplified to a small number of major components. 

Based on mass and stiffness properties of the 

components and connections, the dynamic loading 

imparted to the stack due to base excitation of the 

APU could be calculated across the frequency range 

of interest. This was used as input to a detailed 

model of the SOFC stack, which computes the 

deformation and stresses of the cells due to harmonic 

excitation. Stress analysis results can be compared to 

strength of the constituent materials to determine 

allowable excitation amplitudes. Fracture must be 

considered for brittle materials like the ceramic PEN 

and rigid seals. Finite element models to study anode 

cracks and interfacial seal separation are under 

development and will be similarly used to determine 

allowable excitation amplitudes. Parametric analysis 

will then be performed to identify critical elements in 

APU and stack design. Collection of actual 

excitation loads and experimentally testing of the 

SOFC components and APU will benchmark the 

models to ensure they are usable in real truck and 

transportation applications. 

Results 

Approach 

Task 1: The approach to creating operational models 

of the APU components and system has been to 

combine theoretical operation with experimental 

data, keeping the models broadly applicable but 

realistic. Electrical load profiles from Class VIII 

trucks will be collected with PACCAR to understand 

how APUs are used in practice. Models for 

components such as the diesel partial oxidation 

(POX) reformer, heat exchangers and SOFC stack 

The scope of this research project is to create 

models and controllers that provide design guidelines 

for SOFC-based APU applications. The models 

provide information about what conditions the SOFC 

APU will be subject to in operation and how it 

behaves. Models and controls are verified and 

augmented through experimental testing. 

Task 1: To date, this research has produced 

operational models of the following APU 

components: POX reformers (both diesel and 

3 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

gasoline), combustor, heat exchangers and the SOFC 

stack. These models compute the chemical and 

thermal reactions inside each component. An 

example of the voltage-current (VI) output of the 

SOFC model for various stack temperatures is shown 

in Figure 1. Models of electrical loads such as the 

heating and air-conditioning system have also been 

created. These models have been connected to form 

a complete system for simulation of operations. 

Using the component models, initial controllers 

have been developed. Currently, control is divided 

into two phases: startup and operating. The startup 

controller regulates the temperature of air blown over 

the stack to heat it to operating temperatures (around 

700°C). The rate of temperature increase must be 

strictly regulated to prevent undue thermal stress to 

the stack that would shorten its operational lifespan. 

The operating controller ensures that sufficient fuel is 

reaching the stack to produce enough electricity to 

match the electrical load. As electrical load 

requirements decrease, fuel flow to the stack should 

also decrease, preventing waste and increasing fuel 

efficiency. An example of this controller is shown in 

Figure 2. 

Task 2: Work for this year is exclusive to predictive 

model development and study of dynamic loading 

effects. Modal results for a planar stack indicate the 

fundamental frequency is due to out-of-plane 

vibration of the frame-supported PEN and the 

Figure 1. SOFC Voltage-Current Curves for Various 

Temperatures 

 FY 2003 Progress Report 

interconnect plate, depending on the interconnect 

stiffness as shown in Figure 3. Fundamental 

frequencies from thin plate theory and modal results 

for a stack model are shown in Figure 4, and they are 

much greater than typical engine speeds of 700-2100 

rpm (12-35 Hz). An example curve for the 

permissible harmonic excitation of a five-cell stack is 

shown in Figure 5. Superposition of the elastic 

solutions for thermal-mechanical and dynamic 

stresses was used to predict the maximum amplitude 

based on a single criterion that the Mode I stress 

intensity factor for a 5 or 25 mm semicircular flaw at 

the anode surface be less than a critical stress 

intensity of 1.0 MPa-m1/2. The results indicate that 

a stack vibration of 1-4 G's can be critical, although 

this assumes that the flaw is at the location of 

maximum stress. The union of all potential failure 

Figure 2. Fuel Flow Rate Response to Electrical 

Current Change 

Figure 3. Variation of PEN Fundamental Frequency 

with Interconnect Stiffness 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 4.	 Fundamental Frequencies for SOFC 

Components from Thin Plate Theory and 

Modal Analysis 

Figure 5.	 Permissible Longitudinal and Lateral 

Vibration Amplitudes for a Planar SOFC 

Stack 

criteria with consideration of defect density would 

define the actual critical response curve. Interfacial 

separation of the PEN and seals is expected to be an 

important failure mechanism due to coefficient of 

thermal expansion mismatches. Interfacial fracture 

of dissimilar materials is inherently mixed mode 

(Mode I and Mode II are coupled), and stress 

intensity factors depend on material properties which 

depend on anode porosity and nickel content. 

Relations to determine elastic properties and stress 

intensity factors as a function of porosity and 

composition have been developed using the MoriTanaka method as shown in Figure 6 for the 

properties of the NiO/YSZ anode. 

Conclusions 

• Task 1: 	 State-of-the-art models of an SOFC APU 

system and components were developed to 

describe the operational behavior of the APU. 

The models were used to develop controllers to 

Figure 6.	 Comparison of Model and Experimental 

Results for Elastic Moduli of the NiO/YSZ 

Anode as a Function of Porosity 

regulate fuel utilization under varying electrical 

loads and prevent thermal shock during heat up. 

Performance will be improved by creating higher 

level, optimized controllers and incorporating the 

results of experimental tests on single cell SOFC 

and APU systems in partnership with Delphi. 

Electrical load use profiles will be collected from 

real trucks with PACCAR, and detailed power 

electronic models will be made with University 

of Illinois, Chicago. Further models to describe 

full truck electrification will be done in 

collaboration with an engine manufacturer such 

as Caterpillar. 

• Task 2: 	 Finite element models constructed for 

dynamic analysis of a lumped parameter APU 

system and stress analysis of a detailed SOFC 

stack were used with a simple failure criterion to 

predict permissible vibration load as a function 

of frequency. For the future, continued 

improvement of the finite element analysis and 

failure models will provide wider applicability, 

truck dynamic loads will be determined with 

PACCAR to ensure realistic loading conditions, 

and APU/SOFC component testing will be done 

with Delphi to validate modeling efforts. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

FY 2003 Publications/Presentations 

1. M.A. Khaleel, B.J. Koeppel, and S.J. 

Moorehead, "Solid Oxide Fuel Cell Auxiliary 

Power Units for Long-Haul Trucks: Modeling 

and Control", Hydrogen, Fuel Cells & 

Infrastructure Technologies Program 2003 Merit 

Review and Peer Evaluation Meeting, Berkeley, 

CA (2003). Poster No. 96. 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Montana PEM Membrane Degradation Study, Year 1 Report 

Dan Stevenson (Primary Contact) 

CTA 

1500 Poly Drive, PO Box 1439 

Billings, MT 59103 

Phone: (406) 248-7455; Fax: (406) 248-3779; E-mail: dans@ctagroup.com, 

Lee H. Spangler 

Montana State University (MSU) 

207 Montana Hall 

Bozeman, MT 59717 

Phone: (406) 994-2891; Fax: (406) 994-5407; E-mail: spangler@montana.edu 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

•	 Develop a system capable of measuring current and voltage performance for each membrane in a 

proton exchange membrane (PEM) fuel cell stack and record the performance of each individual cell. 

•	 Develop a single-cell PEM fuel cell to allow in situ synchrotron X-ray measurements of the cell in 

operation. 

•	 Perform initial magnetic resonance microimaging experiments on membrane materials. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Distributed Generation Systems 

•	 E. Durability 

• G. Power Electronics
 

Components
 

•	 P. Durability 

Approach 

•	 Design a system to capture individual cell performance in real time (current, voltage, temperature 

points taken every 0.5 milliseconds). 

•	 Test the stack response as it is subjected to load transients. Monitor each cell in the stack for its entire 

lifetime. 

•	 As failures occur, analyze the cell using X-ray techniques, including methods that provide spatial 

resolution and chemical composition information. 

•	 As failures occur, analyze the membrane material using magnetic resonance imaging (MRI) 

microimaging techniques to get information about membrane permeability.
 

•	 Search electrical records of failed membranes to see if mode of failure or an electrical signature of 

failure can be discerned. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 A fuel cell monitoring system has been constructed and undergone initial testing. 

•	 An individual synchrotron-compatible fuel cell has been constructed and tested at the National 

Synchrotron Light Source (NSLS). 

•	 Initial MRI microimages of membranes have been obtained. 

Future Directions 

•	 Modify the fuel cell monitoring system; then, run and monitor fuel cells under transient load change 

conditions. 

•	 Perform further X-ray analysis of membrane electrode assemblies (MEAs) on new cells to get baseline 

information before degradation occurs. 

•	 Start construction of an electrophoretic MRI probe so mobility in membranes under field testing can be 

measured. 

•	 Perform X-ray work on any degraded membranes. 

•	 Perform MRI work on any degraded membranes. 

Introduction 

The Montana State University PEM Membrane 

Degradation project is geared towards determining 

how and why membranes in fuel cells degrade and 

fail. By monitoring every individual membrane in a 

fuel cell 2000 times/sec while the cell is subjected to 

real-world use, we hope to: 1) cause the types of 

degradation users typically see, but in a controlled 

environment; 2) determine an electrical signature that 

will identify what causes failure, or at least warns of 

impending failure; 3) perform advanced X-ray and 

MRI characterization of the degraded membranes to 

provide information that may result in improvements 

of the membrane material; and 4) perhaps allow 

design of electronic control systems that will prevent 

fuel cells from operating under conditions where 

damage is likely to occur. 

Approach 

The Montana State University PEM Membrane 

Degradation project has three interdependent 

components: 1) Fuel Cell Electrical Characteristics 

Monitoring, 2) Synchrotron Based X-Ray 

Characterization of Membranes, and 3) Nuclear 

Magnetic Resonance (NMR) Microscopy of Polymer 

Electrolyte Membranes. The project will involve 

continuous, comprehensive monitoring of PEM fuel 

cell electrical performance while the cell is being 

subjected to real-world types of loads and transients. 

A fuel cell enclosure will contain 80 membranes 

housed in 8 cartridges. Each side of the cartridge (5 

membranes) will contain an analog-to-digital (A/D) 

converter that will measure voltage for each 

individual membrane, current and temperature at a 

2000 Hz rate. This total of 224,000 data points per 

second will be stored to provide a permanent record 

of performance of each individual membrane over its 

entire life span. This comprehensive set of data has 

promise of yielding an electrical signature of 

impending failure. Membranes in various states of 

degradation and failure will be extracted for 

characterization using the two analytical techniques 

in the project. 

X-ray characterization will be used to investigate 

the catalyst and possible poisoning of the catalyst, 

via X-ray Photoelectron Spectroscopy. In addition, a 

synchrotron-compatible fuel cell has been 

constructed to perform measurements during 

operation. If the electrical monitoring program 

identifies load conditions that generate degradation, 

in situ measurements can be performed under these 

conditions to determine chemical changes in the 

catalyst, and possibly in the membrane material 

itself. These measurements can be performed with 

10 mm or better spatial resolution so localized effects 

and spreading of damage can be studied, which may 

provide insight into the mechanism of failures. NMR 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

microimaging techniques will also be utilized to 

investigate membrane performance. Rather than 

imaging the membrane itself, this technique will 

provide images that contain information about water 

and hydronium ion mobility within the membranes. 

These imaging experiments will be performed on 

membranes in various states of degradation. 

Results 

Fuel Cell Electrical Characteristics 

Monitoring. We have designed, built, and tested 

three prototypes of a USB serial interface, 14-bit, 

280,000 sample/sec analog-to-digital converter 

board. This unit features an AD7856 converter, a 50 

MIPS Ubicom SX28 controller, and a DLP design 

USB interface module. The timebase stability is 50 

ppm. The measured noise variance is typically less 

than 1.5 LSB, or about .009 percent of full-scale. In 

addition to superior signal performance, our custom 

solution is better than commercial alternatives 

because its small size allows us to locate the analogto-digital conversion physically closer to the fuel cell 

cartridges. Most data collection alternatives would 

require us to route hundreds of wires carrying 

sensitive analog measurements in close proximity. 

This would lead to cross-talk and noise pickup 

between the leads that would likely degrade the 

measurements far beyond the inherent capabilities of 

commercial products. 

The data acquisition module is useful for other 

research at CTA. In addition, the Massachusetts 

Institute of Technology (MIT) and Woods Hole 

Oceanographic Institute (WHOI) have expressed 

considerable interest in the hardware. Both groups are 

interested in the novel capabilities and small size of 

our design relative to commercial offerings. MIT 

student Jim Paris is presently rewriting the Linux 

kernel driver for the USB interface and working with 

Greg Linus Torvalds and Kroah-Hartman (creators of 

Linux, and the Linux USB drivers, respectively) to 

ensure that the MSU/MIT enhancements are 

incorporated in future releases of Linux. WHOI is 

interested in using the board for next-generation 

instrument packs that are affixed to marine animals, 

where small size and low power are obvious concerns. 

We are presently designing an analog 

instrumentation-grade front end that goes between the 

USB data acquisition board and the fuel cell 

cartridges. We've identified a wiring scheme for each 

fuel cell cartridge, where voltage and temperature 

measurements are carried from the cartridge to the 

analog board via CAT5e twisted pairs. The fuel cell 

modules plug into the front-end instrumentation using 

modular connectors so that the modules are easy to 

swap out when the membranes fail. A key part of the 

front-end instrumentation is a new Analog Devices 

high-common mode range amplifier with integrated, 

trimmed, precision front end resistors. This unit 

features common mode rejection exceeding the rails, 

which is needed to isolate individual membrane 

potentials from the stack. The Analog Devices unit 

also comes with an auxiliary amplifier to adjust the 

voltage output range to that of the A/D converter. The 

cost of this instrumentation from Tektronix, for 

example, would exceed $100,000 for the number of 

channels we are considering. 

The storage server is at the highest level of the 

data acquisition hierarchy. We have assembled an 

SMP (simultaneous multi-processing) AMD Athlon 

based machine with two 1.4 Terabyte RAID-5 hotswap arrays. These have a combined capacity of 2.8 

Terabytes. In addition to disk hot-swap capability, 

the server has a redundant hot-swapable power 

supply system. All fans and other moving parts are 

also hot-swap. We project that this will be sufficient 

for approximately the first year of measurements 

with appropriate compression. 

A major contribution of the project is that we 

will expose membranes to realistic transient load 

conditions. Creating these conditions requires a 

transient capable DC active load. We've purchased a 

set of these from Agilent and are presently testing 

them. We have also designed and built our own 

active load. Testing for this device has been 

postponed in the interest of proceeding to the 

measurement stage as quickly as possible. 

Synchrotron Based X-Ray Characterization of 

Membranes. For this fiscal year, the following 

accomplishments were made. A graduate student 

(Alex Lussier) and a Research Experience for 

Undergraduates (REU) participant built a synchrotroncompatible fuel cell for in-situ X-ray characterization 

of the catalytic materials of the fuel cell during 

operation to identify performance degradation 

3 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

mechanisms. Chemical state and local structure 

information by X-ray absorption spectroscopy (XAS) 

and by X-ray absorption fine structure (XAFS) will 

identify the environment of the catalytic materials. 

These results will be compared to X-ray 

characterization of fuel cell components that have 

shown performance degradation to identify the failure 

mechanism. We will be able to identify catalytic 

poisoning and map out the poisoning element with 

good spatial resolution (a few microns resolution). 

From the support of this program, MSU is now a 

Participating Member in two beamlines at the National 

Synchrotron Light Source (NSLS) of Brookhaven 

National Laboratory. The first is the soft X-ray MSU 

Nanoscale Materials X-ray Characterization Facility at 

U4B (Spokesperson Y.U. Idzerda), and the second is a 

hard X-ray Absorption Fine Structure beamline at 

X23B (spokesperson Bruce Ravel). Both are open 

facilities for any research programs, but we now have 

guaranteed access. 

For preliminary work, we are characterizing the 

small fuel cell power output as a function of the 

hydrogen gas flow, air flow, and the load. We can 

compare these measurements to the performance 

curves for a commercial fuel cell measured 

elsewhere at MSU. This commercial cell is not 

compatible with the synchrotron techniques, 

although disassembly of the fuel cell and 

characterization of the catalytic and membrane 

materials will be a part of this research project. 

In addition to the in-situ X-ray characterization, 

we have initiated a project of modeling diffusion in 

fuel cells to identify failure modes. Finite element 

modeling of hydrogen ion and heat diffusion in PEM 

fuel cells has identified a possible mechanism for 

thermal failure of the membrane due to membrane 

thickness variations. This modeling will also assist 

us in understanding the performance degradation due 

to diffusion barriers at interfacial regions (from 

structural modifications or alloying) and due to 

catalytic poisoning. 

NMR Microscopy of Polymer Electrolyte 

Membranes. To date, we have focused on obtaining 

PEM samples, establishing the wet lab experimental 

protocol for sample preparations following prior 

NMR work1

 and establishing the NMR microscopy 

 FY 2003 Progress Report 

methods for imaging of PEMs. Before investigation 

of the PEM membrane, polymer hydrogel samples 

were used to establish the NMR methods. Figure 1 

shows NMR microscopy data for a 500 μm thick 

sample of hydrogel material. The hydrogel is cut 

into a 5 mm diameter disk and placed into a 6 mm 

diameter 500 μm thick Teflon (PTFE) sample holder 

with supernatant distilled H2O. The images are of 

calculated NMR parameters-T1 relaxation (Figure 

1a), T2 relaxation (Figure 1b) and translational 

diffusion coefficient (Figure 1c)-and have an inplane spatial resolution of 78 μm/pixel. The NMR 

signal is being obtained from the (1

H) protons on the 

water molecules within and external to the hydrogel. 

Spin-lattice, or T1, relaxation depends on the 

mechanisms available for energy transfer between 

the spins and thermal energy repositories such as 

translations, vibrations and rotations of the lattice. In 

a polymer gel matrix (or a polymer membrane such 

as a PEM), the presence of paramagnetic impurities 

or electron rich elements such as oxygen are a source 

of relaxation which depends on the chemistry of the 

matrix. The physical structure of the matrix-for 

example, the extent of cross linking in a gel-also 

impacts the relaxation by affecting the molecular 

motion of the water within the matrix and the 

resulting fluctuation rate of the magnetic fields. 

Hence, both the matrix mobility and chemical 

composition impact the T1 relaxation behavior in the 

sample. The T1 value for the water in the hydrogel, 

shown in light blue in Figure 1a, is measured to be 2 

s, while that of the free water, shown in purple in 

Figure 1a, is 2.2 s. This indicates enhanced 

relaxation rate 1/T1 of the water within the gel due to 

the restricted motion of the water molecules. 

Spin-spin, or T2, relaxation is due to interactions 

between the nuclear magnetic moments of the 

sample. The relaxation is due to the fluctuations in 

magnetic field from the dipole interactions due to 

molecular mobility [2, 3]. T2 values in solids are 

very short, indicating the fast magnetic relaxation 

rate, 1/T2, due to strong coupling of the dipole 

moments. In liquids, T2 is much longer since the 

motion of the spin generates motional averaging of 

the relaxation mechanism that results in a slow 

relaxation rate. The T2 of the water within the 

hydrogel, shown in light blue in Figure 1b, is 122 ms, 

while that of the free water surrounding the sample, 

shown in purple, is 165 ms. The restricted mobility 

4 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 MRI microimages of a) T1 relaxation, b) T2 

relaxation and c) diffusion coefficient of the 

water constrained within the matrix of a 

polymer hydrogel. The images are a top view 

of a 5 mm disk (light blue in a0 and b0) in a 6 

mm diameter sample cell. 

Figure 2.	 a) MRI microimages of the T1 weighted water 

concentration within a 178 μm thick disk of 

Dupont Nafion 117. The image intensity is 

proportional to water concentration weighted 

by T1 relaxation so that the free water 

surrounding the disk appears as black. Thus, 

the black regions within the disk indicate 

regions where water mobility is similar to free 

water. b) MRI map of the spatial T2 

distribution within the sample. 

within the hydrogel reduces the motional averaging 

of the spin-spin interactions, resulting in enhanced 

relaxation rate 1/T2. Consistent with the spatially 

resolved T1 and T2 data is the molecular translational 

self-diffusion coefficient of the water shown in 

Figure 1c. The orange region shows the slower selfdiffusion of the water within the hydrogel, 1.95 x 

10-9 m2/s, relative to the free water of brighter yellow 

with a diffusion coefficient of 2.45 x 10-9 m2

/s. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

These values of self-diffusion coefficient are in 

excellent agreement with those found from bulk 

NMR measurements without spatial resolution [4]. 

Preliminary images of Dupont Nafion117 PEMs 

have been acquired. While bulk NMR measurements 

of electroosmotic mobility [1] and molecular selfdiffusion of water [5] within PEMs have been 

reported, to our knowledge the images in Figure 2 are 

the first spatially resolved images of water within a 

PEM. The sample cell and in-plane spatial 

resolutions are the same as those used in Figure 1, 78 

mm/pixel, with the data averaged over the 178 μm 

sample thickness. The image in Figure 2a is of the 

water concentration within the PEM weighted by the 

T1 relaxation behavior, in contrast to the calculated 

T1 value maps in Figure 1a where the intensity of the 

image is directly the calculated T1 value. The T1 

weighting is such that the signal from free water is 

completely relaxed and gives no signal. Figure 2b is 

a T2 map of the PEM, with red indicating small T2 

values with increasing T2 through yellow, green, blue 

and purple. Comparison of Figure 2b and Figure 1b 

indicates the significant heterogeneity of the 

magnetic relaxation behavior within the PEM. The 

holes in Figure 2a could be the result of either highly 

mobile water or water in contact with strong 

chemical relaxation centers. Interpretation of these 

images will require significant experimental and 

theoretical analysis, including combining NMR 

measurements of T1, T2 and time dependent selfdiffusion, and is ongoing. 

Conclusions 

The three-pronged approach shows promise for 

yielding insights to degradation mechanisms and the 

changes in materials properties that result. 

FY 2003 Publications/Presentations 

1. Joseph D. Seymour, Sarah L. Codd, James C. 

Mabry, Scott C. Busse and Eric S. Peterson. 

"NMR microscopy of water and methanol 

distribution and dynamics in polymer electrolyte 

membranes." North American Membrane 

Society, 14th Annual Meeting, Jackson Hole, WY, 

May 17-21, 2003. 

References 

1. M. Ise, K.D. Kreuer, and J. Maier, Electroosmotic 

drag in polymer electrolyte membranes: an 

electrophoretic NMR study. Solid State Ionics. 

125: 213 (1999). 

2. E. Fukushima and S.B.W. Roeder, Experimental 

Pulse NMR: A nuts and bolts approach, Reading, 

MA: Addison-Wesley, 1981. 

3. P.T. Callaghan, Principles of Nuclear Magnetic 

Resonance Microscopy, New York: Oxford 

University Press, 1991. 

4. P. McConville and J.M. Pope, A comparison of 

water binding and mobility in contact lens 

hydrogels from NMR measurements of the water 

self-diffusion coefficient. Polymer. 41: 9081 

(2000). 

5. S. Hietala, S.L. Maunu, and F. Sundholm, 

Sorption and diffusion of methanol and water in 

PVDF-g-PSSA and Nafion 117 polymer 

electrolyte membranes. Journal of Polymer 

Science: Part B: Polymer Physics. 38: 3277 

(2000). 

6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Microstructural Characterization of PEM Fuel Cells 

Douglas A. Blom (Primary Contact), Lawrence F. Allard 

Microscopy, Microanalysis, Microstructures Group 

Oak Ridge National Laboratory, P.O. Box 2008, MS 6064, Bldg. 4515 

Oak Ridge, TN 37831-6064 

Phone: (865) 241-3898; Fax: (865) 576-5413; E-mail: blomda@ornl.gov 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Technical Advisor: David Stinton 

Phone: (865) 574-4556; Fax: (865) 574-6918; E-mail: stintondp@ornl.gov 

Objectives 

•	 Use transmission electron microscopy (TEM) characterization techniques to observe the distribution 

of precious metal catalyst, pore space and ionomer in proton exchange membrane (PEM) electrodes 

•	 Understand the processing/structure/property relationship for membrane electrode assembly (MEA) 

electrodes to allow for optimization of the electrode structure for higher performance 

•	 Characterize/quantify microstructural changes and their relation to the performance loss in PEM 

MEAs upon use in a fuel cell system to understand issues relating to durability and lifetime 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 O. Stack Material and Manufacturing Cost 

•	 P. Durability 

•	 Q. Electrode Performance 

Approach 

•	 Prepare thin cross-sections of PEM MEAs via diamond knife ultramicrotomy 

•	 Using TEM techniques, characterize the structure of the electrodes (e.g. size of catalyst particles, 

amount and location of ionomer, spatial distribution of supported catalyst) and relate to performance 

and/or processing 

•	 Investigate the electrode/membrane interfaces for evidence of microchemical degradation of the 

ionomeric membrane after extended use in a fuel cell 

Accomplishments 

•	 Successfully prepared cross-sections of MEAs provided by Los Alamos National Laboratory (LANL) 

•	 Improved the sectioning technique to routinely achieve 100 nm thick sections (vs. former 300 nm 

thicknesses) for greatly improved electron transparency and structural detail 

•	 Characterized the electrode structure effect of boiling the MEA in sulfuric acid 

•	 Characterized the as-prepared catalyst distribution for an advanced MEA design 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Investigate the effects of ionomer content on the structure of the electrodes 

•	 Characterize the microstructural changes which occur between standard decal painting of the 

electrodes and tape casting 

•	 Study the role the catalyst composition plays in the development of the overall electrode structure 

•	 Suggest modifications to the electrode forming process to optimize the use of the precious metal catalyst 

Introduction	 Approach 

Proton exchange membrane (PEM) fuel cells 

hold great promise for use as an environmentally 

friendly power source for automobiles. One of the 

key requirements in making PEMs commercially 

viable is to reduce the cost by reducing the amount of 

precious metal catalyst necessary to provide high 

power density operation at low temperature. In order 

for efficient catalysis to occur, gas molecules must be 

able to easily interact with the surface of the catalyst 

particles. A pathway for diffusion of protons must 

exist in close proximity to the active sites on the 

catalyst, and an electrically conductive pathway from 

the catalyst to the electrodes is required for electron 

transport. Finally, water (the by-product of the fuel 

cell reaction) has to be transported away from the 

catalyst for continuing reaction to occur. These 

requirements show the complexity of building an 

efficient PEM fuel cell and clearly indicate the 

opportunity for atomic-scale microstructural and 

chemical characterization to provide feedback on the 

geometry and distribution of the various components 

for optimum performance. 

PEM fuel cells are well known to "age" upon 

application as a power source. Over time, the 

performance of both individual cells and the overall 

system degrades. By examining the structure and 

composition of the MEAs before and after use in a 

fuel cell environment, the changes which may have 

occurred can provide valuable information on the 

mechanism(s) of performance loss. Understanding 

the primary degradation mechanisms is the first step 

to successfully engineering an improved MEA with 

less performance loss. 

Cross-sections of PEM MEAs were prepared for 

transmission electron microscopy (TEM) by 

techniques of ultramicrotomy. Small sections from 

the MEAs, approximately 3 mm by 8 mm, were 

selected for sample preparation. The samples were 

placed into silicone embedding molds, and an 

Araldite epoxy resin was added to the molds to 

embed the sample. The resin was polymerized at 

least 16 hours at 60°C in order to produce a solid 

epoxy piece with the MEA sample embedded. The 

epoxy embedded sample was trimmed initially using 

a Leica EM Trim tungsten carbide trimming tool. A 

tungsten carbide tip was used to rapidly remove 

excess epoxy from around the MEA sample to 

produce a small, flat area suitable for 

ultramicrotomy. The nature of the MEAs dictated a 

narrow (0.25 to 0.5 mm), long (1-2 mm) area for 

ultramicrotomy. The epoxy-embedded MEA was 

then secured into the cutting arm of a Leica Ultracut 

UCT Ultramicrotome. A 45° diamond knife was 

used to slice several sections of various thicknesses 

from each sample. The goal is always to produce the 

thinnest possible slice for TEM examination. Slice 

thicknesses were typically 100 nm or less under room 

temperature microtomy conditions, facilitated by 

proper development of the appropriate resin mixture. 

The thin slices were floated off the diamond knife 

edge onto distilled water and then collected onto 

copper mesh grids. 

The thin samples were observed in either a Hitachi 

HF-2000 field-emission transmission electron 

microscope (FE-TEM) or in a Hitachi HD-2000 

dedicated scanning transmission electron microscope 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

(STEM, also a field emission instrument). Both high 

resolution TEM imaging of individual catalyst 

particles and their carbon support and atomic number 

(or “Z-contrast”) STEM imaging of the electrode 

structure were performed. The structure of the 

electrodes is key for good performance. The “three 

phase boundary” where porosity, ionomer and catalyst 

particles come together is where effective catalysis 

occurs. Both imaging and chemical composition 

analysis are provided by TEM at the length scale 

which is appropriate for understanding the details of 

the electrode structure. Additionally, the boundary 

between the electrode and the membrane is of great 

interest to the fuel cell community. A number of 

indirect electrochemical measurements suggest that 

the interface between the electrode and the membrane 

is a weak point in the durability of the overall system. 

Analysis of the structure and composition of this area 

for both freshly prepared MEAs and MEAs which 

have been used in a fuel cell for a number of hours 

provides a first step towards reducing the degradation 

of PEM fuel cells over time. 

Results 

Advances in room temperature ultramicrotomy 

this fiscal year have allowed us to prepare MEA 

cross-sections which are below 100 nm in thickness. 

Figures 1 and 2 are Z-contrast micrographs of 

sections from the same MEA electrode illustrating 

the benefits of the thinner section. Z-contrast 

imaging is a technique in the STEM which forms an 

 FY 2003 Progress Report 

image from the electrons, which are scattered to large 

angles by the atoms of the sample (1). Atoms with a 

larger atomic number (Z) scatter electrons to high 

angles more strongly than atoms with lower atomic 

number. In the case of PEM fuel cell electrodes, the 

high atomic number catalyst particles (typically Pt) 

scatter electrons to a much greater degree than the 

surrounding ionomeric material and therefore appear 

as bright specks in the image. The sample shown in 

Figure 1 is 300 nm thick, which is sufficiently thin 

for successful imaging and microanalysis of the 

electrode. Transmission electron microscopy always 

involves the projection of a three-dimensional 

microstructure onto a two-dimensional image. In 

this case, significant overlap of the catalyst particles 

is observed with a thickness of 300 nm. Significant 

data can be extracted from images such as Figure 1, 

including the size distribution of the catalyst particles 

and the gross electrode structure. However, details 

of the spatial distribution of the ionomer and the 

porosity are obscured by the thickness of the section 

shown in Figure 1. Figure 2 is a Z-contrast 

micrograph from a 100 nm thick section of the same 

MEA. The individual catalyst particles are more 

easily seen in Figure 2 versus Figure 1. Additionally, 

the porosity of the electrode is seen in the dark area 

in the lower section of the micrograph. Evidence of 

the carbon black support of the catalyst particles is 

seen in the grayscale difference between the 

background of the image and the brighter areas 

around the catalyst particles. The catalyst particles 

are seen to coat the surface of the carbon black 

Figure 1. Z-contrast Micrograph of a 300 nm Thick
 

Section of an MEA Electrode
 

Figure 2. Z-contrast Micrograph of a 100 nm Thick
 

Section of an MEA Electrode
 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

support. A much more thorough understanding of 

the detailed structure of the electrode is possible from 

the image in Figure 2 as compared to the image in 

Figure 1. The thicker specimen allows for the 

characterization of the catalyst particles and the gross 

spatial distribution of the catalyst, while the thinner 

specimen allows, for the first time, a direct 

observation of the spatial distribution of all three 

phases of an MEA electrode: catalyst and support, 

ionomer and porosity. 

The effect of boiling the MEA in sulphuric acid 

on the initial microstructure of the electrode was also 

investigated this fiscal year. Figures 3 and 4 are 

TEM micrographs of electrode for sections ~100 nm 

thick. Bright-field TEM images are formed from 

unscattered and low-angle scattered electrons. At 

low resolution, the bright areas of the image 

correspond to porosity and/or low scattering parts of 

the sample. The MEA shown in Figure 3 did not 

undergo the boiling step during the preparation 

process for the MEA. The section was sufficiently 

thin that the porosity, catalyst and support and 

ionomer are clearly distinguishable. The small black 

specks are the individual catalyst particles, while the 

larger circular features are the carbon black support. 

The ionomer is the overall light grey background, 

while the porosity is visible as the white areas in the 

 FY 2003 Progress Report 

micrograph. The catalyst clusters are very close 

together in Figure 3, with very little ionomer-only 

area visible. Figure 4 illustrates the electrode 

structure on an MEA which was boiled in sulphuric 

acid as part of the fabrication process. The section 

thickness and micrograph magnification are the same 

as in Figure 3. The catalyst clusters are better 

separated, with obvious areas of ionomer visible in 

the image. Catalyst particles in PEM fuel cell MEAs 

have previously been shown to coarsen with time 

during fuel cell use. The microstructure in Figure 3, 

where the catalyst particles start off much closer 

together than the corresponding structure in Figure 4, 

is much more susceptible to catalyst coarsening and 

the subsequent performance loss. 

Conclusions 

•	 Room temperature ultramicrotomy is 

capable of producing MEA cross-sections 

100 nm thick. 

•	 Sections that are 100 nm thick allow for the 

characterization/analysis of all the 

components of a PEM fuel cell electrode, 

while thicker sections do not. 

•	 Boiling in sulphuric acid has a great effect on 

the initial microstructure of the electrode in a 

PEM fuel cell MEA. 

Figure 3. TEM Micrograph of an MEA Electrode not 

Boiled in Sulphuric Acid 

Figure 4. TEM Micrograph of an MEA Electrode 

which was Boiled in Sulphuric Acid 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 The boiling process is expected to improve 

the durability of the electrode by increasing 

the distance between catalyst particle 

regions. 

References 

1. S. J. Pennycook and D. E. Jesson, “HighResolution Incoherent Imaging of Crystals”, Phys. 

Rev. Lett. , 64 (8), 938. 

FY 2003 Publications/Presentations 

1. D. A. Blom, J. Xie, and L. F. Allard, “TEM 

Characterization of PEMFC MEAs”, 2003 Fuel 

Cell Seminar, Abstract #118. 

2. D. A. Blom and L. F. Allard, “TEM 

Characterization of PEM Fuel Cells”, 2003 DOE 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Merit Review and Peer 

Evaluation Meeting. 

3. D. A. Blom, J. R. Dunlap, T. A. Nolan, and L. F. 

Allard, “Preparation of Cross-sectional Samples 

of Proton Exchange Membrane Fuel Cells by 

Ultramicrotomy for TEM”, J. Electrochem. Soc., 

Vol. 150, p. A414. 

4. D. A. Blom and J. R. Dunlap. “Preparation of 

Cross-sectional Samples of Proton Exchange 

Membrane Fuel Cells for TEM Characterization”, 

Microscopy and Microanalysis, 2003. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Validation of an Integrated System for a Hydrogen-Fueled Power Park 

Todd Carlson (Primary Contact), Dave Guro, Greg Keenan 

Air Products and Chemicals, Inc. 

7201 Hamilton Blvd, Mail Code A5315 

Allentown, PA 18195-1501 

Phone: (610) 481-4217; Fax: (610) 481-3614; E-mail: carlsote@apci.com 

DOE Technology Development Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmund.Gronich@ee.doe.gov 

Objectives 

• Determine the optimal natural gas to proton exchange membrane (PEM) power system 

- Central reformer or local reformers 

- Central PEM or local PEM 

- Waste heat utilization 

- Operating mode 

• Determine the ideal site for a power park 

- Total peak power 

- Power profile 

- Commercial or industrial 

- Utilization 

• Optimize the system for lowest total power price 

• Demonstrate a prototype natural gas to PEM power park at a suitable site 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• E. Durability 

• F. Heat Utilization 

• G. Power Electronics 

• H Startup Time 

Approach 

• Investigate and estimate the cost for each system configuration 

• Determine the optimal (lowest cost of power) system configuration 

• Provide the best cost of power today and in the future 

• Determine building types that are amenable 

• Determine the optimal operating mode (baseload, peakshave, backup, island) 

• Investigate fuel cell capabilities today vs. optimal operating requirements and DOE targets 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Modeled the cost of power as a function of fuel cost, efficiency, maintenance, fuel cell and reformer 

costs, return on investment, and overhead 

•	 Determined the required fuel cost, efficiency, and capital costs to provide 10% return on investment at 

$0.10/kWh cost of power 

•	 Determined the amenable building types 

•	 Determined the unit costs of hot water piping, hydrogen piping, and electrical wiring 

•	 Estimated the impact of waste heat utilization on the cost of power 

•	 Examined current state-of-the-art reformer, purification, power conditioning, and fuel cell systems 

•	 Studied various distributed generation projects to identify the factors that contributed to the decision to 

install distributed generation 

Future Directions 

•	 Hydrogen energy stations (fueling and power generation concurrently) 

•	 Other system cycles that are more efficient 

Introduction 

The goal of this project is to develop an 

optimized power generation system with natural gas 

as the fuel and PEM fuel cells providing the 

conversion to electricity. The first step of this project 

was to identify all possible processes that could be 

used to produce power from natural gas. 

Construction and capital costs were then collected 

from all available vendors of reformers, purification, 

and fuel cells. A cost of power model was built to 

provide rapid calculations while changing inputs. 

The selection of the optimal process was then 

completed based on the cost of power. 

The next step involved a reverse calculation to 

determine what fuel cost, utilization, capital costs, and 

efficiency were required to achieve a target electricity 

cost of $0.10/kWh. These answers determined the 

target size, operating mode, costs, and efficiencies for 

the system to meet DOE targets. The optimal system 

did not meet the DOE targets, so we continue to look 

into hybrid systems, such as the Hydrogen Energy 

Station (joint fueling and power production). 

Approach 

Each process was modeled using ASPEN Plus 

(modeling software) to determine system efficiency 

and potential waste heat. The construction costs 

were estimated by our construction estimating group 

using Penn State as the site with three buildings 

located 200 yards (each) away from a central 

location. The capital cost of reformers, purification 

systems, and fuel cells were determined by obtaining 

quotations from all identified manufacturers. The 

cost of power model was developed from our 

standard cost of gas model. Building power profiles 

were provided by Joe Huang, Lawrence Livermore 

National Laboratory (LLNL). 

Results 

There are a number of improvements that are 

required to achieve $0.10/kWh power cost. These 

include: 

•	 25% increase in overall efficiency 

•	 4000% increase in fuel cell life 

•	 500% increase in power output 

•	 95% reduction in cost of PEM fuel cell and 75% 

reduction in cost of reformer system 

The most effective use of PEM power both in 

terms of power cost and environmental impact would 

be in a baseload power application. 

Combined heat and power has a minor effect on 

the cost of power, as the reformers already utilize the 

majority of the waste heat. The remaining waste heat 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies

is low grade and is most likely only amenable to 

supplementing hot water requirements. 

Conclusions 

•	 Today's cost of power from natural gas fueled 

PEM fuel cells is $0.45/kWh. 

•	 Pressurized steam methane reforming with 

pressure swing adsorption (PSA) purification is 

the optimal system. 

•	 Requirements to reduce cost to $0.10/kWh 

include: 

- 40% total efficiency (31% best today) 

- $3,300/kW capital cost ($14,000/kW today) 

- 15 year life or 131,400 hrs (1,000 hrs today) 

- $3.37/MMBTU natural gas price ($5.65/ 

MMBTU at smaller sizes) 

 FY 2003 Progress Report 

•	 Size of the system needs to be above 800 kW to 

achieve industrial natural gas rates. 

•	 Hydrogen energy station or other complex cycles 

could provide better utilization or efficiencies. 

References 

1. Joe Huang (LLNL) - building power profiles 

2. Vendors - Reformer, PSA, metal membrane, and 

fuel cell costs and performance data. 

FY 2003 Publications/Presentations 

1. Poster Session at 2003 Annual Program Review 

and Peer Evaluation 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Novel Compression and Fueling Apparatus to Meet Hydrogen Vehicle Range 

Requirements 

Todd Carlson (Primary Contact), Bharat Bhatt, David Chalk 

Air Products and Chemicals, Inc. 

7201 Hamilton Blvd, Mail Code A5315 

Allentown, PA 18195-1501 

Phone: (610) 481-4217; Fax: (610) 481-3614; E-mail: carlsote@apci.com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

• Develop or identify components suitable for 700 barg hydrogen refueling 

• Develop an isothermal compressor for low cost, gaseous compression 

• Demonstrate a prototype compressor at a suitable site 

Technical Barriers 

This project addresses the following technical barrier from the Hydrogen Delivery section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan:
 

• B. High Costs of Hydrogen Compression 

Approach 

• Develop a compression cycle that utilizes low cost components 

• Test fluids for use in the compression cycle 

• Develop components for 700 barg fueling 

• Test various components in service 

Accomplishments 

• Developed a compression cycle that is low cost 

• Built a test skid for testing of fluid properties at various hydrogen pressures 

• Developed new components with leading vendors for 700 barg fueling 

• Initiated testing of high pressure components for durability and life 

Future Directions 

• Build a prototype compressor with a capacity of approximately 1 nm3/hr 

• Test alternate working fluids 

Introduction project was to identify all possible processes which 

The goal of this project is to develop a low cost, 

isothermal gaseous compressor. The first step of this 

could be used to compress gaseous hydrogen. 

Construction and capital costs were then estimated, 

and the design was refined based on the target costs. 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

A parallel effort was begun to develop high 

pressure fueling components that have the desired 

cost, life, and performance. 

Approach 

Each process was modeled using ASPEN Plus 

(modeling software) to determine system efficiency 

and to determine component sizing. Local 

fabricators with relevant experience estimated the 

construction costs. 

We approached Air Products preferred vendors 

and began co-development of a number of valves and 

instruments to support 700 barg fueling. 

Results 

We have tested a number of components and 

fitting types in hydrogen fueling service. Based on 

this experience, we have determined that medium 

pressure cone and thread fittings are the most robust 

fittings for these pressures. 

We have also found that a number of hydrogen 

fueling components require additional refinement. 

Permeation of softgoods or diaphragms and 

explosive decompression are two common issues. 

High pressure storage is the most difficult area as 

no cost-effective options exist today. Steel vessels at 

14,000 psig maximum allowable working pressure, 

required for cascade filling, are very expensive. 

Stainless steel machined vessels are also very 

expensive. Composite storage vessels hold the most 

promise. Composite storage vessels have currently 

been granted Department of Transportation 

exemptions for specific tanks of specific design. No 

American Society of Mechanical Engineers (ASME) 

exemptions or certifications exist for a stationary 

application like fueling. 

We have just begun testing various fluids to 

determine their impact on the thermodynamics of 

isothermal compression of hydrogen. 

Conclusions 

•	 An isothermal compressor is feasible. 

•	 Thermodynamics of process fluids with 

hydrogen are unavailable at 700 barg, so we will 

develop our own data. 

•	 High pressure components can be developed at 

reasonable prices for 700 barg fueling. 

•	 Storage is the most difficult component as it must 

be rated at 135% of the fueling pressure. 

•	 Composite cylinders could one day provide a 

viable storage solution with lowered costs and 

ASME approval. 

References 

1. Vendors - Compressor components, instruments, 

fittings, and valves. 

FY 2003 Publications/Presentations 

1. Poster Session at 2003 Annual Program Review 

and Peer Evaluation 

Special Recognitions & Awards/Patents 

Issued 

1. Patent application is pending on the compressor 

cycle. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hawaii Hydrogen Power Park 

Maurice Kaya, Chief Technology Officer
 

State of Hawaii Department of Business, Economic Development & Tourism (DBEDT)
 

P.O. Box 2539 

Honolulu, HI 96804 

Phone: (808) 587-3812; Fax: (808) 586-2536; E-mail: Mkaya@dbedt.hawaii.gov 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Implementing Partner: Hawaii Natural Energy Institute, Honolulu, HI 

Principal Investigator: Richard E. Rocheleau 

Project Manager: Mitch Ewan 

Objectives 

• Demonstrate an integrated hydrogen power park comprised of the following: 

- Electrolyzer powered by a renewable energy source, 

- Hydrogen storage and distribution system, 

- Proton exchange membrane (PEM) fuel cell connected to the grid & building, and 

- Optional hydrogen-fueled vehicle dispensing system; 

• Demonstrate hydrogen as an energy carrier; 

• Investigate interface issues with grid and buildings; 

• Identify codes & standards required to site a power park; 

• Identify barriers to a hydrogen infrastructure; 

• Educate local authorities on hydrogen technologies; 

• Prepare an economic analysis of hydrogen infrastructure development; 

• Generate public interest and support. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Production 

• T. Renewable Integration 

Off-Board Hydrogen Storage 

• U. Codes and Standards 

• V. Life Cycle and Efficiency Analysis 

Technology Validation 

• B. Hydrogen Storage 

• C. Hydrogen Refueling Infrastructure 

• E. Codes and Standards 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 H. Hydrogen from Renewable Resources 

•	 I. Hydrogen and Electricity Co-production 

Education 

•	 A. Lack of Awareness 

•	 B. Lack of Demonstrations or Examples of Real World Use 

•	 C. Institutional Barriers and Access to Audiences 

Approach 

Sequence of steps used to conduct the research: 

Phase 1 

•	 Design the Hawaii Power Park System proceeding from conceptual design, to detailed design, to final 

design; 

•	 Map out the permitting processes and develop a permitting plan; 

•	 Educate the local permitting authorities and prepare a community outreach plan; 

•	 Procure and test the individual system components at the Hawaii Fuel Cell Test Facility ("FCTF") 

located in Honolulu, including use of a UTC single-cell PEM fuel cell; 

•	 Procure initial fuel cell module; 

•	 Procure and install the data acquisition system; 

•	 Develop the Power Park systems model. 

Phase 2 

•	 Procure additional fuel cell power system modules; 

•	 Obtain all necessary permits to relocate to the Natural Energy Laboratory Hawaii Authority (NELHA) 

Distributed Energy Resources (DER) Center; 

•	 Complete necessary site improvements to receive equipment; 

•	 Ship system from FCTF to NELHA DER Center; 

•	 Interface the system with the commercial building and the utility grid; 

•	 Add new systems, high pressure storage, renewable electrolyzer systems as funding allows; 

•	 Conduct community education & outreach program; 

•	 Conduct initial engineering cost & performance analysis. 

Phase 3 

•	 Prepare test plans & procedures; 

•	 Conduct experiments, analyze the data and prepare reports; 

•	 Develop a business case for hydrogen; 

•	 Prepare an overall project Final Report. 

Accomplishments 

•	 Permits for FCTF system development site issued; 

•	 Electrolyzer delivered, installed and commissioned at the Hawaii FCTF; 

•	 Prototype hydrogen gas distribution panels designed, installed and operated; 

•	 Candidate site selected subject to negotiation of a satisfactory lease agreement; 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Negotiations initiated for procurement of first 5-kW PEM fuel cell module from UTCFC; 

•	 Interactive project management web site developed. 

Future Directions 

•	 Continue in accordance with the project plan; 

•	 Seek new partners to expand test bed capabilities for hydrogen technologies. 

Introduction 

Distributed power generation is increasingly 

viewed as an important component of the future 

electrical energy supply in the United States. A 

"Hydrogen Power Park" is a distributed power 

system comprised of locally available energy sources 

such as natural gas or renewable electricity generated 

by wind, geothermal or solar. The natural gas is 

reformed to produce hydrogen. The renewable 

electricity powers an electrolyzer to produce 

hydrogen. The hydrogen is stored and then used in a 

fuel cell or an environmentally acceptable hydrogen 

or hydrogen/natural gas internal combustion engine 

(ICE) to generate electricity to power a building 

complex or industrial facility. The hydrogen could 

also be used to fuel automobiles equipped with fuel 

cells or hydrogen internal combustion engines. As 

hydrogen technologies become competitive with 

conventional energy technologies, the "Hydrogen 

Power Park" concept is considered by the DOE to be 

an important step towards developing the viability of 

using hydrogen as an "energy carrier" in distributed 

power generation applications. 

In addition to the technical barriers being 

addressed through RD&D in laboratories for 

specific components of a hydrogen system, there 

are obstacles to successful implementation of fuel 

cells and the corresponding hydrogen infrastructure 

that can only be addressed by integrating the 

components into complete systems. To have 

confidence in these technologies, they must work as 

designed in "real world" systems. Power Park 

projects are part of the validation process. They are 

comprised of the most current technologies and 

operated in a real-world environment. A byproduct of this approach to technology validation is 

that technical and system problems are revealed, 

and component requirements can be better 

evaluated. 

Approach 

Our project approach was to first assemble a very 

strong public/private team whose members support 

the Power Park's objectives and have relevant 

hydrogen expertise to bring to the project. 

Our project team organization is illustrated in 

Figure 1. Our project partners include those 

companies that are responsible for supporting 

infrastructure for conventional fuels, electricity, and 

utility gas. Their participation will ensure that issues 

critical to integrating hydrogen systems within the 

existing fuels and electricity delivery infrastructure 

are considered. The roles and interests of the team 

members are as follows: 

Figure 1. Project Team & Organization 

State of Hawaii - Hawaii Department of 

Business, Economic Development and 

Tourism (DBEDT): 

•	 DBEDT provides state leadership to the 

introduction of a hydrogen infrastructure in 

the State of Hawaii and to bringing hydrogen 

systems into the marketplace. Through the 

implementation of this project, the state 

envisions the creation of a "living 

laboratory" that will allow the state to 

address a number of issues to overcome 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

impediments for the utilization of DER 

systems and hydrogen development. 

•	 DBEDT is the Prime Contractor. 

•	 DBEDT provides overall program 

coordination and is a cost share partner. 

Hawaii Natural Energy Institute, University 

of Hawaii (HNEI): 

•	 HNEI, a research unit within the School of 

Ocean & Earth Science & Technology 

(SOEST) at the University of Hawaii Manoa, 

has been an active participant in DOE's 

Hydrogen Program since 1986 and, in 1996, 

was named a DOE Center of Excellence for 

Hydrogen Research & Education. 

•	 HNEI is the Implementing Partner to execute 

the project on behalf of DBEDT. 

Sentech: 

•	 SenTech is a Washington DC consulting 

company that provides technical and 

economic analysis, education and outreach, 

and project management support to the DOE 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program. 

UTC Fuel Cells (UTCFC): 

•	 UTCFC has a long history of 

commercializing fuel cells and is considered 

by many to be the premier U.S. fuel cell 

company in both stationary and 

transportation applications. 

•	 UTCFC will supply fuel cell systems and 

engineering support for installation and 

evaluation. 

Stuart Energy Systems: 

•	 Stuart is a major developer and supplier of 

electrolyzers and has an extensive program to 

develop electrolyzers powered by renewable 

energy sources. This project provides a venue 

for testing and demonstrating their products in 

a real world environment. 

•	 Stuart is providing significant cost share. 

Hawaii Electric Light Company (HELCO): 

•	 HELCO is the electric utility on the Big 

Island. HELCO is a subsidiary of HEI, 

which is the holding company for the electric 

utilities on Oahu, Maui and the Big Island. 

•	 HELCO shall provide engineering and staff 

expertise in the permitting process and 

design of the interconnections between the 

grid, the electrolyzer, the fuel cell power 

system and the commercial test building. 

•	 HELCO shall utilize the existing utility 

consumer education programs to provide an 

outreach medium for the Power Park project. 

Hawaiian Electric Company (HECO): 

•	 HECO is the electric utility for the island of 

Oahu and is the largest of the Hawaiian 

electric utilities. 

•	 As part of its ongoing interest in and support 

of renewable energy projects, HECO has 

agreed to participate in the Power Park project 

and is providing engineering and staff time to 

review system designs on a cost share basis. 

The Gas Company (GasCo): 

•	 GasCo is the gas utility for Hawaii. It 

supplies Synthetic Natural Gas (SNG) to 

parts of Oahu and propane to the remainder 

of Oahu and the neighbor islands; 

•	 GasCo is supplying low pressure hydrogen 

storage tanks and related engineering and 

permitting expertise. 

SunLine Services: 

•	 SunLine is providing engineering and staff 

time to transfer its expertise in the permitting 

process, community outreach programs, and 

design of a hydrogen infrastructure. 

•	 Participation in design review meetings to be 

conducted on the Big Island to provide 

valuable "Lessons Learned" and technology 

transfer from the SunLine experience. 

California Energy Commission (CEC): 

•	 CEC has an interest in supporting the 

introduction of hydrogen infrastructure and 

DER in California. The Hydrogen Power 

4 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Park provides the opportunity to leverage 

CEC resources in a dedicated test bed that is 

available to conduct projects of specific 

interest to CEC and California utilities at a 

fraction of the cost of establishing a similar 

facility. 

Sandia National Laboratory Livermore 

(SNLL): 

•	 SNLL is a recent addition to the Hawaii 

Hydrogen Power Park team. 

•	 SNLL is developing flexible systems that 

can be quickly adapted to provide 

engineering analysis of advanced power 

parks for production of both hydrogen and 

electricity. 

The complete Power Park Project spans three 

years and is divided roughly into three 1-year phases 

which closely match the expected cash flow. The 

design of the system shall provide the flexibility to 

add components and new technologies as desired by 

existing and new partners. The "Hawaii Hydrogen 

Power Park" conceptual design is illustrated in 

Figure 2. The diagram shows an optional wind 

hydrogen system, an optional reformer system and an 

optional fuel dispensing system for transportation 

systems. While the initial project called for the 

testing of a PEM fuel cell system, an internal 

combustion engine running on hydrogen or a 

Figure 2. Hawaii Power Park Conceptual Design 

hydrogen rich mixture is an option of interest to the 

CEC and GasCo. The optional systems are subject to 

the availability of additional project funding. 

Project Implementation. Due to funding cash 

flow availability, Phase 1 was subdivided into two 

phases 1A & 1B. Phase 1A constitutes the design 

phase of the project and extends until October 2003. 

Phase 1B constitutes the procurement and assembly 

of the hydrogen production and storage systems and 

the first fuel cell module. Phase 1B extends until 

approximately June 2004 and overlaps with Phase 

1A. In Phase 1A, the overall Power Park system 

shall be designed, starting with a conceptual design 

and going through progressively more detailed 

iterations resulting in a final design. The hydrogen 

production and storage system required to support 

the fuel cell and systems testing will be assembled 

and tested in Phase 1B at the Hawaii Fuel Cell Test 

Facility (FCTF) site in Honolulu. The hydrogen 

during this initial phase will be produced from a 

grid-connected Stuart Energy Systems electrolyzer. 

The first fuel cell module will also be procured and 

integrated into the hydrogen system at the FCTF 

site during Phase 1B. Identifying and resolving 

safety and permitting issues are also critical Phase 1 

tasks. Analytical tasks in Phase I will focus on 

defining the power requirements for the Power Park 

and calculating the costs of hydrogen from the 

various primary energy options (solar, wind, 

geothermal etc.). 

In Phase 2, the primary emphasis will be on 

installing and demonstrating the hydrogen and fuel 

cell systems at the Gateway Center facility. Funding 

permitting, we will expand and diversify the 

hydrogen production technologies by adding a 

second electrolyzer connected directly to a wind 

turbine at a Big Island wind farm and transport the 

hydrogen by means of high pressure tanks to the 

Power Park site. The system will be modular (trailer 

or skid-mounted) and portable so that it can be 

moved to other renewable energy source sites on the 

Big Island and to other Hawaiian islands. 

Phase 3 will consist of a series of system 

experiments for system optimization, market 

development activities and an expansion of the 

education and outreach program. A series of studies 

and analyses will be performed to evaluate system 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Stuart Energy Systems Electrolyzer at the 

FCTF 

design differences between automotive and 

stationary applications. 

Results 

The project is in the early stages of designing and 

assembling the system. To date we have prepared a 

conceptual design of the Power Park and are working 

on the detailed design. The electrolyzer, a long lead 

item, has been delivered to the FCTF and has been 

commissioned. The electrolyzer is pictured in Figure 

3. We have also gone through the process of 

permitting the FCTF site and have received the 

permits. This experience will help in the permitting 

process required by the County of Hawaii on the Big 

Island. We have assembled a high pressure gas 

storage system and connected the electrolyzer 

hydrogen output. Negotiations are currently 

underway for the supply of the first PEM fuel cell 

module, which will be tested at the FCTF. 

Conclusions 

•	 This project is in the formative stage and no 

conclusions can be drawn at this time. 

FY 2003 Publications/Presentations 

1. Poster presentation at the 2003 Hydrogen & Fuel 

Cells Merit Review Meeting - 19-22 May 2003 

at Berkeley California 

6 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Power Park 

Rob Regan (Primary Contact), Ryan Waddington, Murray Davis, Bruce Whitney 

DTE Energy Company 

2000 2nd Avenue 

Detroit, MI 48226-1279 

Phone: (313) 235-9152; Fax: (313) 235-0239; E-mail: reganr@dteenergy.com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811, E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

Discover and document whether the power park concept is technically and economically viable as a clean 

energy system, and if so, under what operating and market conditions. Specific objectives include: 

•	 Identify the drivers of economic performance for multi-use hydrogen energy systems including energy 

sources (renewable & conventional fuel sources), capital costs, operation and maintenance (O&M) 

costs, and emissions (cost benefit analysis vis-à-vis pollution non-attainment areas). 

•	 Determine conditions for system optimization and cost reduction for hydrogen systems, including 

design footprint and multi-use energy station applications. 

•	 Identify the characteristics of an economically viable hydrogen-based energy system designed for peak 

shaving and vehicle fueling applications. 

•	 Accelerate the development of technology delivery, system operations, and applications experience in 

hydrogen energy systems. 

•	 Collect and evaluate operational, durability, and efficiency information for an integrated renewable/ 

electrolyzer system. 

•	 Contribute to development of relevant safety standards and protocols for hydrogen-based power 

systems. 

•	 Evaluate the market for integrated hydrogen energy systems: develop a business plan for distributed 

hydrogen energy systems, as appropriate; test potential for "green power" customers. 

•	 Educate the public: promote awareness of hydrogen-based energy systems through development of 

educational materials and group sponsored events. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 C. Hydrogen Refueling Infrastructure 

•	 D. Maintenance and Training Facilities 

•	 E. Codes and Standards 

•	 H. Hydrogen from Renewable Resources 

•	 I. Hydrogen and Electricity Coproduction 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

•	 Develop, install, and operate a hydrogen co-production facility capable of delivering ~500 kWh/day of 

on-site electricity and ~15 kg/day of compressed hydrogen for vehicle refueling. 

•	 Integrate renewable energy into an end-to-end hydrogen energy station concept that utilizes solar & 

biomass power combined with electrolysis and stationary PEM fuel cell technology to take advantage 

of power during off-peak hours to generate hydrogen for on-peak power generation and vehicle 

fueling. 

•	 Using the latest hydrogen generation, storage, regeneration and control technologies, evaluate 

opportunities to reduce overall system cost and maximize performance through optimization of system 

design & operation, practical approaches to permitting, and integration of power and transportation 

applications using a common hydrogen infrastructure. 

•	 Obtain permits and install an integrated electrolytic hydrogen production, storage, on-site power 

generation, and vehicle refueling facility in the State of Michigan. 

Accomplishments 

•	 Selected team 

•	 Established optimal technologies and sources 

•	 Developed work plan & budget 

•	 Established codes & standards framework 

•	 Selected system site 

•	 Began system design & permitting - 20% complete 

•	 Procured equipment - 75% complete 

Future Directions 

•	 Install & commission system 

•	 Develop education & outreach program 

•	 Operate, monitor, and maintain system 

•	 Develop project technical report 

•	 Assess economics & develop business plan, as appropriate 

•	 Document and publish project results 

Introduction 

Given the potential for the commercialization of 

hydrogen as a replacement energy carrier for fossil 

fuels, this demonstration project, which models a 

complete renewable hydrogen system, from biomass/ 

solar power to hydrogen generation and storage to 

electrical generation and vehicle fueling, will provide 

meaningful information to overcoming the technical 

and economic challenges of realizing a hydrogenbased economy. 

The project develops, installs, and operates a 

hydrogen co-production facility capable of delivering 

~500 kWh/day of on-site electricity and ~15 kg/day 

of compressed hydrogen for vehicle refueling (Figure 

1). By incorporating the most commercially 

representative units into a complete system operated 

under realistic scenarios, this approach can provide 

data necessary to validate component technical 

targets and feedback for efficient Department of 

Energy R&D program management. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1. DTE Energy Hydrogen Power Park, 

Southfield, MI 

Approach 

This project integrates renewable energy into an 

end-to-end hydrogen energy station concept that 

utilizes solar & biomass power combined with 

electrolysis and stationary PEM fuel cell technology 

to take advantage of power during off-peak hours to 

generate hydrogen for on-peak power generation and 

vehicle fueling (Figure 2). 

Using the latest hydrogen generation, storage, 

regeneration and control technologies, the project 

will evaluate opportunities to reduce overall system 

cost and maximize performance through 

optimization of system design and operation, 

practical approaches to permitting, and integration of 

power and transportation applications using a 

common hydrogen infrastructure. 

Figure 2. Hydrogen Power Park - Conceptual Drawing 

The system components include: ~170 kW 

electrolyzer (effective for low volume on-site 

hydrogen requirements); compressed gas storage at 

+5,000 psi (proven, safe, relatively cost effective); 25 

- 75 kW fuel cell bank (quiet, clean, efficient); 

refueling dispenser at up to 5,000 psi (state-of-theart). 

Results 

Phase I (months 1 - 6) of the overall project plan 

has been completed with Phase II (months 7 - 18) in 

progress. Milestones achieved in Phase I included 

project team selection, establishment of optimal 

component/system technologies and sources, 

development of work plan and budget, establishment 

of codes and standards framework, and system site 

selection. 

Key activities currently underway include 

system design & permitting - 20% complete, and 

equipment procurement - 75% complete. Future 

milestones include installation and commissioning of 

system (April 2004); development of an education 

and outreach program; operation, monitoring, and 

maintenance of the system; development of the 

project technical report; assessment of the economics 

and development of a business plan for distributed 

hydrogen energy systems, as appropriate; and 

documentation and publication of project results. 

Conclusions 

The project remains on-schedule with the 

original plan, despite a delay in reimbursement 

monies from FY03 to FY04 and a lack of fully 

developed subsystems that are representative of 

commercial units. Industry dynamics resulting from 

increased economic pressures and changing target 

markets have resulted in a lack of fuel cell power 

generation and hydrogen production subsystems that 

are ready for market. This presents increased risk of 

execution for system designers and integrators, as 

these subsystems must first be demonstrated and 

tested before being incorporated into complete 

systems and tested under real-world operating 

conditions. 

In addition to these challenges, the current 

level of hydrogen codes and standards 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

development has resulted in modifying system 

design and implementation plans to mitigate 

project execution risk. 

The above challenges have, however, accelerated 

the development of component and hydrogen system 

applications knowledge within the company. This 

kind of rapid experience building is an important 

outcome of the technology validation program that 

increases the likelihood of successful development of 

technically and economically viable hydrogen energy 

systems. 

FY 2003 Presentations 

1. R. Regan, "DTE Energy Hydrogen Power Park" 

poster session, DOE Merit Review, Berkeley, CA 

(2003) 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Power Parks System Simulation 

Andrew Lutz 

Sandia National Laboratories 

MS 9053 

Livermore, CA 94551-0969 

Phone: (925) 294-2761; Fax: (925) 294-1004; E-mail: aelutz@sandia.gov 

DOE Technology Development Manager: Sigmond Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmond.Gronich@ee.doe.gov 

Objectives 

•	 Develop a flexible system model to simulate distributed generation in power parks that use H2 as an 

energy carrier. 

•	 Analyze the dynamic performance of demonstration systems to examine the thermal efficiency and 

cost of both H2 and power production. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 C. Hydrogen Refueling Infrastructure 

•	 I. Hydrogen and Electricity Coproduction 

Approach 

•	 Develop a library of Simulink modules for the various components. 

•	 Assemble the components into system models for the different power parks. 

•	 Compare simulations to the operational data from demonstration sites. 

Accomplishments 

•	 The library of components includes reformers (steam methane reformers - SMR, autothermal 

reformers - ATR), a fuel cell stack, a multi-stage compressor, a high-pressure storage vessel, an 

electrolyzer, a photovoltaic (PV) collector, and a model for incident solar radiation. 

•	 Simulation of the sub-components in the SunLine system compared favorably to the observed data. 

The model evaluates the thermal efficiencies of the PV and electrolyzer systems. 

Future Directions 

•	 Continue to develop additional modules in the Simulink library, including a wind turbine, a H2-fueled 

internal combustion engine (ICE) generator, and a power conditioning system. 

•	 Develop a layer of analysis to compute the cost of the power and H2 generated, including the initial 

capital costs of the components and the continuous operation costs during the life of the simulation. 

•	 Compare the simulations of dynamic performance with data collected from demonstration sites at 

SunLine, Las Vegas, and Hawaii (HNEI). 

•	 Implement a control strategy to direct the power within the park to meet the internal load while 

optimizing the energy efficiency and cost. 

1 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Introduction 

The hydrogen program research plan [1] 

envisions the transition to widespread H2 distribution 

will likely begin with distributed generation of H2. 

This avoids, at least in the near term, the construction 

of H2 pipelines, using existing distribution 

capabilities for fuels like natural gas. In addition, the 

cost of H2 produced at small-scale facilities may be 

reduced by combining power generation by fuel cells 

or engines to supply local needs. Such distributed 

energy sites where power generation is co-located 

with businesses or industrial energy consumers are 

called power parks. 

Proposed power parks use combinations of 

technologies. A local power source is often 

combined with a storage technology to adapt the 

dynamic nature of the source to the load. In some 

cases, the system operates completely separate from 

the utility grid. Alternatively, the power park may 

use the utility grid as a storage device, selling power 

to the utility when there is excess and drawing power 

when the local source cannot meet the load. The 

refueling facility at the City of Las Vegas is an 

example of this approach. The system is designed to 

operate the SMR in steady state, with the H2 

produced being split between a refueling station and 

a fuel cell stack selling power to the grid. 

Often, power parks are sited in order to take 

advantage of a renewable energy source. Generation 

by photovoltaic collectors or wind turbines can be 

combined with energy storage technologies. Power 

parks provide an excellent opportunity for using 

hydrogen technologies. Electricity from the 

renewable source can be used to generate hydrogen 

by electrolysis, which is then stored for use in fuel 

cells or to refuel vehicles. The SunLine Transit 

Agency has been demonstrating the PV-electrolyzerrefueling system for a couple years, with the plan to 

bring some wind turbines on line in the next year. 

The variety of technologies and their 

combinations that are being proposed for power 

parks suggests that each system will be novel, at least 

in some aspect of its design. Consequently, a flexible 

simulation tool will be very useful in evaluating the 

various systems and optimizing their performance 

with respect to efficiency and cost. 

 FY 2003 Progress Report 

Approach 

The deliverable of the project will be a flexible 

tool for simulation of the local power generation 

system, constructed in the language of Simulink 

software [2]. Simulink provides a graphical 

workspace for block diagram construction. The 

workspace provides the flexibility to quickly assemble 

components into a system, or to morph one system 

into another. Simulink performs dynamic simulation 

by integrating the system in time using a collection of 

ordinary differential equation solvers. After the 

simulation is completed, the solution can be examined 

by plotting variables at various states in the system. 

Simulink also contains modules for dynamic control 

and solution of iterative loops within the system. 

The software design begins with development of a 

library of Simulink modules that represent 

components in the power system. The component 

models are based on fundamental physics to the extent 

practical. These models are generic, in that they are 

not customized to represent a specific brand or 

manufacturer's features for the component. However, 

the generic components from the library can be tied to 

a specific unit by relying on performance data. The 

library components can be quickly modified to 

represent new or specialized components, thereby 

expanding the library's collection. 

Many of the basic modules that represent 

hydrogen and other gas mixtures use the Chemkin [3] 

software package to provide thermodynamic 

properties of the species and mixtures. For example, 

the SMR module uses equilibrium solutions for the 

chemical composition of both the catalytic reactor 

and the combustor sub-components. 

Results 

We have developed a library of Simulink 

modules for some of the various components being 

proposed for power parks. Existing components 

include reformers (SMR and ATR), a fuel cell stack, 

a multi-stage compressor, a high-pressure storage 

vessel, an electrolyzer, a PV collector, and a model 

for the incident solar radiation. 

The reformer modules take an input flow rate of 

methane and compute the hydrogen output. The SMR 

module performs an internal balance to supply the 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

energy required by the catalytic reactor by combusting 

the reformate stream. The ATR module includes some 

air in the process to balance the endothermic 

reforming with some partial oxidation of the fuel. In 

either type of reformer, the temperature at which the 

equilibrium reforming occurs depends on the energy 

balance and the mixture parameters (steam-to-carbon, 

oxygen-to-carbon). More detailed analysis of the 

reformer sub-systems is presented in references [4, 5], 

where the predictions of the models have been 

compared to data from small-scale reformers operated 

in our laboratories. 

Combining electrolyzer and compressor modules 

provides a comparison to the electrolyzer operation 

data from the SunLine facility [6]. The electrolyzer 

module uses a simple energy balance, which is 

defined by a specified thermal efficiency. The 

compressor module represents an ideal multi-stage 

compression with uniform efficiency in each state. 

Figure 1 compares the steady-state model to 

SunLine's operation data for two electrolyzer units 

manufactured by Stuart Energy and Teledyne Energy 

Systems. The solid lines represent the thermal 

efficiency of the electrolyzers, while the dashed lines 

represent the combined efficiency that includes the 

power required to compress the H2 from the output 

pressure of the electrolyzer to the storage pressure. 

 FY 2003 Progress Report 

The electrolyzer efficiency is adjusted so the 

combined efficiency matches the observed average. 

This analysis procedure backs out an estimate for the 

efficiency of the electrolysis step by using the 

computed compression power. The Stuart unit has a 

low-pressure output of 1 psig from the electrolysis, 

coupled to a 4-stage compressor that is estimated to 

be 50% efficient in each stage. From this input, the 

model matches the average data with an electrolysis 

efficiency of 70%. The Teledyne unit has a highpressure output of 100 psig from the electrolysis, 

coupled to a 2-stage compressor that is estimated to 

be 20% efficient in each stage. For this comparison, 

the model suggests the average electrolysis 

efficiency is 55%. 

The simulation of SunLine's data [6] for collection 

of electricity from the PV arrays is shown in Figure 2. 

The model uses an analytical formulation for the 

incident solar radiation [7] as a function of the location 

(longitude, latitude, and altitude) and time of year. 

The model for PV arrays is parameterized by the area, 

elevation angle, solar-to-electric conversion efficiency, 

and the tracking method. The solid curve in Figure 2 

is the computed monthly solar energy collected for the 

PV arrays in Palm Springs through the year. The 

Figure 1.	 Comparison of the Simulated Thermal 

Efficiency for the Electrolyzers Operating at 

SunLine Transit Agency 

Figure 2.	 Comparison of the Simulated Electricity 

Collection for the PV Arrays Operated at 

SunLine Transit Agency 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

model integrates the daily solar collection, then sums 

over each month to compare to the SunLine data. The 

symbols show SunLine's data collected over the fall of 

2001 (circles) and the entirety of 2002 (squares). 

There are two adjustments made in the simulation to 

match the observed data. First, the PV efficiency is 

7%, which sets the overall power collected (solid 

curve); this represents the maximum solar energy 

collection for clear sky radiation. Secondly, SunLine's 

record for number of cloudy days per month is used to 

correct the clear-sky estimate on a monthly basis to 

produce the dashed curve in Figure 2. The corrected 

curve agrees quite well with data for SunLine's 

operation. 

Conclusions 

The power system simulations can be compared 

to operation data for demonstration power parks, like 

the facility at SunLine transit. Comparisons of the 

simulations to observed performance provide 

feedback on energy efficiency and real capability of 

the technologies. For example, without the 

simulation, SunLine personnel did not have a way to 

estimate that their PV system was operating at 7% 

solar-to-electric efficiency. Similarly, while they 

could infer the overall efficiency of the electrolyzer 

units, the model can provide estimates of the separate 

efficiencies of the compression and electrolysis 

stages of the operation. 

Future efforts will apply the simulation tool to the 

entire system at SunLine, as well as demonstration 

sites at Las Vegas and Hawaii (HNEI). Model 

development will enhance the existing library modules 

and add new modules for wind turbines, ICE 

generators, and power conditioning. In preliminary 

development is a layer of analysis to compute the cost 

of the power and hydrogen generated. The cost 

analysis will accept input of the initial capital costs of 

the components, as well as the continuous operation 

costs during the life of the simulation, and add the 

costs using capital recovery factors. The simulation 

tool can be used in the planning and design of 

hydrogen technologies in distributed power systems. 

References 

1. U. S. Department of Energy, “Hydrogen, Fuel 

Cells, and Infrastructure Technologies Program 

Multi-Year Research, Development, and 

Demonstration Plan,” draft, June, 2003. (http:// 

www.eere.energy.gov/hydrogenandfuelcells/ 

mypp/). 

2. Simulink. The MathWorks, Inc, MA 

(www.mathworks.com) 2002. 

3. The CHEMKIN program and subroutine library 

are part of the Chemkin Collection. R J Kee, F. 

M. Rupley, J A Miller, M E Coltrin, J F Grcar, E 

Meeks, H K Moffat, A E Lutz, G Dixon-Lewis, M 

D Smooke, J Warnatz, G H Evans, R S Larson, R 

E Mitchell, L R Petzold, W C Reynolds, M 

Caracotsios, W E Stewart, and P Glarborg, 

Chemkin Collection, Release 3.5, Reaction 

Design, Inc., San Diego, CA (1999). 

4. Lutz, A. E., Bradshaw, R. W., Keller, J. O., and 

Witmer, D. E., “Thermodynamic Analysis of 

Hydrogen Production by Steam Reforming,” Int. 

J. of Hydrogen Engy, 28 (2003) 159-167. 

5. Lutz, A. E., Bradshaw, R. W., Bromberg, L., 

Rabinovich, R., “Thermodynamic Analysis of 

Hydrogen Production by Partial Oxidation 

Reforming,” accepted for publication in the Int. J. 

of Hydrogen Engy (2003). 

6. SunLine Transit Agency, “Hydrogen 

Commercialization: Transportation Fuel for the 

21st Century,” final report to the Department of 

Energy, February, 2003. 

7. Duffie, J. A. and Beckman, W. A., Solar 

Engineering of Thermal Processes, Wiley & Sons, 

NY, 1980. 

FY 2002 Publications/Presentations 

1. Lutz, A. E., Bradshaw, R. W., Keller, J. O., and 

Witmer, D. E., “Thermodynamic Analysis of 

Hydrogen Production by Steam Reforming,” Int. 

J. of Hydrogen Engy, 28 (2003) 159-167. 

2. Lutz, A. E., Bradshaw, R. W., Bromberg, L., and 

Rabinovich, A., “Thermodynamic Analysis of 

Hydrogen Production by Partial Oxidation 

Reforming,” Int. J. of Hydrogen Engy, accepted 

for publication. 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Filling Up With Hydrogen 2000 

Matthew Fairlie (Primary Contact), Hank Wedaa, Alex Lambert 

Stuart Energy USA 

5499 Paseo Gilberto 

Yorba Linda, CA 92886 

Phone: (714) 779-1604; Fax: (714) 693-0588; E-mail: mfairlie@stuartenergy.com 

DOE Technology Development Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmond.Gronich@ee.doe.gov 

Objectives 

•	 Design and build fuel appliances based on new low-cost electrolyser technology. 

•	 Demonstrate hydrogen vehicle re-fueling using fuel appliance systems. 

•	 Obtain '3rd party operating experience feedback' in refueling applications. 

•	 Establish precedents for development of codes and standards. 

•	 Determine cost effectiveness of fuel supply pathway. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Storage 	 

•	 C. Hydrogen Refueling Infrastructure 

•	 D. Maintenance and Training Facilities 

•	 E. Codes and Standards 

•	 H. Hydrogen from Renewable Sources 

Approach 

Prototype development involving building 8 different appliances: six Fleet Fuel Appliances and 2 Personal 

Fuel Appliances; each appliance project includes five phases: 

• Design 	 

• Build 	 

• Test 	 

•	 Customer evaluation 

•	 Tear-down and post mortem 

Accomplishments 

•	 All six Fleet Fuel Appliance prototypes have been constructed, featuring different technical advances. 

All units have entered the customer evaluation phase. The Community Fuel Appliance (CFA) is now a 

commercial product offered at fixed scope and price. 

•	 The Personal Fuel Appliance part of the program has been completed, and the final report for this part 

of the project has been submitted. The units continue to operate as demonstration prototypes. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Complete installation of Mark I unit at SunLine Transit, 1000 Palms, California. 

•	 Analyze performance of systems in the field; determine operating and manufacturing costs. 

•	 Complete project by September 31, 2003. Report results and recommend improvements for next cycle 

of fuel appliance development. 

Introduction 

"Filling Up with Hydrogen 2000" is a 

prototyping development project intended to validate 

the Stuart Fuel Appliance Model for hydrogen 

vehicle fuel supply infrastructure. Stuart fuel 

appliances are purpose built on-site electrolytic 

hydrogen generators for refueling gaseous hydrogen 

vehicles. Using only electricity and water and 

having no emissions beyond oxygen, electrolytic fuel 

appliances can be readily deployed to create a highly 

distributed fuel supply network. 

The objective of the Stuart/DOE project is to 

design, build and deploy a variety of fuel appliances. 

Two types of appliance are being built under this 

program: Fleet Fuel Appliances and Personal Fuel 

Appliances, both of which target the needs of nascent 

hydrogen vehicle commercialization. The Fleet Fuel 

Appliance targets buses, trucks and other centrally 

fueled fleet vehicles, where fuel production rates in 

excess of 400 SCFH are required. The Personal Fuel 

Appliance is geared towards consumer vehicles at the 

home or office and can be powered by the utilities 

found in the typical North American home. The 

production rate of these units is in the range of 50 

SCFH. Both types of appliances are capable of 

delivering gaseous hydrogen at high pressure (up to 

5000 psig) to the vehicle. 

Approach 

As presented in our Business Plan (Ref.1), the 

successful development and demonstration of fuel 

appliance technology will enable a cost effective 

pathway for building a hydrogen fuel supply 

infrastructure to support hydrogen vehicles in their 

early commercialization phase. The fuel appliance 

addresses the issue of fuel delivery by providing 

point-of-use fuel generation using existing energy 

utilities. Using the existing electricity grid, a full 

service infrastructure can be built up as a distributed 

network of small electricity-to-hydrogen fuel 

converters. 

Key to meeting the market requirements is 

reducing the cost of electrolysis. Stuart’s patented 

alkaline water electrolysis cell technology is 

designed to achieve the cost targets demanded by 

transportation fuels. The Compact Stuart 

Technology (CST) uses low-cost polymer and metal 

sheets, which are easily assembled in a stack. The 

CST electrolyser can be configured either as a singlestack or multi-stack electrolyser. The multi-stack 

electrolyser, having multiple cells in parallel, can run 

cell currents up to 30,000 amps and is suitable for 

large fueler applications. All the prototypes built 

under “Filling Up With Hydrogen 2000” use CST 

technology. The electrolyser packaged with the 

power system, compressor, purification and controls 

needed in a refueling application make up the fuel 

appliance. 

“Filling Up With Hydrogen 2000” will provide 

an experience base with the cell stack technology for 

later commercialization and is a cost effective 

approach for equipment testing in that the user/ 

customer picks up operating costs for the benefit of 

the hydrogen produced. In addition to testing the cell 

technology, the prototype development plan provides 

public exposure to the fuel appliance concept, 

introducing customers to the idea of distributed onsite hydrogen production, and provides valuable 

precedents for the development of codes and 

standards and hydrogen project risk assessment. The 

operation of the bus fuel appliance (P3-1A) at 

SunLine Transit provides public access to the 

technology through SunLine. The low-pressure 

fueler (P3-1B LP) provides a demonstration of a 

system which can refuel metal hydride gas storage. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

The high-pressure fueler (P3-1B HP) demonstrates 

the concept of a distributed “community fueler”. The 

design of the bus fueler, P3-5, demonstrates the large 

format cell technology which could be used in large 

bus fleet fueling applications. The P4 prototypes are 

being used to test different configurations of the cell 

stack and integration with the compressor, including 

a pressurized stack configuration and integration 

with a wind turbine in a semi-stand-alone energy 

system. Testing of the personal fuel appliance (PFA 

P1 Model 25) by major automakers will provide the 

auto industry the opportunity to evaluate the concept 

of a small onsite hydrogen generator and a potential 

home-based fueling appliance. 

Results 

P3-1A: Bus Fuel Appliance, is now undergoing 

post-operation analysis. Over the three years at 

SunLine, it operated 3100 h and produced over 3.5 

million SCF of hydrogen fuel. The appliance was 

used to fuel a variety of hydrogen and Hythane 

vehicles. 

P3-1B (HP): Community Fuel Appliance, which 

produces up to 400 SCFH at 5000 psig, has operated 

for 5000 hours, producing 2 million SCF. The 

appliance has been used to test/certify hydrogen 

vehicle fuel tanks and fuel a fleet of Hythane 

vehicles. An identical version of this appliance has 

been delivered to the California Fuel Cell 

Partnership. (See Figure 1.) 

 FY 2003 Progress Report 

P3-1B (LP): Community Fuel Appliance, which 

produces up to 400 SCFH at 200 psig, operated inhouse for over 3000 h. It was refitted on a mobile 

deck and used for re-fueling a metal hydride - 

hydrogen fuel cell mining locomotive in a joint 

project with Fuel Cell Propulsion Institute (FCPI). 

(See Figure 2.) 

P4-1A: Fuel appliance, capable of 400 SCFH at 

6000 psig, incorporating higher-pressure stack, was 

tested in-house. Problems arose because of 

contamination on sensors used to control pressure in 

cell. Approach to CST cell pressurization has been 

abandoned with the company’s acquisition of 

Vanderborre Hydrogen Systems and related cell stack 

technology. 

P4-1B: Community Fuel Appliance, which can 

produce up to 900 SCFH, was used to test hydrogen 

motor generator set at Southwest Research Institute 

and is now being used to generate hydrogen from 

wind energy at a Palm Springs wind farm as part of a 

project with Southern California Air Quality 

Management District (SCAQMD). (See Figure 3.) 

Mark 1: Commercial prototype of CFA-450 has 

been delivered to SunLine Transit 1000 Palms to 

replace P3-1A. This unit embodies all advancements 

learned from program. (See Figure 4.) 

PFA Model 25: Personal fuel appliance has 

completed tour with Ford fuel cell vehicle. Final 

report has been issued. 

Figure 1. P3-1B Fuel Appliance at Alameda County 

Transit, Richmond, CA Figure 2. P3-1B Mobile Fuel Appliance for FCPI 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. P4-1B Fueler for SCAQMD Wind-Hydrogen 

Project 

Conclusions 

Fuel appliances can reliably meet the needs of 

hydrogen vehicle refueling, delivering gas up to 5000 References 

psig. Prototyping has indicated further work is 

required to reduce equipment and installation costs 1. Stuart Energy USA, Filling Up With Hydrogen, 

and refine process automation. 1998, under DOE Cooperative Agreement No. 

DE-97GO10221 

Figure 4. Mark 1 Fueler for SunLine Transit 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Refueling Technology 

Michele R. Davies (Primary Contact), Robert Heffley 

HyRadix, Inc. 

175 W. Oakton 

Des Plaines, IL 60018 

Phone: (847) 375-7094; Fax: (847) 391-2596; E-mail: Michele.Davies@HyRadix.com 

DOE Technology Development Manager: Lucito Cataquiz 

Phone: (202) 586-0729; Fax: (202) 586-9811; E-mail: Lucito.Cataquiz@ee.doe.gov 

Subcontractor: SunLine Services, Thousand Palms, CA 

Objectives 

•	 Demonstrate hydrogen fueling station 

•	 Develop and demonstrate on-site autothermal reforming (ATR) of natural gas 

•	 Analyze hydrogen cost vs. target of $5/kg in 2003 

•	 Evaluate fuel cell vehicle refueling under real-world conditions 

•	 Support public education on hydrogen and fuel cells 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Production 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance 

•	 E. Control and Safety 

Technology Validation 

•	 C. Hydrogen Refueling Infrastructure 

•	 D. Maintenance and Training Facilities 

Education 

•	 B. Lack of Demonstrations or Examples of Real World Use 

Approach 

•	 Fabrication and testing of prototype (50 Nm3/hr) natural gas reformer with pressure swing adsorption 

(PSA) 

•	 Design and fabrication of demonstration (100 Nm3/hr) natural gas reformer with PSA 

•	 Installation and commissioning of demonstration unit 

•	 Process design of compression, storage & dispensing (CS&D) system 

•	 CS&D equipment design and selection 

•	 CS&D installation and permitting 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Training of system operator 

• Demonstration of integrated system 

• Data acquisition, analysis and reporting 

• Continuing public education on hydrogen and fuel cells at SunLine 

Accomplishments 

• Built and tested prototype reformer, including PSA system 

• Completed design and began fabrication of demonstration reformer, including PSA system 

• Designed, selected, and purchased CS&D equipment 

• Obtained permitting required for demonstration at SunLine 

Future Directions 

• Complete fabrication of demonstration unit 

• Deliver and install demonstration unit at SunLine 

• Commission demonstration unit 

• Install & commission CS&D equipment 

• Demonstrate and evaluate integrated hydrogen refueling station 

Introduction 

The objective of this project is to develop and 

demonstrate a hydrogen refueling station that 

combines HyRadix’s on-site hydrogen generation 

technology with compression, storage and dispensing 

facilities designed by SunLine Services Group. The 

refueling station will be located at the SunLine 

facility in Thousand Palms, California, and will 

provide low cost hydrogen to fuel three fuel cell 

buses and several fuel cell cars and street sweepers. 

The refueling station will also provide hydrogen that 

will be blended with compressed natural gas (CNG) 

to form a hydrogen-compressed natural gas (HCNG) 

blend and used in SunLine’s fleet of converted CNG 

buses. 

HyRadix’s hydrogen generation technology is 

based on ATR of natural gas combined with a PSA 

unit to purify the hydrogen. HyRadix’s reformer will 

produce 100 Nm3/hr of high purity (99.95%+) 

hydrogen. SunLine is drawing on their unique 

experience of being one of the few experienced 

operators of fuel cell vehicles to design and build a 

compression, storage and dispensing system to be 

integrated with the HyRadix reformer. The hydrogen 

will be compressed and stored at a pressure of 6250 

psi to allow for dispensing at 5000 psi. The target 

refueling rates are 15 minutes per bus and 3-5 

minutes per car. SunLine will also continue their 

directive to educate the public on hydrogen as an 

energy carrier and fuel cells. 

Approach 

The HyRadix hydrogen generation technology is 

based on autothermal reforming at a small scale, 

producing a reformate stream of 40-50% hydrogen. 

This gas stream is then purified to 99.95+% through 

a purpose-designed small-scale pressure swing 

adsorption unit. HyRadix built and tested a 

prototype 50-Nm3

/hr unit – half the output of the 

final demonstration unit – in order to incorporate 

improvements into the final design of the 100-Nm3

/ 

hr demonstration unit. Autothermal reforming 

combines partial oxidation and steam reforming, 

making efficient use of heat, but does not require 

exotic metallurgy. 

The SC&D system designed by SunLine will 

compress the hydrogen to 6250 psi, store it at that 

pressure and then dispense to the vehicles at a 

maximum of 5000 psi. The compression system 

comprises two-stage diaphragm compressors, which 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

maximize energy efficiency, reduce manufacturing 

costs and increase flexibility while maintaining 

contamination-free hydrogen. The two-stage design 

permits startup under the high inlet pressure of the 

gas stream coming from the PSA. The storage 

component consists of high-pressure carbon fiber 

wrapped cylinders rated at a maximum pressure of 

7250 psi. The dispenser system is a two-hose 

dispenser capable of dispensing at 3600 psi on one 

side and at 5000 psi on the other side for HCNG and 

fuel cell vehicles, respectively. The entire dispensing 

system will be rated for 7250 psi for safety reasons. 

HyRadix will develop operations and 

maintenance manuals for the demonstration unit and 

provide on-site training to SunLine personnel. 

SunLine staff will be responsible for the operation of 

the unit during the demonstration phase. 

Results 

The most important result of the project to date 

has been the learning from the operation and testing 

of the prototype unit, which has resulted in improved 

design for the unit that will be placed in service at 

SunLine. Several burner designs and control 

schemes were tried. This helped give us a robust 

burner design. Operation of the prototype has also 

brought to attention the importance of reducing 

thermal mass for both the start-up time and for 

process efficiency. The unit was tested at several 

different flow rates. This is important to determine if 

any anomalies exist that may limit the range of 

performance. In addition, the unit was started and 

stopped many times. This provides confidence that 

the unit can be run safely and with repeatable results. 

Smooth start-up has been achieved in less time than 

is required for conventional steam reforming plants. 

In addition, extensive logic testing has taken place. 

These tests helped create the software that will run 

the 100-Nm3

/hr hydrogen unit. 

The operation of the prototype (see Figure 1) has 

confirmed that it produces both reformate and highpurity hydrogen consistent with the project targets. 

Stream qualities were monitored, and these results 

helped prove that the unit removes the sulfur in the 

natural gas stream, has a stack-gas very low in NOx 

 FY 2003 Progress Report 

and SOx, and provides product hydrogen at target 

purity with almost undetectable levels of CO. The 

PSA unit was tuned to give optimum hydrogen 

purity. This tuning will help set the standard for all 

future units. 

The 100-Nm3

/hr demonstration plant that will be 

installed at SunLine is in the final stages of 

fabrication, incorporating the learning from the 

prototype plant. (See Figure 2.) The unit is 

mechanically complete. 

• All structural components are fabricated. 

• All equipment is installed on the structure. 

• All piping is installed between equipment. 

Figure 1. Prototype Unit Operating at HyRadix 

Figure 2. Demonstration Unit in Final Stages of 

Fabrication 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 All tubing is installed between equipment. 

•	 All tie-in connections are complete and ready for 

connection on site. 

•	 All instrumentation is installed and wired. 

•	 All power and control wiring is complete. 

The enclosure is complete and painted. 

•	 The enclosure protects the equipment from the 

elements. 

•	 The enclosure is partially installed for shipping 

protection. 

•	 The enclosure panels will be installed on site. 

Testing is under way. 

•	 All hydrostatic testing is complete. 

•	 Leak testing is 50% complete. 

•	 Instrument and electrical check-out is 35% 

complete. 

Conclusions 

•	 Operation and testing of the prototype unit has 

resulted in improved design for the 

demonstration unit. 

•	 The prototype unit produces hydrogen consistent 

with targets and with very low emissions and CO. 

FY 2003 Publications/Presentations 

1. Davies, M., D. Cepla, and D. Sioui, "Small Scale 

On-site Hydrogen Generation for Refueling 

Applications from Multiple Feedstocks," National 

Hydrogen Association Conference, March 2003, 

Washington D.C 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Cell Installation and Demonstration Project In Gallatin County, Montana 

Warren Bauder, Bruce Nelson (Primary Contact), Bill Hangas, Tony Rosanova, Tim Codding, 

Rob Norman 

Zoot Enterprises, Inc. 

555 Zoot Enterprises Lane 

Bozeman, MT 59718 

Phone: (406) 586-5050; Fax: (406) 586-8005; E-mail: bnelson@zootweb.com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

•	 Demonstrate operation of fuel cells and provide the hydrogen industry and the general public with a 

high-technology application of the units. 

•	 Determine the degradation rate of the fuel cells and the point at which it becomes economically 

necessary to "restack" by essentially replacing the fuel cells themselves. 

•	 Provide operational data to the Montana State University Electrochemical Engineering Research and 

Education Center to assist in the development of control equipment to optimize fuel cell performance 

when combined with other electrical sources. 

•	 Maximize efficiency of the heat recovery (cogeneration) system. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Multi-Year R,D&D Plan: 

Fuel Cells section 

•	 E. Durability 

•	 F. Heat Utilization 

Technology Validation section 

•	 I. Hydrogen and Electricity Coproduction 

Education section 

•	 B. Lack of Demonstrations or Examples of Real World Use 

Approach 

•	 Construct suitable stationary fuel cell installation site at a high-tech facility. 

•	 Install redundant stationary fuel cells. 

•	 Operate stationary fuel cells according to manufacturing and engineering specifications. 

•	 Study/analyze performance and reliability of installed fuel cells based on operational data collection. 

•	 Work in conjunction with Montana State University (MSU) to enhance complimentary fuel cell studies. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Completed construction and preparation of fuel cell installation site and related electrical/mechanical 

systems. (October, 2002) 

•	 Purchased two (2) 250-KW stationary fuel cells from Pennsylvania Power and Light, engineered and 

manufactured by Fuel Cell Energy (FCE). (October, 2002) 

•	 Facilitated physical installation and start-up of purchased fuel cells. (June, 2003) 

Future Directions 

•	 Finalize interconnection agreement with local energy supplier (Northwestern Energy) to allow for sale 

of surplus electricity. 

•	 Capture and analyze data applicable to reliability and performance of fuel cells. 

•	 Continue providing access to MSU for monitoring and analysis purposes. 

•	 Investigate formation of local "micro-grid" to allow for expansion and distribution of demonstration 

site installation to neighboring facilities. 

Introduction	 Results 

In December 2001, a Design Team Conference 

was held at Zoot Enterprises, Inc. headquarters in 

Bozeman, Montana, to address basic design and 

operation issues relating to fuel cell installation and 

ownership. At this time, parties were designated to 

assist with architectural, engineering, construction, 

and installation tasks. 

Two (2) 250-KW fuel cells were delivered and 

installed at the Zoot Enterprises facility in June 2003. 

Both units have completed the warm-up process and 

are currently being brought to full generation 

capacity. 

Approach 

Zoot Enterprises has taken an active role in the 

design, construction, and installation phases. It is 

expected that through this active involvement, we 

will be most successful in meeting the objectives of 

this project. 

Monitoring systems and devices have been 

installed both by MSU and also as part of the fuel 

cell package supplied by FCE. Zoot Enterprises will 

collect supplemental operational data through 

maintenance records, billing records, and 

demonstration experiences. 

No results are available at this time, as the fuel 

cell operation phase has not begun. Installation is in 

progress. 

Conclusions 

As the operational phase of this project is due to 

begin in July 2003, no conclusions have been 

formulated from this project at the current time. 

FY 2003 Publications/Presentations 

1. Department of Energy - Technical Progress 

Report - October 2002 

2. Department of Energy - Technical Progress 

Report - March 2003 

Special Recognitions & Awards/Patents 

Issued 

1. "Fuel Cells Delivered to Zoot Technologies" - 

June 18, 2003 article - Bozeman Daily Chronicle 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Global Assessment of Hydrogen-Based Technologies 

Fouad H. Fouad (Primary Contact), Virginia Sisiopiku, Robert Peters, Steven Jones, Keith Hardy, 

Danilo Santini, Maxime Pasquier, Andrew Sullivan 

University of Alabama at Birmingham 

Hoehn Engineering Building 

Birmingham, Alabama 35294 

Phone: (205) 934-8431; Fax: (205) 934-9855; E-mail: ffouad@uab.edu 

DOE Technology Development Manager: Sigmond Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmond.Gronich@ee.doe.gov 

Subcontractor: Argonne National Laboratory, Argonne, Illinois 

Objectives 

• Synthesize the state-of-practice for four potential hydrogen-based vehicle technologies. 

•	 Compare performance, emissions, and fueling characteristics of the four technologies 

(instrumentation). 

• Compare the four technologies in light of their potential role in a full-scale deployment. 

• Assess hydrogen infrastructure needs to support deployment (at local, regional, and national levels). 

• Offer education and training programs to increase the knowledge of the new technologies. 

•	 Increase the awareness of the new technologies through various mechanisms such as promotional 

materials for public media, a web-site, college programs, and a Hydrogen Fair in the southeastern U.S. 

to demonstrate the various vehicle technologies, pumping stations, hydrogen storage, safety issues, etc. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Vehicles 

• C. Hydrogen Refueling Infrastructure 

Approach 

•	 Evaluate candidate hydrogen-fueled vehicles for near and long-term use in the southeastern U.S. in 

terms of their efficiency, performance, and emissions. Four types of hydrogen-fueled vehicles are 

being assessed: hythane-fueled internal combustion engines (ICEs), hydrogen-fueled ICEs, hydrogenfueled hybrid electric propulsion vehicles (HEV), and direct hydrogen fuel cells. 

• Conduct rigorous performance and exhaust emissions testing of hydrogen technologies: 

1.	 ICE vehicles fueled with hydrogen-compressed natural gas (CNG) fuel mixtures (15-50% hydrogen, 50-85% CNG), 

2. ICE vehicles fueled with pure hydrogen, and 

3. Hydrogen-powered fuel cell vehicles. 

•	 Estimate resource requirements and costs for the infrastructure needed to deliver new fuels to 

advanced technology vehicles. Argonne's Natural gas Infrastructure Component Cost (NICC) model 

will be applied to the southeastern U.S., specifically the Birmingham/Atlanta region, to develop cost 

1 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

estimates and define additional hydrogen pathways. In addition, practical considerations in the design 

and development of fuel delivery facilities will be investigated. 

•	 Evaluate the ability of the vehicle technologies described previously to contribute to improved air 

quality in the Southeast, with special attention given to the Atlanta metropolitan area. Argonne's Air 

Quality Credits (AIRCRED) and Greenhouse Gas Energy and Emissions in Transportation (GREET) 

models will be used to assess impacts of a large-scale deployment on pollution emissions. 

•	 Determine the feasibility of using hydrogen fuel cell technologies for electric power generation. The 

potential to conduct an actual demonstration in the greater Birmingham, Alabama, area in such electric 

power applications as recreation parks, student housing facilities, or heavy industrial applications will 

be assessed to identify possible deployment locations and potential benefits. Measurements will be 

made to determine if the fuel cell technology will lead to pollution reduction and air quality 

enhancement, especially in an ozone non-attainment area such as Birmingham. 

•	 Establish the Southeast Hydrogen Technology Consortium (SHTC) to examine ways to establish a 

hydrogen infrastructure in the Southeast and enhance the infrastructure and application of the 

technology. The members will be experts in the field and representatives of different areas and sectors 

with interest in hydrogen technologies for both power generation and transportation. 

Accomplishments 

•	 A Ford F-150 was tested at Argonne National Laboratory using the dynamometer facility in their 

Transportation Technology R&D Center during May, 2003. The Ford F-150 was run on a fuel mixture 

(hythane) of ~50% hydrogen and ~50% compressed natural gas. Emissions data were collected for 

carbon monoxide (CO), carbon dioxide (CO2), total hydrocarbons (THC), nitrous oxides (NOx), and 

particulate matter. The equivalent miles per gallon fuel consumption was also monitored. Results 

were obtained using cold starts, hot starts, standard vehicle testing, and highway testing. The 

University of Alabama at Birmingham (UAB) compared the results with typical (high and low) 

emissions performance for CO, THC, and NOx, for light-duty and heavy-duty vehicles. The results 

indicated that using the 50% hythane fuel mixture, reductions in CO, THC, and NOx exceeded 97%, 

95%, and 94%, respectively, indicating that the emissions were reduced by more than an order of 

magnitude. 

•	 The UAB study team has received training on use of the PSAT vehicle simulation model to compare 

the efficiency and emissions of hydrogen-fueled vehicles with conventional internal combustion 

vehicles. 

• Data has been collected for inputs to the regional AirCred model. 

Future Directions 

•	 Evaluate additional test vehicles (hydrogen ICE and hydrogen fuel cell) for performance and 

emissions. 

• Simulate and compare hydrogen-fueled vehicles to conventional ICEs. 

•	 Use results of vehicle tests and simulations to evaluate potential impacts of a hydrogen vehicle 

deployment. 

•	 Investigate infrastructure requirements for a hydrogen vehicle deployment, including potential 

hydrogen producers and transport mechanisms. Investigate codes and standards related to hydrogen 

fueling stations. 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

Hydrogen-fueled vehicles hold the potential to 

reduce the emissions of pollutants and greenhouse 

gases currently associated with conventional 

gasoline- and diesel-fueled vehicles. Hydrogenbased vehicle technologies, however, are still in the 

very early stages of development, and their 

performance characteristics compared to 

conventional internal combustion engines (ICEs) are 

not well established. There are currently several 

promising hydrogen technologies available, but their 

potential for widespread deployment requires further 

evaluation. In the near term, hydrogen-fueled 

internal combustion engines (similar to conventional 

engines but modified to run on hydrogen or 

hydrogen-CNG blends) may prove to be the most 

immediately feasible technology. Another promising 

near-term technology are hydrogen-fueled hybrid 

electric vehicles, similar to the gasoline-powered 

hybrid electric vehicles already available, but with 

the gasoline motor replaced by a hydrogen-fueled 

motor. Hydrogen fuel cell vehicles may ultimately 

provide the lowest emissions of any hydrogen 

technology, but their development is also the most 

complex, and they are therefore generally considered 

a longer term option. 

Any assessment of the potential for large-scale 

deployment of these hydrogen technologies must be 

based on measured vehicle performance 

characteristics, not simply estimates. Only with 

realistic emissions and vehicle performance measures 

can we develop reasonable estimates of what impacts 

a large-scale deployment would have on air quality 

and which vehicle technologies offer the most 

promising near-term and long-term benefits. Such an 

assessment will also need to consider the cost of the 

infrastructure required to fuel and maintain these 

vehicles. Large fleets of hydrogen vehicles will 

require hydrogen production plants, transport systems, 

and fueling stations that do not yet exist and whose 

costs are not yet known. The purpose of this study is 

to evaluate the performance characteristics of various 

hydrogen vehicle technologies, identify the most 

promising near- and long-term technologies, and fully 

understand the infrastructure that a large-scale 

deployment will require. 

Approach 

The research will follow two primary tracks: (1) 

an evaluation of the performance characteristics of 

four hydrogen-fueled vehicle technologies, and (2) 

an investigation of hydrogen infrastructure 

requirements. The study will examine four 

promising hydrogen vehicle technologies: hythanefueled ICE vehicles, hydrogen-fueled ICE vehicles, 

hydrogen-fueled hybrid electric vehicles, and 

hydrogen fuel cell vehicles. The performance and 

emission characteristics of each type of vehicle will 

be measured at the Argonne National Laboratory test 

facility. The results of these tests will be 

incorporated into the PSAT vehicle simulation model 

and used to further compare the performance and 

emissions characteristics of each vehicle technology 

to conventional gasoline- and diesel-powered 

vehicles. The PSAT model outputs will then be input 

into the AirCred and GREET models to estimate the 

air quality impacts of a large-scale deployment of 

hydrogen vehicles in thes United States. 

The second thrust of the research will be to 

investigate the infrastructure that such a large-scale 

vehicle deployment would require. Current 

hydrogen production and production capacity in the 

southeastern United States will be assessed, as will 

the production of fuels and resources required to 

produce hydrogen (CNG, coal, methane) and the 

Figure 1.	 Ford F-150 Truck on Dynamometer at 

Argonne National Laboratory 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

transport systems (truck, rail, and pipeline) currently 

available to convey them. Based on the results from 

earlier portions of the study, estimates of the 

hydrogen demand for a large-scale vehicle 

deployment will be developed, and the cost of the 

additional infrastructure required to meet this 

demand will be assessed. The study will also 

examine the practical considerations involved in 

constructing and supplying hydrogen fueling stations 

in an urban environment. 

Results 

The study is currently getting underway. Results 

and conclusions will be provided as they become 

available. 

FY 2003 Publications/Presentations 

1. Presentation by Fouad H. Fouad to the Southern 

Research Institute at the Department of Energy 

Atlanta Regional Office on June 16, 2003. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Advanced Thermal Hydrogen Compression 

David H. DaCosta (Primary Contact), Mark Golben 

Ergenics, Inc. 

373 Margaret King Ave. 

Ringwood, NJ 07456 

Phone: (973) 728-8815; Fax: (973) 728-8864; E-mail: dacosta@ergenics.com 

DOE Technology Development Manager: Mark Paster 

Phone: (202) 586-2821; Fax: (202) 586-9811; E-mail: Mark.Paster@ee.doe.gov 

Objectives 

•	 Develop a hydride thermal hydrogen compressor that operates in conjunction with advanced hydrogen 

production technologies and improves the efficiency and economics of the compression process. 

•	 Construct and test a single-stage thermal compressor that employs miniature hydride heat exchangers 

and three purification technologies to determine threshold contamination levels (levels at which 

compressor performance is affected) for H2O, O2, CO, CO2 and CH4. 

•	 Investigate compressor capabilities to perform the dual function of compression and purification for 

impurities that adversely affect fuel cell operation (CO and CH4). 

•	 Engineer and test hydride alloys suitable for long-term operation at high pressures over 5,000 psig. 

•	 Validate the entire compressor process in a multi-stage, pilot-scale system. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Delivery 

•	 B. High Costs of Hydrogen Compression 

Hydrogen Storage 

• S. Cost 	 

•	 T. Efficiency 

Approach 

•	 Feasibility 

- Quantify H2 quality anticipated from renewable production techniques. 

- Conduct preliminary design and safety analysis. 

•	 Validate and Test 

- Determine hydride alloys’ resistance to disproportionation. 

- Validate compressor operation to >5,000 psi. 

- Determine hydride alloys’ tolerance to impurities while cycling. 

- Test effectiveness of three purification techniques (passive purification for H2O & O2, elevated 

temperature desorption for CO & CO2, inert gas venting for N2 & CH4). 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Refine Product Design 

- Determine if compression with purification is a viable alternative for improving fuel cell
 

performance.
 

- Reduce capital cost via miniature hydride heat exchangers and rapid cycling. 

Accomplishments 

•	 Determined that hydride compression's low energy cost will substantially reduce the cost of highpressure hydrogen. 

•	 Demonstrated thermal compression to 8,000 psia with a clear path to 10,000 psia. 

•	 Reduced hydrogen CO content from 300 ppm to less than 10 ppm to protect fuel cell catalyst. 

Future Directions 

•	 Determine upper limits and removal efficiencies for contaminants that might damage either fuel cells 

or advanced storage media. 

•	 Refine product design. 

•	 Demonstrate full-scale hydride thermal compression at a hydrogen refueling station. 

Introduction 

The hydride thermal compressor is an 

absorption-based system that uses the properties of 

reversible metal hydride alloys to silently and cleanly 

compress hydrogen; hydrogen is absorbed into an 

alloy bed at ambient temperature and, subsequently, 

is released at elevated pressure when the bed is 

heated. Compression energy can be supplied by hot 

water and, for the very high pressures being 

considered for on-board hydrogen storage, is a 

fraction of the energy cost of mechanical 

compression. The primary technical objective of this 

project is to determine whether hydride compressors 

can be used for non-pure hydrogen streams likely to 

result from advanced hydrogen production methods 

(i.e. from renewable resources), with the commercial 

objective of developing a viable hydride compressor 

that offers substantial benefits over mechanical 

compressors. 

A pilot-scale hydride thermal compressor was 

built and is being tested to determine the extent to 

which a hydride compressor can both tolerate and 

remove impurities from the hydrogen stream. In 

particular, CO is present in hydrogen from many 

advanced production processes and must be removed 

to prevent damage to fuel cell electrode catalyst. 

Removing CO in the compression process can be 

more cost effective than other hydrogen purification 

schemes. A novel process has been developed that 

reduces carbon monoxide levels to less than 10 ppm. 

In addition, the compressor employs miniature 

hydride heat exchangers to reduce capital cost and 

has operated to pressures in excess of 8,000 psia. 

Approach 

Advanced Thermal Hydrogen Compression is a comprehensive project with three phases: feasibility, validation and test, and product refinement. A full-scale 

demonstration at a hydrogen refueling station is anticipated following the completion of the current project. 

In the feasibility phase of the project, Ergenics, 

Inc. investigated the application of thermal hydrogen 

compression to hydrogen produced from renewable 

resources and developed a preliminary thermal 

compressor design for comparison with conventional 

mechanical compressors. A hazardous operation 

safety analysis of the thermal compressor system was 

completed. Thermal hydrogen compression was 

found to have distinct operational and economic 

advantages over mechanical compression for a 

majority of advanced hydrogen production 

processes. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

In the validation and test phase of the project, a 

pilot-scale compressor and test stand were built and 

are being operated to determine the extent to which a 

hydride compressor can both tolerate and remove 

impurities from the hydrogen stream. While testing 

is on-going, excellent results have been achieved and 

are reported below. 

Product refinement has included the 

demonstration of hydride compression to 8,000 psia 

with a clear path to 10,000 psia. In addition, 

complexity and cost of the compression process have 

been reduced through the identification of 

disproportionation resistant hydride alloys [1]. A 

competitive analysis of compressor efficiency and 

fuel costs for operation at 5,000 and 10,000 psia 

indicates that hydride compression has eight times 

lower energy cost than mechanical compression, 

which will be necessary to meet the hydrogen 

delivery cost goals of $3.00 per gallon of gasoline 

equivalent by 2004 and $1.50 per gallon of gasoline 

equivalent by 2010. 

Results 

Effect of CO on Alloy Capacity. Ergenics 

developed and demonstrated a novel CO elimination 

process that allows the hydride compressor to 

tolerate and remove CO from the hydrogen stream. 

Figures 1 and 2 show the effect of CO on alloy 

capacity with cycling. Figure 1 shows that hydride 

alloy capacity undergoes a gradual reduction with 

cycling when hydrogen with CO is fed to the 

compressor without the CO elimination feature. If 

left alone, compressor performance would rapidly 

degrade. The positive impact of the novel CO 

elimination process is shown in Figure 2, where alloy 

capacity remains stable as the alloy is cycled. 

During testing with CO, the compressor alloy 

behavior was periodically checked for changes by 

pressure-composition-temperature (PCT) isotherm 

tests. Figure 3 shows that the CO elimination feature 

allows the compressor alloy to maintain its 

performance over repeated cycles. In order to verify 

that the PCT performance was not being affected by 

potential test stand leakage, two additional 

absorption tests, numbers 3 and 4, were done after 10 

cycles. The results conform to the isotherm of “Abs. 

2” and have been omitted from Figure 3 for clarity. 

The slight differences in plateau pressure are a result 

of ambient temperature differences on the days the 

tests were performed. 

CO Elimination. The composition of the 

compressor discharge with the CO elimination 

feature is depicted in Figure 4. The CO elimination 

process results in a reduction of CO from 300 ppm at 

Figure 2. The CO Elimination Feature Maintains Alloy 

Capacity at a Constant Level 

Figure 1. When 300 ppm CO Is Added to Feed 

Hydrogen, Alloy Capacity Gradually 

Figure 3. PCT Tests Indicate the Hydride Alloy Is Not 

Damaged During Testing with CO
 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

the compressor inlet to the 10 ppm level necessary to 

protect fuel cell catalyst. Figure 4 illustrates that 

most of the CO is converted into methane (CH4) and 

the methane is released in large spikes (>1,000 ppm) 

at the beginning of each cycle. This suggests that 

methane can be removed from the hydrogen stream 

via inert gas venting using an economically small 

amount of hydrogen. A momentary opening of the 

vent valve will sweep the methane away. Ultimately, 

the vent gas will be routed to the hot water heater for 

recapture of its heating value. 

Very High Pressure. The compression capability of 

the advanced hydride compressor is presented in 

Figure 5, which plots inlet and outlet hydrogen 

pressure and inlet water temperature vs time for one 

compression cycle. Compressed hydrogen is vented 

via a back-pressure regulator. For this test, the 

regulator was set at 8,200 psia (56 MPa). The slight 

fluctuation in water temperature is associated with 

the natural gas heater cycling on and off and, 

interestingly, causes a slight, but detectable, 

fluctuation in hydrogen pressure. 

The test stand uses an ethylene glycol-water 

mixture for the heat transfer fluid, which has an 

upper temperature limit of 175°C to prevent boiling. 

Substituting the ethylene glycol-water mixture with a 

silicone-based heat transfer fluid will permit 

operation to 200°C with pressures over 10,000 psia. 

Energy Cost and its Effect on the Delivered Cost 

of Hydrogen. The hydride thermal compressor is a 

form of “heat engine” based on the Carnot 

thermodynamic cycle [2]. Its energy efficiency is 

based on the temperature difference between a hot 

energy source and a cold heat sink (i.e. hot water and 

cooling water), with efficiency increasing with a 

larger difference in temperature. 

By using a traditional form of heat energy, such 

as natural gas, cycle economics benefit from an 

increase in hot water temperature. Using a heat 

transfer fluid from a gas-fired heater at 130°C and 

30°C cooling water, hydride compressor efficiency is 

approximately 15 percent. While 15 percent is about 

1/2 that for an electric-motor-driven mechanical 

compressor operating around 3,000 psia, electricity is 

about 6 times costlier than natural gas, so the hydride 

compressor will enjoy a 67% lower energy cost. 

Figure 5. Testing to 8,000 psia 

Figure 4. The CO Elimination Feature Reduces Outlet 

CO Concentration from 300 to 10 ppm 

Figure 6.	 Hydride Thermal Compression's Low Energy 

Cost Will Substantially Reduce the Cost of 

Hydrogen 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

The energy cost savings are magnified at the 

high pressures being looked at for the first generation 

of hydrogen vehicles. Mechanical compressor 

efficiencies decline to a range of 8% to 12% at 5,000 

psia and only 4% to 6% at 10,000 psia. Hydride 

compression efficiencies remain in the 15% and 10% 

range, respectively. A table relating compression 

energy cost as a function of the DOE hydrogen cost 

targets is presented in Figure 6. Hydride 

compression reduces energy cost from 5 to 8 times. 

Conclusions 

The hydride thermal hydrogen compressor 

demonstrated high compression, tolerance to 

impurities, and the ability to both compress and 

purify hydrogen. An energy cost analysis shows 

hydride compression substantially reduces the 

delivered price of high-pressure hydrogen. 

Advanced thermal hydrogen compression 

directly supports the technical targets established in 

the Department of Energy’s Multi-Year Research, 

Development and Demonstration Plan as follows: 

•	 H2 Cost: Reduce compression energy costs by 

up to an order of magnitude to meet the H2 cost 

goals of: 

- Long Term: $1.50/gallon of gasoline 

equivalent (2010)
 

- Near Term: $3.00/gallon of gasoline 

equivalent (2004)
 

•	 Energy Density: Demonstrate pressures of 

5,000 and 10,000 psi to support high pressure 

tank development. 

 FY 2003 Progress Report 

•	 H2 Purity: Increase H2 quality to protect both 

fuel cell catalyst and advanced hydrogen storage 

materials (<10 ppm CO). 

•	 Complex/Carbon Materials: Knowledge of 

impurity effects on compressor hydrides will 

establish a baseline for understanding impurity 

impact on advanced storage materials (alanates 

& carbon nanomaterials). 

References 

1. D. DaCosta, M. Golben. "Disproportionation 

Resistant Alloy Development for Hydride 

Hydrogen Compression", Proceedings 2002 U.S. 

Department of Energy Hydrogen Program Annual 

Review Meeting, Golden, May 6-8, 2002, NREL/ 

CP-610-32405. 

2. D. DaCosta, M. Golben, D.C. Tragna. "Metal 

Hydride Thermal Hydrogen Compression", 

Proceedings 14th World Hydrogen Energy 

Conference, Montreal, June 9-13, 2002. 

FY 2003 Publications/Presentations 

1. D. DaCosta, M. Golben. "Thermal Hydrogen 

Compression with Purification", International 

Energy Agency Hydrogen Implementing 

Agreement, Task 17 - Solid and Liquid State 

Hydrogen Storage Materials Workshop, Geneva, 

Switzerland, September 9-11, 2002. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Uninterrupted Power Source 

Robert R. Aronsson (Primary Contact), Karl Kordesch, Martin Cifrain, Gerold Koscher, Gottfried 

Faleschini, Viktor Hacker 

Apollo Energy Systems, Inc. 

4747 North Ocean Drive 

Fort Lauderdale, Florida 33308 

Phone: (954) 783-7050; Fax: (954) 785-0656; E-mail: electricauto@worldnet.att.net 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

To supply a fuel cell/battery power plant system which can supply immediate power (from l to 5 kW) to the 

grid in case of power failure 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

Approach 

•	 Design a 1- to 5-kW fuel cell/battery power plant system 

•	 Test at in-house and in outside laboratories 

•	 Analyze the results of the tests and finalize the design 

Accomplishments 

•	 Since the inception of this project, testing of a 300-watt Apollo alkaline fuel cell coupled with a lead 

cobalt battery has been carried out. 

•	 In December, 2002, a 2.2-kW alkaline fuel cell and lead-acid battery were tested at Hydrolec
 

Incorporated of Jacksonville, Florida, one of Apollo's customers.
 

•	 From January to June, 2002, a 2.5-kW alkaline fuel cell was tested by Apollo at a fuel cell
 

manufacturing plant in Cologne, Germany.
 

•	 Preparations are being made in September, 2003, to test a 2-kW alkaline fuel cell and lead cobalt 

battery at the Florida Atlantic University. 

•	 An ammonia cracker was developed and tested at the Technical University of Graz in Austria under 

the direction of Dr. Karl Kordesch. This provides an excellent method of delivering hydrogen to the 

fuel cell. 

•	 The ammonia cracker has been in continuous operation at Apollo's laboratory in Fort Lauderdale, 

Florida. 

•	 A larger and more advanced version of the ammonia cracker was developed and tested at the Apollo 

Fuel Cell Laboratory in Austria and has been sent to Fort Lauderdale, Florida, for further testing and 

evaluation. Plans are to test it at the Florida Atlantic University. 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Production of a special battery for the Apollo Power Plant system has been subcontracted to 

Millennium Battery Company, a manufacturer of batteries in Miami, Florida. 

•	 A study of power plant-to-grid switches has been made. 

•	 A study of hydrogen sensors has been made. 

Future Directions 

•	 A 2-kW Apollo Power Plant has been built and will be installed at the Florida Atlantic University in 

Boca Raton, Florida, for demonstration to interested parties. 

•	 A 5-kW Apollo Power Plant will be built, using experience gained from the 2-kW unit, to be delivered 

to DOE. 

Introduction 

Many companies are developing fuel cells which 

can be used to supply instant power to the grid in 

case of grid failure. In the low temperature fuel cell 

field (70-80°C), development has proceeded on two 

types of fuel cells: the alkaline fuel cell (AFC), 

which has been used by the National Aeronautics & 

Space Administration (NASA) since the Apollo 

Moon Mission of the 1960s, and the proton exchange 

membrane (PEM) fuel cell. The AFC has the highest 

cell voltage and efficiency of any fuel cell but was 

considered too expensive for commercial 

applications. However, it has been shown that the 

AFC can be produced at a much lower cost than its 

competitor for earth applications, and it has been 

demonstrated that the AFC is less complicated, not 

requiring humidification and air compressors. Also, 

it has been shown that the AFC can be 

advantageously shut down during periods when its 

energy is not needed, while the PEM fuel cell can 

never be routinely shut down. To take advantage of 

this shut-down feature, Apollo Energy Systems has 

developed a system wherein a battery can be 

paralleled with the AFC and can do most of the work 

while the AFC is dormant. This prolongs the life of 

the AFC and results in lower overall cost since the 

fuel cell (which operates only intermittently) is more 

expensive than the battery (which is in continuous 

operation). It has also been found that the AFC can 

operate on far less noble metal catalyst than the PEM 

fuel cell, resulting in a lower manufacturing cost. 

Therefore, Apollo Energy Systems has embarked 

on a program of AFC development coupled with 

battery development and plans to produce Apollo 

Power Plants for residential, commercial and 

industrial applications and Apollo Electric 

Propulsion Systems for application in land, water and 

air vehicles. 

Approach 

Several prototype Apollo Power Plants of 

different electrical sizes will be tested and evaluated 

so as to create a performance base for sizing the final 

prototype fuel cell and battery combination (see 

Figure 1). Tests will be carried out at Apollo's 

laboratory in Fort Lauderdale, Florida, at the 

laboratory of one of Apollo's customers, at a fuel cell 

facility in Germany, at a local university (Florida 

Atlantic University of Boca Raton, Florida), and 

finally at Apollo's pilot plant in Florida which is 

planned to be constructed in the last quarter of 2003. 

Figure 1.	 2 kW Apollo Power Plant with Alkaline 

Fuel Cell stack, Lead Cobalt Battery and 

DC to AC Inverter 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Results 

•	 A 300-watt Apollo Power Plant has been built 

and is under constant test in Apollo's laboratory 

in Ft. Lauderdale, Florida. Results to date are 

positive. 

•	 A 2-kW Apollo Power Plant has been built and 

will be installed at the Florida Atlantic 

University in Boca Raton, Florida. 

Conclusions 

•	 The basic concept of combining an AFC with a 

lead cobalt battery has been shown to be 

technically viable. 

•	 As a result of this work, Apollo believes that 

Apollo Power Plants for stationary use and 

Apollo Electric Propulsion Systems for use in 

vehicles, boats and aircraft can be produced and 

effectively utilized, at reasonable prices. 

FY 2003 Publications/Presentations 

Six papers published in the Handbook of Fuel Cells - 

Fundamentals, Technology and Applications (ISBN: 

0-471-49926-9), by John Wiley & Sons, Ltd., 

Chichester, UK, 2003: 

1. Hydrogen/Oxygen (Air) Fuel Cells with Alkaline 

Electrolytes, M. Cifrain and K. Kordesch, 

Volume 2, Part 4, pp 267-280 

2. Stack Materials and Design, K. Kordesch and V. 

Hacker, Volume 4, Part 4, pp 765-773 

3. Ammonia Crackers, V. Hacker and K. Kordesch, 

Volume 3, Part 2, pp 121-127 

4. A Comparison Between the Alkaline Fuel Cell 

(AFC) and the Polymer Electrolyte Membrane 

(PEM) Fuel Cell, K. Kordesch and M. Cifrain, 

Volume 4, Part 4, pp 789-793 

 FY 2003 Progress Report 

5. Alkaline Methanol/Air Power Devices, G. A. 

Koscher and K. Kordesch, Volume 4, Part 9, pp 

1125-1129 

6. Automotive Development, V. Hacker and K. 

Kordesch, Volume 4, Part 11, pp l217-1223 

Abstracts of four papers to be presented at Fuel Cell 

Conferences in 2003 

1. Electronic Abstract, Ammonia as Hydrogen 

Source for an Alkaline Fuel Cell-Battery Hybrid 

System, K. Kordesch, V. Hacker, G. Faleschini, G., 

Koscher, M. Cifrain, Fuel Cell Seminar, Miami 

Beach, Florida, November 3-6, 2003 

2. Flowing Electrolyte Direct Methanol Fuel Cells, 

D. James, X. Deng, K. Kordesch, Fuel Cell 

Seminar, Miami Beach, Florida, November 3-6, 

2003 

3. Alkaline Fuel Cells (An Overview) - Tutorial on 

Fuel Cells, K. Kordesch and M. Cifrain, 

204th Meeting of the Electrochemical Society, 

Orlando, Florida, October 12-17, 2003 

4. Can Refillable Alkaline Methanol-Air Systems 

Replace Metal-Air Cells?, K. Kordesch and G. 

Koscher, 23rd Power Sources Symposium, 

September 22-24, Amsterdam, Holland 

Special Recognitions & Awards/Patents 

Issued 

1. 2 Patent Applications have been filed on Alkaline 

Fuel Cells, Karl Kordesch, M. Cifrain 

2. 1 Patent Application has been filed on an 

Ammonia Cracker, Gottfried Faleschini, Viktor 

Hacker, Karl Kordesch 

3. 3 Patent Applications have been filed on Tri-Polar 

Lead-Cobalt Batteries, Robert Aronsson 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Hydrogen Fuel Based Power Park (New FY 2004 Project) 

Raymond S. Hobbs 

Pinnacle West Capital Corporation 

Mail Station 9110 - Box 11D 

P.O. Box 53999 

Phoenix, AZ 85072-3999 

Phone: (602) 250-1510; Fax: (602) 256-2606; E-mail: Raymond.Hobbs@pinnaclewest .com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Subcontractors: 

Collier Technologies - Reno, Nevada 

Arizona Public Service - Phoenix, Arizona 

Objectives 

•	 Develop the process requirements for a hydrogen fuel based power park utilizing photovoltaic and 

electric grid energy inputs and providing hydrogen energy storage for electricity generation, hydrogen 

for vehicle fueling, potable water, and chilled water cooling. 

•	 Demonstrate each component required to support the power park concept. 

•	 Analyze the economic viability of the power park based on component costs and performance, and 

estimates of power park construction cost. 

•	 Develop safe design practices for hydrogen handling. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Maintenance and Training Facilities 

•	 H. Hydrogen from Renewable Resources 

•	 I. Hydrogen and Electricity Coproduction 

Approach 

The focus of this project is to evaluate the 

technical and economic feasibility of a hydrogen 

fuel based power park. The project will develop the 

process requirements for a hydrogen fuel based 

power park designed to provide a maximum 

electrical power of 100 kW, daily electric energy 

output of 200 kWh and daily hydrogen motor fuel 

output of 18 kg. The viability of the process will be 

demonstrated by development and testing of 

prototype equipment for each component of the 

power park process. Based on the results of this 

testing, performance and cost data will be projected 

for full size process components. The economic 

feasibility of the power park will then be evaluated 

based on alternative resources for electricity 

generation, hydrogen motor fuel production, 

production of potable water and chilled water for 

cooling. 

Energy inputs to the power park will include 

photovoltaic and electric utility grid. A 6-kW 

photovoltaic array will be used to demonstrate the 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

photovoltaic component of the power park process. 

Energy storage will be in the form of gaseous 

hydrogen produced from either electrolysis of water 

or a proton exchange membrane (PEM) fuel cell. 

The hydrogen will be compressed and stored at high 

pressure (as much as 700 bar). A hydrogen 

compression and storage system with 172 kg of high 

pressure hydrogen storage will be used to 

demonstrate the storage component of the power 

park concept. 

During periods of peak electrical demand, power 

park electrical output will be supplemented by 

generation resources fueled with stored hydrogen. A 

100-kW hydrogen fueled engine generator will be 

used to demonstrate the generation component of the 

power park process. A fuel cell will be incorporated 

in the power park generation component if found to 

be economically feasible based on published 

performance data and prices. 

In addition to electrical energy output, the power 

park will provide hydrogen motor fuel. The Arizona 

Public Service hydrogen fueled internal combustion 

engine powered fleet will be used to demonstrate the 

 FY 2003 Progress Report 

vehicle fueling component of the power park. The 

vehicle fleet consists of thirteen vehicles utilizing 

hydrogen and hydrogen blends with compressed 

natural gas. 

As a byproduct of the electric generation using 

hydrogen fuel, the power park will provide potable 

water and cooling. The cooling component of the 

power park process will be demonstrated using 

exhaust heat from the 100-kW hydrogen fueled 

engine generator to produce up to 20 tons of cooling 

in absorptive cooling units. The potable water 

component of the power park process will be 

demonstrated by collecting and processing water 

from the exhaust of the 100-kW hydrogen fueled 

engine generator. 

With both cost and performance results available 

from the power park concept component testing, the 

overall power park performance and economics will 

be modeled and compared with alternative sources of 

energy production, storage and delivery. 

Additionally, power park system safety issues will be 

evaluated, including design, regulatory, standards 

and building code issues. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Research and Development of a Proton Exchange Membrane Fuel Cell, Hydrogen 

Reformer, and Vehicle Refueling Facility 

Venki Raman (Primary Contact), Robert Sinuc, Mark Wait 

Air Products and Chemicals Inc. 

7201 Hamilton Boulevard 

Allentown, PA 18195 

Phone: (610) 481-8336; Fax: (610) 706-7463; E-mail: ramansv@apci.com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Subcontractor: Plug Power Inc., Latham, NY 

Objectives 

•	 Design, develop, and demonstrate small on-site H2 production system for stationary fuel cells and H2 

fuel stations. 

•	 Design, construct, and operate a multipurpose refueling station to dispense H2/CNG blends and pure 

H2. 

•	 Design, construct, install and operate a H2-fueled stationary 50-kW fuel cell. 

•	 Maintain safety as a top priority in the design and operation of the fueling station and fuel cell. 

•	 Evaluate operability, reliability, and economic feasibility of integrated power generation and vehicle 

fueling system. 

•	 Obtain adequate operational data on fuel station to provide basis of future commercial fueling station 

designs. Develop appropriate "standard" designs for commercial applications. 

A related goal, beyond the scope of the current project, is to expand the current "Energy Station" facility to 

serve as the first commercial facility when sufficient hydrogen demand develops. A vision is to have this 

facility ultimately serve as a link in an emerging regional/national H2 corridor. 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 C. Hydrogen Refueling Infrastructure 

•	 E. Codes and Standards 

•	 I. Hydrogen and Electricity Coproduction 

Approach 

•	 Several small-scale natural gas based fuel processing technologies under development by others were 

tested in the laboratory and field environments prior to and during the period of the current project. 

These included partial oxidation (POX), autothermal reforming (ATR), and steam methane reforming 

(SMR) technologies. 

•	 POX technology was eliminated from further consideration prior to the start of the current project. 

•	 The ATR and SMR fuel processors were integrated with small-scale pressure swing adsorption (PSA) 

systems and tested extensively. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Based on the experience from the testing and on the results of an economic analysis, the final 

technology selection was made.
 

•	 The 50-kW fuel cell stack design was based on existing 7.5-kW reformate-based stack modules 

developed for residential power generation. Modifications were made to allow operation on pure 

hydrogen. 

•	 Fuel station design was based on previous experience gained from over 15 H2 and H2/CNG fuel 

stations. The ability to dispense various blends of H2 and CNG is provided for in the design. 

•	 Extended duration operation of the fully integrated hydrogen generation, fuel cell, fuel station system 

will be conducted to address robustness, performance, and economic feasibility of this "Energy 

Station" concept. 

Accomplishments 

•	 Based on extensive test results and an economic analysis, SMR technology was selected for the fuel 

processor. 

•	 An SMR fuel processor from Harvest Energy Technologies integrated with a PSA system from 

QuestAir Technologies was installed and started up at the Las Vegas site in August 2002. The unit 

operated well and achieved H2 product purity in excess of 99.95%. 

•	 The multipurpose fuel station was commissioned in July 2002 (started up with delivered liquid 

hydrogen). CNG/H2 and H2 fuel dispensing have been successfully performed on a fueling test rig, 

CNG/H2 internal combustion engine (ICE) vehicles and H2 fuel cell vehicles. 

•	 The 50-kW stationary fuel cell was started up in August 2002 on hydrogen supplied by the SMR unit. 

Future Directions 

•	 Begin extended unattended operation of the stationary fuel cell. 

•	 Achieve extended integrated operation of the reformer, fuel cell and fuel station. 

•	 Collect site performance data to assess overall operation of the system. 

•	 Build up vehicle fleet to include 6 H2/CNG buses and several light duty vehicles. This is dependent on 

a separately funded effort. 

Introduction 

Small-scale on-site hydrogen production 

technology that can operate on readily available fuels 

such as natural gas will be required to provide 

hydrogen fuel stations in certain locations where 

delivered hydrogen is not readily available. 

However, small-scale natural gas based hydrogen 

reformers are not fully developed and will suffer 

from poor economics due to their small scale and due 

to poor utilization rates in the early years of hydrogen 

vehicle development. One approach to achieving 

high utilization rates of the reformer is to baseload it 

with a stationary fuel cell that produces electric 

power while the intermittent vehicle-fueling load is 

handled by diverting a portion of the hydrogen from 

the fuel cell to the fuel station as and when needed. 

This co-production of hydrogen fuel and electric 

power is referred to as an "Energy Station". The 

objective of this project is to demonstrate the 

technology and validate the commercial viability of 

an alternative fuel station for dispensing blends of 

hydrogen and compressed natural gas (CNG) and 

pure hydrogen to vehicles, and the co-production of 

electricity from a stationary fuel cell. A team of 

three organizations-Air Products and Chemicals Inc., 

Plug Power Inc., and the City of Las Vegas-come 

together to develop, design, procure, install, and 

operate this "Energy Station" in Las Vegas, Nevada. 

This refueling station includes onsite hydrogen 

generation equipment supplied by Air Products and a 

stationary fuel cell powered electric generator 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

supplied by Plug Power under a subcontract. The 

City of Las Vegas (CLV) is providing the site 

location and the operating and maintenance staffing 

for the refueling station. The DOE cooperative 

agreement covers a five-year nominal period (1999-

2004) for development, design, installation, startup, 

and operation of the refueling station. 

Figure 1 is a block diagram of the proposed 

refueling facility. In addition to the on-site hydrogen 

generation, a standard merchant liquid hydrogen 

supply system (liquid hydrogen storage tank and 

vaporizers) was installed to satisfy initial demand for 

hydrogen at the refueling station and to provide backup supply for additional system reliability. The 

hydrogen compression, storage, blending and 

dispensing systems are capable of supplying predetermined blends of H2 and CNG to be dispensed to 

trucks and buses with ICEs converted to run on H2/ 

CNG mixtures. The station will also be able to 

dispense pure hydrogen to vehicles. Currently there 

are one light duty vehicle (LDV) and one para-transit 

bus fueled with the CNG/H2 blend. The fuel cell 

operates on pure hydrogen to generate electric power, 

which is put back on the local power grid. The fuel 

cell will be operated to balance the hydrogen demand 

on the hydrogen generator for vehicle refueling. 

Upon successful testing/operation of the first 

CNG/H2 fueled para-transit bus, CLV will proceed to 

convert six new CNG fueled buses to CNG/H2 

blended fuel operation. They expect to have all six 

buses converted over a six-month period, nominally 

one bus per month through December 2003. H2 

demand growth is expected to continue as additional 

Figure 1. Overall Integration System Configuration 

 FY 2003 Progress Report 

buses and light duty vehicles are converted to the 

alternative fuels over the remaining two years of the 

demonstration project. It is also proposed that a 

natural gas-based onsite hydrogen generator will be 

installed and operated at the refueling station. 

Should the alternative vehicle refueling 

demonstration station prove to be successful, it is 

anticipated that vehicle fleets would continue to grow. 

Approach 

Air Products evaluated various small-scale 

developmental natural gas reformation technologies 

via extensive laboratory and field testing. These 

technologies included partial oxidation, autothermal 

reforming and steam methane reforming. These test 

results were the basis for technology selection for the 

fuel processor. The fuel processor was integrated 

with a PSA system supplied by QuestAir to develop 

the on-site system capable of generating pure 

hydrogen from natural gas. 

The 50-kW fuel cell was built by assembling 

eight 7.5-kW residential fuel cell stacks developed 

by Plug Power for the residential power market. 

The residential system was designed to operate on 

reformate; thus, modifications were required for the 

pure hydrogen service in this project. Extensive 

testing of the fully-assembled module at Plug 

Power's Latham, New York, facility was conducted 

to qualify individual systems and the final system 

configuration. 

Results 

Hydrogen Generator. The hydrogen generator (see 

Figure 2) was installed, commissioned and placed into 

Figure 2. View of the Hydrogen Generator (Left) and 

Fuel Cell (Right) 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

operation in the summer of 2002. On-spec hydrogen 

production, with purity in excess of 99.95%, was 

established in August 2002. Successful process 

operation of the hydrogen generator was achieved 

without process modification to the system after exworks delivery of the unit to the site for operation. 

Since the initial establishment of hydrogen 

production, the unit has achieved an aggregate runtime of over 2200 hours. The integrated hydrogen 

generator system controls have been demonstrated to 

achieve the full range of expected operability control. 

The hydrogen generator is capable of one-button start, 

with automated start-up ramping and subsequent load 

following capability. The hydrogen generator can be, 

and is, operated remotely, including remote start-up 

where the appropriate control permission exists based 

on the automated system's diagnosis of the unit status. 

In other words, the system is engineered to recognize 

the potential of conditions from a shutdown mode that 

necessitate a physical check prior to restart. 

Consequently, the system can also recognize the safe 

condition from which a remote start can be initiated 

via telemetry with the appropriate control program 

interface. Consistent with this, remote operation and 

monitoring of the hydrogen generator has been 

demonstrated during this period. 

Produced hydrogen has been utilized for electrical 

power production by the fuel cell power plant, as well 

as for fueling of ICE vehicles with H2/CNG blends 

and fuel cell vehicles with hydrogen when required. 

The fuel cell continues to establish the majority of 

demand for the on-site generated hydrogen during fuel 

cell availability. The availability of the fuel cell, 

however, has not been highly reliable. As expected, 

vehicle-fueling demand is insufficient for utilization of 

the full hydrogen generator production capacity. The 

fuel cell has been able to present a demand for the 

produced hydrogen during the anticipated fleet buildup period. 

Fueling Station. Operation of the fueling station was 

established in July 2002. The fueling station segment 

of the Energy Station consists of liquid hydrogen 

storage, gaseous hydrogen storage, product 

compression, CNG/H2 fuel blending, and CNG/H2 

and hydrogen fuel dispensing (see Figure 3). 

The CNG/H2 fuel dispensing was tied into the 

City of Las Vegas's fuel consumption accounting 

system for seamless accounting with their existing 

fleet of CNG vehicle operations. 

Since operation of the fueling station was 

established, satisfactory vehicle fueling functionality 

has been demonstrated. Fueling operations have been 

performed for both hydrogen fuel cell vehicles as well 

as blend CNG/H2 internal combustion engine 

vehicles. 

Fully integrated control functionality of the 

Energy Station has been demonstrated. 

Stationary Proton Exchange Membrane (PEM) 

Fuel Cell . The 50-kW PEM fuel cell was initially 

started up in August 2002, and a continuous run time 

of 160 hours was logged. The unit successfully ran for 

three days before it was tripped by the reformer. It 

was restarted successfully and ran another three days 

before it was tripped due to single cell failure. 

Several operational issues were identified and 

fixes implemented: 

•	 Scanning of individual cell voltage was unreliable and was traced to a design issue with the cell 

scanner approach in multiple-stack configurations. The scanner cards were redesigned, successfully installed, and operational in April 2003. 

•	 There was inadequate draining of water from 

multiple stacks with a common drain. The water 

Figure 3. View of the Fuel Station 

4 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

drain valve was successfully modified in April 

2003. 

Following these fixes, the unit continued to have 

operational issues with cell voltage falloff that made 

continuous operation an issue. This issue appears to 

fault the concept of multiple stacks with no provision 

to accommodate the need of each stack with respect to 

voltage output, over stoichiometric flows to both 

anode and cathode, humidity of both anode and 

cathode, and temperature of each stack. The fuel cell 

stack will be replaced during the week of July 16, 

2003, and will be restarted. 

A possible issue with timing of electric load 

shedding on shutdown has been identified. The timing 

will be analyzed and software and/or hardware 

modifications made to eliminate potential ground 

looping, which may be contributing to stack failures. 

Conclusion 

•	 The Energy Station is a viable operational 

concept. The fuel cell has provided a demand for 

hydrogen during the initial stages of fleet buildup with low levels of vehicle fueling demand. 

•	 Integrated control functionality is critical to 

system-wide reliability and operability. 

•	 Vehicle fleet build-up continues to be a primary 

challenge to satisfactory utilization of hydrogen 

fueling infrastructure efforts. 

•	 The fuel cell design approach of multiple stacks 

with no ability to independently manage gas 

flows, temperature, humidity and power is in 

question. 

•	 An excellent list of lessons learned has been 

compiled. Additional lessons learned from Plug 

Power single-stack 5-kW systems will be 

combined in future designs. 

 FY 2003 Progress Report 

•	 Current operating performance predicts we will 

meet the 2-3 months operation with minor 

tweaks. 

FY 2003 Publications/Presentations 

Presentations on the "Energy Station" concept 

and the Las Vegas project have been given to various 

audiences separately or in conjunction with a 

discussion of developing hydrogen infrastructure, 

including: 

1. Hydrogen Expo 2002, Hamburg, Germany, 

October 10-12, 2002 - "Pathways to Building 

Infrastructure to Support the Hydrogen Economy" 

2. U.S. - Australian Climate Action Partnership 

Opportunities Roundtable, Washington, DC, 

November 4, 2002 - "Role of Hydrogen as an 

Energy Resource for the United States" 

3. Hydrogen Energy Systems Society of Japan 

Symposium, Tokyo Institute of Technology, 

Tokyo, Japan, December 11, 2002 - "Hydrogen 

Economy Strategies- a U.S. Perspective" 

4. SAE Telephone/Webcast, April 3, 2003 - The Path 

to the Emission-Free Vehicle through the Use of 

Hydrogen as a Fuel - "Hydrogen Fuel 

Infrastructure - Creating the Future" 

Special Recognitions & Awards/Patents 

Issued 

1. Special Member award from the National 

Hydrogen Association for " ... development of the 

Las Vegas Refueling Station, the world's first 

energy station featuring the co-production of 

hydrogen and electricity ..." 

5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Choice for Fuel Cell Vehicles: Stakeholder Risk Analysis 

Stephen Lasher (Primary Contact), Peter Teagan, Stefan Unnasch 

TIAX, LLC 

Acorn Park 

Cambridge MA, 02140 

Phone: (617) 498-6108; Fax: (617) 498-7054; E-mail: lasher.stephen@tiax.biz 

DOE Technology Development Manager: Peter Devlin 

Phone: (202) 586-4905; Fax: (202) 586-9811, E-mail: Peter.Devlin@ee.doe.gov 

Objectives 

•	 Assess opportunities and risks of various fuel cell vehicle (FCV) and fuel pathways, with specific 

focus on a transtion to a hydrogen infrastructure options. 

•	 Assess impact on the various stakeholders (e.g. car manufacturers, energy companies, government, 

etc.) and how risks could be shared and minimized. 

•	 Determine what range of factors might trigger the introduction of FCVs (e.g. oil price increase, carbon 

taxes, FCV cost reduction). 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Production 

•	 AD.Market and Delivery 

Hydrogen Delivery 

•	 A. Lack of Hydrogen/Carrier and Infrastructure Options Analysis 

Hydrogen Storage 

•	 V. Life Cycle and Efficiency Analysis 

Approach 

•	 Develop a net present worth (NPW) analysis of both the fuel and vehicle aspects, but with the focus on 

the transitional risks of a hydrogen fuel infrastructure. 

•	 Generate a "straw-person" scenario of the hydrogen infrastructure introduction based on results from 

previous work, literature sources, and additional analysis. 

•	 Present the straw-person scenario assumptions and NPW results to a quorum of FCV developers, fuel 

distributors, and fuel producers. 

•	 Refine the analysis and rank the fuel pathways with respect to a set of performance criteria, in
 

particular to overall financial risk.
 

Accomplishments 

•	 Constructed a NPW analysis for hydrogen. 

•	 Generated a straw-person scenario focusing on two hydrogen fuel chains: forecourt (i.e. on-site, 

distributed) natural gas-based production and central natural gas-based production with liquid 

hydrogen delivery. 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Presented the straw-person results to a limited number of stakeholders. 

•	 Updated the NPW analysis assumptions based on stakeholder input to date. 

Future Directions 

•	 Define "lowest-cost" and "most likely" hydrogen infrastructure scenarios and present NPW results to a 

larger stakeholder audience. 

•	 Define a straw-person FCV scenario and present NPW results to a limited number of stakeholders. 

•	 Evaluate feedback and update model as appropriate based on stakeholder input. 

•	 Evaluate the technology risk, financial exposure, and safety and regulatory risks associated with the 

various fueling options for each respective stakeholder. 

•	 Generate final report for DOE vetted by key stakeholders. 

Introduction 

In the previous phase of work, TIAX assessed 

the well-to-wheel energy use, greenhouse gas 

emissions and ownership costs of various fuel 

choices for fuel cell vehicles (FCVs) at a future point 

in time assuming high capacity factors and high 

manufacturing production volumes for equipment 

(Lasher, et al 2001). However, alternative fuels, 

especially hydrogen, will require significant up-front 

investment during a transition period, representing a 

risk to both vehicle manufacturer and fuel provider. 

The financial risks involved in each of the fuel 

options vary, and the risk may shift from one player 

in the value chain to another. Dealing with this risk 

represents a formidable barrier to the use of 

alternative fuels, especially hydrogen, for FCVs. In 

the current phase of work, the DOE has 

commissioned TIAX to assess the relative risks of 

various fuel pathways for use in FCVs. 

Approach 

In order to evaluate financial risks and the effect 

that potential triggers may have on the various 

stakeholders, we will develop a net present worth 

(NPW) analysis. The NPW analysis will take into 

account the time value of money so that early 

investments are weighted more heavily than future 

profits. We will start with an assumed number of 

FCVs on the road and estimate how the alternative 

The NPW analysis will include both the fuel and 

vehicle aspects, but with the focus on the transitional 

risks of a new fuel infrastructure. 

We will generate a "straw-person" scenario of the 

hydrogen infrastructure introduction based on results 

from previous work, literature sources, and additional 

analysis. We will present the straw-person scenario 

assumptions and results to a quorum of FCV 

developers, fuel distributors, and fuel producers, to 

verify and refine the assumptions and the analysis and 

discuss the risk aspects for each stakeholder. Based on 

the feedback from these presentations, we will refine 

our analysis and rank the fuel chains with respect to a 

set of performance criteria, in particular to overall 

financial risk. 

Results 

We have developed a straw-person scenario with 

preliminary input assumptions. The assumed 

hydrogen FCV introduction is based on the 

conservative scenario results from DOE's Vision 

Model. Hydrogen infrastructure introduction is 

assumed to be built up regionally with 10% regional 

coverage achieved in the 3rd year (10% coverage 

means one in ten existing fueling stations would have 

hydrogen capacity). Hydrogen infrastructure 

proceeds from region to region so that local coverage 

can be achieved while maintaining reasonable 

capacity factors. In a single region, hydrogen fueling 

fuel infrastructure (i.e. hydrogen) will be introduced stations are carefully constructed to coincide with 

over time. Other inputs will include capital costs as a appropriate FCV introduction over a 15-year period. 

function of production volume, operating costs, fuel A single region is assumed to be similar in size and 

prices (e.g. gasoline, hydrogen), and fuel savings. make-up to the South Coast Air Quality Management 

2 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

District (SCAQMD). The 50-year infrastructure of the cash flow and capital investment of the entire 

introduction for the whole U.S. is presented in Figure hydrogen infrastructure. 

1. Note that we have assumed installations will favor 

smaller stations (30 FCV/day capacity) with their 

higher capacity factors in the early years (0-20 years) 

compared to larger stations. However, larger stations 

(300 FCV/day capacity) are favored overall when 

demand increases due to their lower capital costs per 

unit hydrogen capacity. Capital costs for the fueling 

station equipment are reduced using progress ratios 

as production volumes (i.e. number of fueling 

stations) increase. 

A NPW model was constructed for forecourt and 

central plant hydrogen generation for use in direct 

hydrogen FCVs. The model can be used to track the 

NPW results for various input assumptions, such as 

FCV and hydrogen infrastructure introduction 

scenarios, central plant size, hydrogen selling price, 

fueling station capital and energy costs, and many 

others. Figure 2 is an example of the sensitivity of 

the hydrogen infrastructure NPW to various input 

parameters. The straw-person baseline scenario 

assumes hydrogen is sold for $2.80/kg (excluding 

tax), which would result in cost parity with a 

conventional vehicle on a $/mi basis assuming 30 

mpg and $1.07/gal for a conventional vehicle and 80 

mpeg for a hydrogen FCV. The model is also set up 

to track cash flow and capital investment over time 

for the various stakeholders. Figure 3 is an example 

Figure 1. National Hydrogen Stations Buildup - Strawperson Scenario 

It should be noted that the straw-person 

assumptions are based on projections of the future 

cost of a high efficiency hydrogen infrastructure. We 

did not use DOE targets, and there is on-going work 

at DOE and various industries to improve costs and 

performance beyond those projected here. In 

addition to refining the straw-person analysis, 

incorporating the potential improvements from the 

following could improve the straw-person NPW and 

cash flow results: 

Figure 2. Hydrogen Infrastructure 50-Year NPW 

Sensitivity - Straw-person Scenario 

Figure 3.	 Cash Flow and Capital Investment for 

Hydrogen Infrastructure - Straw-person 

Scenario 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

•	 Utilize existing excess hydrogen capacity (e.g. 

methanol and ammonia plants) 

•	 FCV demonstrations and fleets (e.g. buses, government vehicles, etc.) 

•	 Hydrogen internal combustion engine vehicles 

•	 Energy stations (i.e. hydrogen forvehicle fueling 

and stationary power) 

Conclusion 

Using the straw-person scenario for hydrogen 

infrastructure introduction, a few general conclusions 

can be drawn: 

•	 Hydrogen production costs could ultimately be 

low (<$2/kg), but initial costs are high due to 

high capital cost and low capacity factors in the 

early years (see Figure 4). 

Figure 4. Projected Hydrogen Costs from Forecourt
 

Stations - Straw-person Scenario
 

 FY 2003 Progress Report 

•	 If hydrogen were priced to provide cost-parity 

with conventional vehicles, the hydrogen infrastructure stakeholders could turn a profit in the 

long-run, but break-even would not be achieved 

for many years. 

•	 Near-term pathways are needed to improve 

capacity factors and reduce capital cost of the 

hydrogen infrastructure. 

References 

1. Lasher, S., J. Thijssen, S. Unnasch, "Guidance for 

Transportation Technologies: Fuel Choice for 

Fuel Cell Vehicles", 2001 Annual Progress Report 

- Fuels for Advanced CIDI Engines and Fuel 

Cells, EERE OTT, November 2001 

FY 2003 Publications/Presentations 

1. Lasher, S., "Guidance for Transportation 

Technologies: Fuel Choice for Fuel Cell 

Vehicles", presented at 2002 American Chemical 

Society Meeting, Boston MA, August 18-22, 2002 

2	 Thijssen, J., "Fuel Choice for Fuel Cell Vehicles: 

Near-Term and Long-Term Perspectives", poster 

at 2002 Fuel Cell Seminar, Palm Springs CA, 

November 18-21, 2002 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Commercialization: Transportation Fuel for the 21st Century 

William L. Clapper (Primary Contact), Gayl Biondi, Tommy Edwards, Polo Del Toro, 

Michael Johnston 

SunLine Services Group 

32-505 Harry Oliver Trail 

Thousand Palms, CA 92276 

Phone: (760) 343-3456; Fax: (760) 343-0576; E-mail: bclapper@sunline.org 

DOE Technology Development Manager: Christopher Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-5860; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

•	 Relocate and reassemble the Clean Air Now Project and the Schatz Energy Research Center Project 

(SERC). 

•	 Produce, compress, store, and dispense hydrogen using grid, solar, and wind electricity and
 

determine cost.
 

•	 Move fuel cell vehicles to SunLine from the City of Palm Desert for continued testing. 

•	 Produce hydrogen from a natural gas autothermal reformer. 

Approach 

•	 Hire a construction manager to implement the detailed construction plans developed in the earlier 

phase of the project and adapt them to the SunLine site. 

•	 Prepare the site. 

•	 Construct the following: 

•	 SERC Hydrogen Production Building 

•	 The Palm Desert Vehicle Building 

•	 The Zweig Community and Outreach Building (contribution by SunLine Transit Agency) 

•	 Pad and distribution system for the Solar Flat Plate Arrays 

•	 Pad and distribution system for the Solar Photovoltaic Tracking Arrays 

•	 Pad and utilities for the Stuart Energy electrolyzer 

•	 Pad for the 4,000 psi ground storage tanks 

•	 Pad for the 3,130 psi hydrogen tube trailer 

•	 Pad, utilities and wall for small vehicle refueling area 

•	 Hydrogen underground distribution system 

•	 Pad for hydrogen dispenser at the SunLine public fueling island 

Accomplishments 

•	 Installed the following: 

- 0.1-kg Teledyne Energy Systems electrolyzer 

- PDC hydrogen compressor and fueling area for small vehicles 

- 3-kg Stuart Energy electrolyzer 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

- 218 Solar Flat Plate Arrays 

- 144 Solar Photovoltaic Tracking Arrays 

- 4,000 psi ground storage tanks 

- 3,130 psi hydrogen tube trailer 

- Dispensing system for small vehicles 

- Dispensing system for buses and automobiles 

- Hydrogen Burner Technologies natural gas partial oxidation reformer 

- 5000 psi ground storage 

- 5000 psi compressors 

- 5000 psi dispenser 

- Controls and valving 

•	 Tested three fuel cell golf carts. 

•	 Tested one street legal neighborhood electric vehicle. 

•	 Tested one EXCELLSiS (formerly-now Ballard) 40-foot fuel cell bus for 13 months. 

•	 Tested one 30-foot ISE Research, Thor Industries, El Dorado, UTC Fuel Cells fuel cell bus for 6 

months in fixed route transit service. 

•	 Tested two older model L-10 Cummins internal combustion engine (ICE) buses operating on blended 

hydrogen and compressed natural gas (CNG) buses. 

•	 Upgraded and modified two new Cummins-Westport 5.9 l B+ internal combustion engines to operate 

on blended hydrogen and CNG (HCNG). 

•	 Developed the first hydrogen technician training manual, "Hydrogen Fuel Cell Engines and Related 

Technologies," which is posted on the National Renewable Energy Laboratory's (NREL's) website, 

and from October 2002 to August 14, 2003, there were 508,321 "hits". 

•	 Demonstrated the production of hydrogen using the Stuart Energy P-3 electrolyzer to support the 

operation of the XCELLSiS fuel cell (FC) bus and the ThunderPower hybrid electric FC bus (see 

Figure 1). 

•	 Demonstrated the production of hydrogen from solar energy using the Teledyne Energy Systems Altus 

20 electrolyzer (see Figure 2). 

Stuart P3 Hydrogen Production 

Year Scf H2 KWh 

2000 833,500 108,100 

2001 1,754,737 209,524 

2002 832,536 107,933 

Figure 2.	 Hydrogen Production Data for the Teledyne 

Electrolyzer 

Figure 1. Hydrogen Production Data for the Stuart 

Energy Electrolyzer 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Demonstrated the production of hydrogen from solar energy using the Teledyne electrolyzer (see 

Figure 3). 

•	 Demonstrated the production of hydrogen from the Hydrogen Burner Technology (HbT) natural gas 

reformer. 

Future Directions 

•	 Collect data on the operation of two blended HCNG ICE buses in fixed route service and two
 

Cummins Engine CNG 5.9 l B+ buses in fixed route service, and compare the results.
 

•	 In cooperation with Alameda County (AC) Transit, who is purchasing 3 Van Hool 40-foot fuel cell 

hybrid electric buses, purchase through a Federal Transit Administration (FTA) grant a Van Hool 40-

foot fuel cell hybrid electric bus for fixed route service for SunLine Transit Agency. 

•	 Purchase, using SunLine's replacement bus program, a 40-foot New Flyer hydrogen ICE bus for fixed 

route service. 

•	 Investigate the emissions reduction effects of adding an oxidation catalyst to the ICE HCNG and CNG 

buses in testing. 

•	 Install and operate a HyRadix natural gas auto-thermal reformer. 

•	 Collect data and investigate the parameters affecting the production of hydrogen from the natural gas 

reformer. 

Solar Production Solar Arrays theData for

Period Energy (kWh) 

Jan-02 2,166 

Feb-02 2,349 

Mar-02 2,757 

Apr-02 2,612 

May-02 2,774 

Jun-02 1,961 

Jul-02 1,962 

Aug-02 2,330 

Sep-02 2,275 

Oct-02 2,502 

Nov-02 1,746 

Dec-02 1,791 

Total 27,225 

Figure 3. Siemens Solar Panels and Eco-Energies
 

Photovoltaic Tracking Arrays
 

Introduction 

The President's call to reverse America's growing 

dependence on foreign oil harkens to the decision 

SunLine Transit Agency's board of directors made in 

1994. That was the year SunLine accomplished the 

unthinkable by becoming the first transit agency in 

the world to park all of its diesel buses and switch 

overnight to a fleet powered 100% by clean-burning 

compressed natural gas (CNG). That was only the 

beginning. 

Since 1999, SunLine Transit Agency has worked 

with the U.S. Department of Energy (DOE), U.S. 

Department of Defense (DOD), and the U.S. 

Department of Transportation (DOT) to develop and 

test hydrogen infrastructure, fuel cell buses, a heavyduty fuel cell truck, a fuel cell neighborhood electric 

vehicle, fuel cell golf carts and internal combustion 

engine buses operating on a mixture of hydrogen and 

compressed natural gas (CNG). 

SunLine has cultivated a rich history of testing 

and demonstrating equipment for leading industry 

3 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

manufacturers in a pre-commercial environment. 

Visitors to SunLine's "Clean Fuels Mall" from 

around the world have included government 

delegations and agencies, international journalists 

and media, industry leaders and experts and 

environmental and educational groups. 

This is the final report of a three-year success 

story, which began with the DOE's decision to 

establish a hydrogen infrastructure in Southern 

California at SunLine Transit Agency in Thousand 

Palms, California. SunLine was tasked with taking 

two then-current DOE projects and moving them to 

SunLine to create an infrastructure that produced, 

compressed, stored and dispensed hydrogen to fuel 

cell vehicles using grid, solar and wind power. 

The investment made by the DOE has yielded 

significant benefits. Not only was the project 

constructed as scheduled, but it has surpassed the 

original goals under SunLine's Best Test Center for 

Alternate Energy Technologies to become part of 

SunLine's daily operations and maintenance 

activities. In other words - our "rolling laboratory" 

has taken the technology out of the science lab and 

into the real world. 

Approach 

The basic approach to the development of the 

hydrogen infrastructure and the testing of fuel cell 

vehicles was to treat all of the equipment as if it were 

commercialized. With this philosophy, all of the 

problems and issues would be brought forward in 

terms of operability, maintainability, supportability, 

reliability, and durability. This type of field testing is 

valuable to manufacturers and developers because it 

gives them the areas that need solutions before the 

product is declared commercialized. It educates the 

early adopters of technology in the requirements to 

employ the technology in service. The downside is 

that early adopters are placed on the "bleeding edge" 

of cash flow unless the new expensive technology is 

subsidized by government or private investment. 

Results 

One of the project's significant objectives was to 

educate the public on the safety and reliability of fuel 

cell vehicles. By demonstrating fuel cell bus service 

using compressed hydrogen in a normal transit 

 FY 2003 Progress Report 

operation, officials and riders alike got to experience 

for themselves the pollution-free transportation 

technology of the future. Another objective was to 

show the potential to other transit operators for using 

a liquid fuel reformed to hydrogen in fuel cell buses. 

To further enhance the public education 

component of the project, SunLine developed several 

additional strategies. Thirteen two-minute "Energy 

Matters" videos were distributed to PBS stations in 

major California media markets. The videos covered 

such topics as alternative fuels, electricity and the 

grid, fuel cells, micro-turbines, and new car 

technologies. The videos were also made available 

to teachers and administrators for classroom use. 

SunLine worked with College of the Desert and 

other partners to develop the first training manual for 

hydrogen fuel cells and related technologies. The 

curriculum, funded in part by the Federal Transit 

Administration and the Department of Defense, is set 

to be delivered to students at College of the Desert 

and other community colleges throughout the state 

through the California Community Colleges' EdNet 

initiative. 

The Hydrogen Fuel Cell Engines and Related 

Technologies training manual has also been posted 

on the NREL website. From its introduction in 

October 2002 to August 14, 2003, the manual 

received 508,321 hits. According to NREL, this is 

the largest number of hits they have ever recorded in 

that short of a time span. From April 28, 2000, to the 

current date, over 6,000 visitors from 31 countries 

have visited SunLine Transit Agency to see and hear 

the story of the development of the Clean Fuels Mall. 

Conclusions 

Other than cost, SunLine's track record of 

experience has identified several challenges to 

hydrogen commercialization: 

•	 The need to improve fuel cell reliability 

•	 The need to engage the insurance industry in 

overcoming liability issues 

•	 The establishment of reasonable codes and standards 

•	 The implementation of comprehensive hydrogen 

education and outreach programs to elevate public awareness to mainstream levels 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies

SunLine has effectively demonstrated the need 

for a path of continuous improvement. Investments 

in fuel cell technology should be made on a measured 

basis of how they contribute to the global body of 

knowledge. While it is important to test and 

demonstrate the technology, it is also important to 

invest wisely. Finite resources should be devoted to 

those organizations and programs that have 

demonstrated a passion to make things work, the 

policies and political will to further hydrogen and 

fuel cell development and the capability to perform 

technology transfer to future organizations. 

Selective investment is a must. 

References 

1. Final Report to the Department of Energy, 

February 2003, "Hydrogen Commercialization: 

Transportation Fuel for the 21st Century", 

Contract Number: DE FC36-96GO10139 

 FY 2003 Progress Report 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Turnkey Commercial Hydrogen Fueling Station 

David E. Guro (Primary Contact) 

Air Products and Chemicals, Inc. 

7201 Hamilton Boulevard 

Allentown, PA 18195 

Phone: (610) 481-4625; Fax: (610) 481-4260; E-mail: gurode@apci.com 

DOE Technology Development Manager: Arlene Anderson 

Phone: (202) 586-3818; Fax: (202) 586-9811; E-mail: Arlene.Anderson@ee.doe.gov 

Subcontractors: 

H2Gen Innovations, Inc. - Alexandria, VA 

Pennsylvania State University - University Park, PA 

QuestAir Technologies Inc. - Burnaby, BC, Canada 

Objectives 

To demonstrate the potential for an economically viable stand-alone, fully integrated hydrogen fueling 

station based upon the reforming of natural gas by striving to: 

•	 Develop a cost-effective solution to the reforming of natural gas to produce a reformate stream; 

•	 Develop an efficient, cost-effective means to purify the hydrogen-rich reformate to pure hydrogen 

employing pressure swing adsorption (PSA); 

•	 Develop a commercially acceptable system to compress, store, meter, and dispense hydrogen into 

vehicles; 

•	 Efficiently integrate the process steps mentioned above into a safe, user-friendly, cost-effective fueling 

station; 

•	 Demonstrate the operation of the fueling station at Penn State University; 

•	 Maintain safety as the top priority in the fueling station design and operation; and 

•	 Obtain adequate operational data to provide the basis for future commercial fueling stations. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance (O&M) 

•	 E. Control and Safety 

Approach 

This nine-quarter project is being managed in three phases, with Stage Gate reviews between each phase. 

•	 In Phase 1, conceptual designs and preliminary cost evaluations for each major sub-system in the 

fueling station will be completed. Options will be developed and compared for the reformer system, 

PSA system, compression, storage, and dispenser. 

•	 In Phase 2, sub-system R&D will be performed to test the concepts put forth in Phase 1. Technical 

viability and fueling station costs will be validated. 

1 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Phase 3 will include fabrication, installation, and testing of the full-scale hydrogen generator and 

dispenser at Penn State. This fueling station will be designed to deliver 50 nm3/hr of hydrogen. 

Accomplishments 

•	 Completed Phase 1 study. Held Stage-Gate meeting between U.S. DOE and Air Products
 

management. Decision made to proceed with the project.
 

•	 Initiated Phase 2 development work, as outlined below. 

Future Directions 

•	 Complete Phase 2 - Subsystem Development. In this phase, the most promising subsystem designs 

assessed in Phase 1 will be further developed. Lab testing of certain components will be carried out. 

Recommendations for the optimal fueling station components will be made. Phase 2 is currently 

underway. 

•	 Execute Phase 3 - System Deployment. Scale-up and detailed engineering design of all equipment will 

be completed. Fabrication of all equipment and installation at Penn State will follow. Finally, the 

fueling station will be started up and put into operation at Penn State University. This will include 6 

months of operation and testing. 

The expected schedule for all three Phases is outlined in the table below: 

Task Date 

Phase 1 Pre-Contract Technical Development Oct 2001 - March 2002 

Cooperative Agreement Award 29 March 2002 

Phase 1 Conceptual Design and Economic Evaluation April 2002 - June 2002 

Phase 2 Subsystem Development July 2002 - July 2003 

Phase 3 System Deployment August 2003 - June 2004 

Phase 3 System Deployment - Operation & Testing July 2004 - December 2004 

Introduction 

The transition to hydrogen as a fuel source 

presents several challenges - one of the major hurdles 

is the cost-effective production of hydrogen in small 

quantities. In the early demonstration phase, 

hydrogen can be provided by bulk distribution of 

liquid or compressed gas from central production 

plants; however, the next phase to fostering the 

hydrogen economy will likely require onsite 

hydrogen generation to institute a pervasive 

infrastructure. Providing inexpensive hydrogen at a 

fleet operator's garage or local fueling station is a key 

enabling technology for direct hydrogen fuel cell 

vehicles (FCVs). The objective of this project is to 

develop a comprehensive, turnkey, stand-alone 

hydrogen fueling station for FCVs with state-of-theart technology that can be cost-competitive with 

current hydrocarbon fuels. Such a station will help to 

promote the advent of the hydrogen economy for 

buses, fleet vehicles, and ultimately personal 

vehicles. 

Approach 

The development efforts are expected to build on 

preliminary work accomplished by the major 

partners. Air Products, as the overall project 

manager, is responsible for the total system 

integration and final development of the installed 

equipment. As the system integrator, Air Products 

will ensure that the system is fully optimized and that 

2 
 

 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

all of the individual components are compatible to 

deliver the lowest cost hydrogen fuel. This ninequarter project is being managed in three phases, 

with Stage Gate reviews between each phase. 

During Phase 1 of the project, subsystem 

conceptual designs were formulated and costed. 

Options were developed and compared for the 

reformer system, PSA system, compression, storage, 

and dispenser. Air Products has worked with H2Gen 

and other reformer suppliers to develop and to 

evaluate the applicability of auto-thermal reforming 

(ATR), partial oxidation (POX), and steam methane 

reformer (SMR)-based reforming systems. At the 

end of Phase 1, Air Products confirmed the team's 

ability to reach the cost targets via a confirmed 

definition of scope and execution costs and identified 

the partners for further development of components 

in Phase 2. 

In Phase 2, currently underway, the most 

promising subsystem designs assessed and selected 

in Phase 1 will be further developed. Lab testing of 

certain components will be carried out. 

Recommendations for the optimal fueling station 

components will be made. Air Products engineers, 

working with the selected reforming partner, will 

optimize the design of the reformer and build and test 

components of this reactor in a laboratory. Air 

Products will be directly responsible for the design of 

the dispenser, which will be tested in a shop prior to 

installation on site. Because of the partners' 

relationships with the automotive manufacturers, we 

will solicit their assistance for inclusion of 

commercial features such as vehicle communication. 

Finally, Air Products will act as the system integrator 

to pull together the various pieces into a 

comprehensive turnkey unit and to minimize the total 

cost of delivered hydrogen. 

During Phase 3, scale-up and detailed 

engineering design of all equipment will be 

completed. The engineered system will be analyzed 

for DFMA (Design for Manufacture and Assembly), 

and the assembled system will include 

instrumentation for data collection and provisions for 

remote monitoring of operation. Fabrication of all 

equipment and installation at Penn State will follow. 

Then, the fueling station will be started up and put 

into operation at Penn State University. This will 

include 6 months of operation and testing. Finally, 

we will validate the cost of hydrogen delivered from 

the installed fueling station, and we will estimate the 

impact of mass-producing components. 

Results 

General: 

Phase 1 work completed. Presentation made to DOE 

headquarters representatives on August 7, 2002. 

Major conclusions of Phase 1 report: 

•	 Project schedule validated – on target. 

•	 Project budget validated – on target. 

- Completed general process specifications for 

all major equipment. 

- Obtained quotes and updated cost estimates. 

- Re-validated development costs with principal 

investigators for each area of the fueling 

station. 

•	 Cost-effective route to production and delivery 

of hydrogen from a commercial fueling station 

identified. 

- Cost of hydrogen from stations improves with 

mass production and with scaling to larger 

station sizes. 

- $1.50/gallon gasoline equivalent is a stretch 

goal, but attainable. 

- Stand-alone hydrogen station is technically and 

economically feasible. 

Phase 2 kicked-off. Of critical importance to the 

success of this project is the availability of vehicles 

(or other hydrogen demand) at the Penn State site to 

validate the performance of the installed fueling 

station. Penn State (PSU) and Air Products 

recognized that fuel cell hydrogen buses will not be 

available by January 2003, the targeted 

commissioning date for the hydrogen fueling station. 

A team was established to develop a plan for the 

station and for making vehicles available. The team 

met in January, February, and March 2003 and 

consisted of representatives from Air Products, PSU 

Hydrogen Institute, DOE (Philadelphia Regional 

Office), State of Pennsylvania Department of 

Environmental Protection (DEP), Center Area 

Transport Authority (CATA), PSU Pennsylvania 

Transportation Institute, and PSU Office of Physical 

3 
 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Plant (OPP). The team’s recommended plan is for 

the PSU Hydrogen Institute to take the lead in a 

project to: 

1.	 convert several CATA compressed natural gas 

(CNG) buses to run on a H2/CNG blend, 

2.	 convert several PSU OPP utility vans from CNG 

to H2/CNG blend, 

3.	 purchase for PSU OPP one hydrogen internal 

combustion engine utility van, 

4.	 upgrade the CATA and PSU facilities for 

operation with a H2/CNG blend, 

5.	 provide required training, and 

6.	 run and maintain the fueling station for a period 

of 3 years. 

This proposal has met with the approval of PSU 

and Air Products, and it is being reviewed by 

Pennsylvania DEP for a funding decision. In order to 

match station and vehicle availability, the Phase 2 

end-date was extended from March 2003 to July 

2003, and system startup will be rescheduled from 

January 2004 to July 2004. 

Currently, Phase 2 work is ongoing. Progress 

towards Phase 2 goals is outlined below: 

Reformer: 

•	 Air Products completed a Phase 1 engineering 

study to update the comparison of ATR, POX, 

and SMR technologies to determine the optimum 

route to small-scale H2 production. The major 

conclusions were: 

- Advanced Technology SMR’s are more cost 

competitive than the other evaluated 

technologies for small-scale reforming 

applications used in hydrogen fueling stations. 

- Of the reformers evaluated, H2Gen’s heat 

exchange reformer and Harvest’s regenerative 

reformer offer the lowest cost of hydrogen. Of 

the two, H2Gen’s system has the greatest 

potential to provide the low-cost option, but 

H2Gen’s system is also the higher risk option, 

both technically and economically. 

 FY 2003 Progress Report 

•	 H2Gen development work continued into the 

Fall of 2002. Then, a meeting was held between 

DOE headquarters and Air Products project 

personnel to determine the best technical path 

forward on Phase 2 with respect to the reformer 

development. Conclusions: While H2Gen 

continued to make progress, they were behind 

scheduled milestones. A decision was reached to 

switch to another reformer vendor as the 

reformer supplier for the remainder of this 

project. 

•	 Process engineering development work 

continues on optimization of reformer system, 

including desulfurization, shift, steam 

generation, heat exchange, and valving. 

•	 A preliminary process flow diagram (PFD) has 

been developed. 

Hydrogen PSA Purifier: 

•	 Air Products’ adsorbent development continued. 

Novel structured adsorbents and advanced 

beaded adsorbents show significant 

improvement in bed size and hydrogen recovery. 

PSA cycle development work concluded – it was 

used to fully utilize the advanced adsorbents’ 

capabilities. Laboratory experiments have been 

completed. 

•	 The lab to test the new PSA rotary valve was 

completed, and testing has commenced. Thus 

far, the valve has over 800,000 cycles and is 

leak-tight. An outside supplier for the valve has 

been identified and has made the first valve for 

testing. 

•	 Air Products concluded the successful testing of 

its “alpha” prototype hydrogen PSA unit at an 

Air Products hydrogen production facility. The 

data collected on this PSA unit served to verify 

several of the significant technical “step-outs” 

being taken in the new PSA design being 

developed by the Air Products team. The system 

ran continuously since July 2002, successfully 

producing hydrogen at <2 ppm CO with high 

hydrogen recovery. The system met all 

engineering targets for hydrogen production, 

hydrogen recovery, and purity. 

•	 Air Products fabricated a “beta” hydrogen PSA 

test unit. The unit has been placed next to the 

“alpha” test unit mentioned above. The “beta” 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

PSA unit is now in operation, and data is being 

collected. 

•	 QuestAir completed their Phase 1 work to 

improve their HyQuestor hydrogen purifier. 

Preliminary design and cost summaries are done 

and are included in QuestAir’s Phase 1 report to 

Air Products. QuestAir initiated Phase 2 work. 

•	 QuestAir continued their Phase 2 development 

work. They have optimized the design of their 

system and have built their laboratory test rig. 

QuestAir tested their PSA system and is 

preparing their Phase 2 summary report. 

Hydrogen Compression, Storage, and Dispensing: 

•	 Air Products has completed the preliminary 

engineering work to determine the optimum 

configuration and selection of components for 

the hydrogen dispenser. 

•	 Laboratory equipment to test hydrogen flow 

meters for use in the dispenser has been 

purchased, and the lab unit is being fabricated. 

The test plan is prepared –initiation of testing is 

anticipated in late Summer 2003. 

Conclusions 

Work progresses on Phase 2 of this aggressive 

project to determine the viability of a commercial 

turnkey hydrogen fueling station. Over the past year, 

the team completed Phase 1 and derived the 

following conclusions from its Phase 1 study: 

•	 A cost-effective route to production and delivery 

of hydrogen from a commercial fueling station 

was identified. 

•	 The cost of hydrogen from stations improves 

with mass production and with scaling to larger 

station sizes. 

•	 The $1.50/gallon gasoline equivalent cost is a 

stretch goal, but attainable. 

•	 Stand-alone hydrogen stations are technically 

and economically feasible. 

FY 2003 Publications/Presentations 

1. Quarterly and Annual Reports to U.S. DOE, as 

required per the Cooperative Agreement, were 

submitted by Air Products. 

2. Annual Program Merit Review presentation was 

made by David Guro of Air Products at the DOE 

meeting held in Berkeley, CA, in May 2003. 

5 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of a Natural Gas to Hydrogen Fuel Station 

William E. Liss (Primary Contact), Mark Richards 

Gas Technology Institute (GTI) 

1700 S. Mount Prospect Road 

Des Plaines, IL 60018 

Phone: (847) 768-0753; Fax: (847) 768-0501; E-mail: william.liss@gastechnology.org 

DOE Technology Development Manager: Sigmund Gronich 

Phone: (202) 586-8012; Fax: (202) 586-9811; E-mail: Sigmund.Gronich@ee.doe.gov 

Subcontractor: FuelMaker Corporation 

Objectives 

•	 The overall objective is to develop cost-competitive technology suitable for distributed production of 

high-pressure hydrogen from natural gas to fuel hydrogen-powered vehicles. 

•	 Design and test a fast-fill natural gas to hydrogen fueling system with 40-60 kg/day delivery capacity. 

•	 Produce high-pressure hydrogen at $2.50/kg or less to meet intermediate cost targets. 

•	 Demonstrate innovative, compact natural gas steam reforming system and appliance-quality hydrogen 

compressor technologies. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen Production section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Fuel Processor Capital Costs 

•	 B. Operation and Maintenance (O&M) 

•	 C. Feedstock and Water Issues 

•	 E. Control and Safety 

•	 Z. Catalysts 

•	 AB.Hydrogen Separation and Purification 

Approach 

•	 Undertake system design and analysis to identify pathways for meeting cost and performance targets. 

•	 Conduct subsystem development and laboratory testing to confirm unit operation and suitability for 

complete system application. 

•	 Combine subsystems into an overall integrated system that incorporates system controls and safety 

features. 

•	 Conduct lab and field experiment testing to validate the complete system for performance, operability, 

and reliability. 

Accomplishments 

•	 Comprehensive subsystem and system design report completed. 

•	 Laboratory prototype fuel processor (alpha unit) subsystem built and tested under a wide range of 

operating conditions, including start-up, steady-state, turndown, and dynamic response rates. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Full-scale high-pressure hydrogen cascade and environmental chamber constructed. 

•	 First-principle hydrogen cylinder filling model developed (CHARGE H2). 

•	 Comprehensive set of hydrogen fast-fill tests conducted on two different types of cylinders, including 

tests beginning at cold and hot ambient temperatures. 

•	 Documented and reported on degree of in-cylinder temperature rise and spatial variability during fastfilling process. 

•	 Paper presented at National Hydrogen Association (NHA) meeting on fast filling of hydrogen 

cylinders. 

•	 Advanced hydrogen filling dispenser algorithm developed (H2 AccuFill). 

•	 All-new, oil-free primary hydrogen compressor designed and built for compressing reformed gases 

(80% hydrogen/20% carbon dioxide) up to 100 psig. 

•	 Pressure swing adsorption (PSA) test facility constructed. 

•	 PSA tests initiated to evaluate multi-component fuel treatment and removal strategies. 

•	 Comprehensive model developed for analyzing hydrogen-fueling station costs, including capital, 

operating, and maintenance cost elements. Program includes Monte Carlo techniques to account for 

uncertainty and variability in cost drivers. 

•	 Paper on hydrogen fueling system economics prepared and presented to World Hydrogen Energy 

Conference. 

•	 Engaged in various technology transfer and communications efforts, including: display of system 

design at event for President Bush, presentation at SAE TOPTEC, presentation for SAE IndustryGovernment meeting, International Energy Agency Forum, and one-on-one meetings with various 

North American, European, and Asian organizations and companies. 

Future Directions 

•	 Complete subsystem testing and evaluation of fuel processor, primary compressor, PSA fuel 

purification, secondary compressors, and dispenser filling algorithm. 

•	 Continue building of the first-generation integrated natural gas to hydrogen fueling system, beginning 

with system "front end" that includes fuel processor, water treatment and recovery, and primary 

compression, followed by the system "back end" including PSA subsystem, secondary compression, 

storage, and dispenser hardware. 

•	 Work with various parties interested in technology transfer, licensing, and/or testing of core 

subsystems and overall integrated fueling station. 

Introduction 

A key impediment to expanded fuel cell vehicle 

use is fueling infrastructure. The use of distributed 

hydrogen fueling systems is seen as an intermediate 

pathway to permit infrastructure development (with 

future development of a hydrogen pipeline delivery 

infrastructure). This project aims to leverage the 

substantial natural gas delivery infrastructure by 

developing a distributed natural gas to hydrogen 

fueling system. 

Several key technologies are being developed in 

this project. This includes a highly compact, costeffective steam methane reformer and fuelprocessing technology originally developed by GTI 

for stationary proton exchange membrane (PEM) 

fuel cells. This unit has been adapted to serve as a 

hydrogen generator for fueling stations. Experience 

with compressed natural gas vehicles is being 

leveraged through modification and development of 

intermediate and high-pressure hydrogen 

compressors with FuelMaker Corporation. An 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

additional core effort is development of a hydrogen 

dispenser with an advanced filling algorithm that will 

permit accurate and complete filling of compressed 

hydrogen vehicles under a range of conditions. 

These advanced subsystems - reforming, fuel 

cleanup, compression, storage, and dispensing - will 

be incorporated into an integrated and costcompetitive small natural gas to hydrogen fueling 

station that will support hydrogen fueling 

infrastructure development and expansion. 

The specific goals for this project are a fast-fill 

natural gas to hydrogen fueling system with 40-60 

kg/day delivery capacity. DOE goals include 

providing hydrogen at costs of $2.50/kg or less, as 

part of an intermediate path to $1.50/kg. 

Approach 

The project approach is to develop and test key 

subsystems (fuel processor, compression, fuel 

purification, storage, and dispensing) and then 

integrate these subsystems with controls into an 

overall cost-effective hydrogen fueling solution. The 

project approach includes three phases: 1) Design, 

2) Development and Lab Testing, and 3) Field 

Testing. Through these progressive phases, GTI 

anticipates building a proven small natural gas to 

hydrogen fueling system that can support the 

development and expansion of a distributed 

hydrogen-fueling infrastructure. 

This project is leveraging developments in the 

stationary PEM fuel cell and compressed gas vehicle 

market sectors. GTI has developed a high-efficiency, 

compact steam methane reformer and fuel processor 

for stationary fuel cells. Modification of this fuel 

processor comprises a core element of this project. 

GTI is working with FuelMaker Corp. to develop 

intermediate-pressure (100 psig and less) and highpressure hydrogen compressors based on experience 

with their oil-free designs, as well as fuel purification 

solutions. An advanced filling algorithm is being 

developed and tested to allow for complete and 

accurate filling of vehicles. 

Results 

The project began in February 2002 with a focus 

on subsystem and system design. A comprehensive 

 FY 2003 Progress Report 

design and analysis report was submitted in September 

2002. This covered all of the key subsystems as well 

as a first-generation integrated system design. Figure 

1 shows a detailed description of the key subsystems. 

The footprint for the system (excluding hydrogen 

storage) is approximately 8’ by 14’. This could be 

made more compact in the future, but the current 

emphasis is on system functionality over form. 

Work has been conducted using the GTI compact 

fuel processing system. Normally, this unit contains 

a steam methane reformer, shift conversion system to 

maximize hydrogen yield, and methanation reactor 

for CO control. Testing of the complete system 

indicates the ability to reliably obtain high hydrogen 

concentrations of 80% with CO levels reliably below 

10 ppm. 

An additional set of tests was conducted with the 

methanation reactor removed from the fuel 

processing system. This testing was to determine CO 

levels under different conditions so that sizing of the 

PSA system could be considered for CO control. In 

this way, there was an effort to look at the capital and 

operating cost trade-offs between methanation and 

additional PSA subsystem material used for CO 

removal. Figure 2 shows one set of results when 

testing the fuel processor without the methanation 

step in a repeat test mode. These data are being 

incorporated into the PSA system design and testing. 

GTI completed a comprehensive set of tests on 

fast-filling of high-pressure hydrogen cylinders 

under a range of starting ambient temperature 

conditions, starting pressure levels, varying time of 

fill, and other key parameters. Figure 3 shows 

representative test results, with thermocouples placed 

on the exterior of a Type 4 cylinder and at various 

Figure 1. Hydrogen Fueling System Details 

3 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

points along the internal central axis of the cylinder. 

The degree of temperature rise in this example is 

over 140o

F. Depending on the point of measurement 

and time of measurement, there can be substantial 

differences in temperature within the cylinder. 

Additional tests were also run on a Type 3 cylinder. 

Figure 4 shows a summary of the testing results 

to date. As a first order, the degree of temperature 

rise is proportional to the change in pressure from the 

beginning to the end of the fill process. Secondary 

factors come into play to result in variations in the 

degree of temperature rise (e.g., cylinder type, time 

of fill, etc.). 

Testing on hydrogen cylinder filling was 

conducted at low, moderate, and high ambient 

temperature conditions using the GTI full-scale 

environmental chamber equipped with a hydrogen 

 FY 2003 Progress Report 

storage cascade (Figure 5). This facility is fully 

instrumented with data acquisition equipment 

GTI has developed a first-principle 

thermodynamic model of the hydrogen cylinder 

filling process (a program called CHARGE H2). We 

are now using this model and empirical data from the 

testing program to develop a dispenser control 

algorithm that will enable proper hydrogen cylinder 

filling. This algorithm is called H2 AccuFill and 

leverages a GTI patented approach. 

A brand new compressor, referred to as a 

primary compressor, has been designed and built by 

FuelMaker during the past year. This unit is 

designed to take reformate gas (H2/CO2) from low 

Figure 2. Compact Fuel Processor Testing Without 

Methanation for CO Control
 

Figure 3. Temperature Measurements During
 

Hydrogen Cylinder Filling
 

Figure 4. Summary of Hydrogen Fill Tests 

Figure 5. GTI Hydrogen Environmental Chamber 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

pressure to levels of 60-100 psig. The output of the 

primary compressor is then fed to a PSA system for 

removal of CO2 and other trace gases. Figure 6 

shows a computer-aided design (CAD) drawing of 

the primary compressor. 

Work is underway in building the first-generation 

completely integrated natural gas to hydrogen fueling 

system. An 8’ by 14’ steel skid has been constructed, 

and the front end of the system (fuel processor, water 

treatment and recovery, and primary compressor) is 

being installed and readied for testing. The back end 

of the system will be installed during the second half 

of CY 2003. 

Conclusion 

1. There are challenges with meeting the system cost 

targets in the near term; a substantial element of 

the cost target rests on the price of natural gas. 

2. The application of a natural gas fuel processing 

system originally developed for stationary PEM 

system application has proven successful. 

3. Fuel processor start-up time and dynamic 

response rates are acceptable for fast-fill stations 

that incorporate high-pressure cascade storage 

systems. 

Figure 6. FuelMaker Primary Compressor Design 

 FY 2003 Progress Report 

4. Fuel processor efficiencies up to 83% are 

anticipated based on testing and evaluation efforts 

to date. 

5. Preliminary data indicates an optimum cost tradeoff for CO control using a combination of shift 

conversion and PSA system operation. 

6. Significant thermal effects are seen with fast 

filling of high-pressure hydrogen cylinders. 

7. Meaningful spatial variations in hydrogen gas 

temperature occur with a hydrogen cylinder 

during fast filling. 

8. Preliminary results indicate that a dispenser-based 

filling algorithm should be suitable for achieving 

a complete cylinder filling under most conditions. 

FY 2003 Publications/Presentations 

1. Richards, M. and Liss, W., "Reformer-Based 

Hydrogen Fueling Station Economics," World 

Hydrogen Energy Conference, June 2002. 

2. Liss, W., "Development of Hydrogen Fueling 

Systems," Presentation to Japan Gas Association, 

June 2002. 

3. Richards, M. and Liss, W., "Natural Gas 

Reformer-Based Hydrogen Fueling Station 

Modeling," NGV International Conference 2002, 

Oct. 2002. 

4. Richards, M., Liss, W., and Kountz, K., "Natural 

Gas Reformer-Based Hydrogen Fueling Station 

Modeling," GTI Natural Gas Technologies 

Conference, Oct. 2002. 

5. Liss, W., "Distributed Hydrogen Fueling System 

& Infrastructure Development," Presentation to 

International Energy Agency Annex XV, Nov. 

2002. 

6. Richards, M., Liss, W., and Kountz, K., 

"Modeling and Testing of Fast-Fill Control 

Algorithms for Hydrogen Fueling," NHA Annual 

Meeting, March 2003. 

7. Liss, W., "Developing a Retail Hydrogen Market," 

SAE Fuel Cell TOPTEC, April 2003. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fuel Cell-Powered Front-End Loader Mining Vehicle 

David L. Barnes (Primary Contact), Arnold R. Miller 

Vehicle Projects, LLC 

621 Seventeenth Street, Suite 2131 

Denver, Colorado 80293-2101 

Phone: (303) 296-4218; Fax: (303) 296-4219; E-mail: david.barnes@vehicleprojects.com 

DOE Technology Validation Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-1637; E-mail: Sigmund.Gronich@ee.doe.gov 

Subcontractors: 

AeroVironment Inc., Monrovia, California 

Carleton University, Ottawa, Ontario, Canada 

Caterpillar Inc., Peoria, Illinois 

HERA Hydrogen Storage Systems, Longueuil, Québec, Canada 

Natural Resources Canada, Ottawa, Ontario, Canada 

Newmont Mining, Elko, Nevada 

Nuvera Fuel Cells, Cambridge, Massachusetts 

Placer Dome Technical Services, Vancouver, British Columbia, Canada 

Southwest Research Institute, San Antonio, Texas 

Stuart Energy Systems, Mississauga, Ontario, Canada 

University of Nevada, Reno, Nevada 

Objectives 

•	 Develop a mine loader powered by a fuel cell 

•	 Develop associated metal-hydride storage and refueling 

•	 Demonstrate the loader in an underground mine in Nevada 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Vehicles 

• B. Storage 	 

Approach 

•	 Perform a cost/benefit analysis of fuel cell mine vehicles including cost of producing hydrogen, 

method of hydrogen transfer, vehicle manufacturer costs, mine recurring costs, and ventilation savings 

•	 Develop an electrolysis refueling station and demonstrate refueling concepts in Nevada 

•	 Determine power requirements (duty cycle), drive system, hybridization options, and onboard energy 

storage for a Caterpillar-Elphinstone R1300, 165 hp (123 kW), 3.5 cubic yard mine loader 

•	 Perform a detailed engineering design of powerplant, metal-hydride storage, drive system, and control 

system 

•	 Fabricate powerplant and metal-hydride storage and bench test 

•	 Integrate powerplant, metal-hydride storage, and system components into base vehicle 

•	 Complete risk assessment and certify for underground demonstration 

•	 Test entire vehicle and demonstrate in an underground mine in Nevada 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Completed manufacturing of electrolyzer and demonstrated refueling concepts in Nevada with a fuel 

cell-powered locomotive 

•	 Completed final reports for cost/benefit analysis including "Best Methods of Hydrogen Transfer", 

"Operating Costs of Hydrogen Production", and "Ventilation Benefit Analysis" 

•	 Completed preliminary design identifying duty cycle, single electric drive motor, battery hybrid 

configuration, and amount of metal hydride storage 

•	 Received diesel-powered R1300 from manufacturer for verification of detailed component layout 

•	 Ordered 100 kW fuel cell stacks from manufacturer 

Future Directions 

•	 Complete detailed engineering design for powerplant, metal-hydride storage, drive system, hydraulics, 

and operating controls 

•	 Fabricate and test powerplant, metal-hydride storage, drive system components, hydraulic
 

components, operating controls, and cooling components
 

•	 Integrate associated fuel cell powertrain components into R1300 base vehicle 

•	 Test fuel cell system and compare to baseline diesel-powered performance parameters 

•	 Complete risk assessment and underground certification with the Mine Safety and Health
 

Administration (MSHA)
 

•	 Evaluate performance and durability in an underground mine in Nevada 

Introduction 

Underground mining is the most promising 

application in which fuel cell vehicles can compete 

strictly on economic merit (1). The mining industry, 

one of the most regulated, faces economic losses 

resulting from the health and safety deficiencies of 

conventional underground traction power. 

Conventional power technologies - tethered 

(including trolley), diesel, and battery - are not 

simultaneously clean, safe, and productive. Solution 

of this problem by fuel cells would provide powerful 

cost offsets to their current high capital cost. Lower 

recurring costs, reduced ventilation costs, and higher 

vehicle productivity could make the fuel cell vehicle 

cost-competitive several years before surface 

applications. The diesel-powered version of the test 

loader is shown in Figure 1. 

Approach 

A joint venture between the Fuelcell Propulsion 

Institute (a nonprofit consortium of industry 

participants) and Vehicle Projects LLC (project 

management) provided the basis for this three-phase 

project, a key production element of underground 

mining. To ensure the design meets industry needs, 

various mining industry participants will evaluate 

and provide input regarding performance, 

productivity, and operator ergonomics. 

Figure 1. Diesel-Powered Mine Loader. 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

The first phase of the project will perform a cost/ 

benefit analysis comparing diesel and fuel cell vehicle 

recurring costs, fuel costs, energy efficiency, and 

ventilation costs that will determine the feasibility of 

commercialization. Different refueling concepts will 

be verified by manufacturing an electrolyzer and using 

Vehicle Projects' fuel cell-powered locomotive. To 

understand all of the power requirements, a duty cycle 

based on real operating conditions, will be established. 

This will assist in determining the type of drive motor, 

onboard energy storage, and whether a standalone fuel 

cell or hybrid powerplant will be used. Software 

modeling will be used to understand the energy 

requirements needed to satisfy the duty cycle over an 

entire operating shift. 

In Phase 2, detailed engineering design, project 

partners will design the powerplant, metal-hydride 

storage, hydraulic interface, cooling system, system 

controls, and layout. Engineering drawings and the 

bill of materials will be the deliverables. 

The final phase involves fabricating the 

powerplant, metal-hydride storage, and all 

subsystems; integrating them into the base vehicle; 

testing all systems; completing the risk assessment 

and certifying the vehicle for underground 

evaluation; and testing in a production mine in 

Nevada. 

Results 

The cost/benefit analysis indicates substantial 

savings in ventilation costs of anywhere from 24% to 

53%, depending on the type of mine operation. This 

can result in up to $1.5 million a year in savings in 

primary ventilation system costs if the existing 

diesel-powered loader fleet were replaced with fuel 

cell power. This is a substantial cost savings that 

could offset higher fuel cell-power capital costs. In 

addition, the cost of producing hydrogen via 

electrolysis is under $5.00 per kg based on $0.06 per 

kW for electricity. With the fuel cell powerplant 

being almost twice as efficient as a diesel engine, the 

cost of hydrogen approaches the cost of diesel. 

Two methods of refueling the metal-hydride 

storage, recharging directly onboard and swapping of 

storage modules, were successfully demonstrated 

with the use of Vehicle Projects' fuel cell-powered 

locomotive in Nevada. Recharging of 3 kg of 

hydrogen can be accomplished in under one hour. 

Ongoing detailed design, based on the 

established duty cycle shown in Figure 2, has 

identified a hybrid powerplant design. In 

conjunction with using 100 kW (continuous) proton 

exchange membrane fuel cell stacks, an additional 70 

kW, stored in lead-acid batteries, will be available to 

provide enough power to handle the peak-power 

requirements. Regenerative braking will not be used 

in this design due to the complexity and reliability. 

Conclusions 

The problems of vehicle emissions and noise have 

negative economic consequences for underground 

vehicle applications. Fuel cells coupled with 

reversible metal-hydride storage, by solving these 

problems, offer cost offsets - higher productivity and 

lower operating costs - that can make underground 

fuel cell vehicles cost-competitive sooner than surface 

applications. Our fuel cell-powered, electric drive 

loader with metal-hydride storage will exhibit greater 

torque characteristics than the diesel equivalent and is 

anticipated to be more productive, while emitting zero 

emissions and lower noise. Because of the stringent 

regulations for underground mines, metal-hydride 

storage is an ideal technology that has been proven 

with Vehicle Projects' fuel cell-powered locomotive. 

References 

A. R. Miller, Tunneling and Mining Applications 

of Fuel Cell Vehicles. Fuel Cells Bulletin, July 2000, 

pp. 5-9. 

Figure 2. Duty Cycle for the Fuel Cell-Powered Loader 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Presentations 

1. R. Sage, "Fuelcell Mine Loader and Prototype 

Locomotive", Canadian Institute of Mining 

Annual Conference & Exhibition, Vancouver, 

British Columbia (2002) 

2. A.R. Miller, "The Fuelcell Mining Vehicles 

Development Program: An Update", Canadian 

Institute of Mining Annual Conference & 

Exhibition, Montreal, Quebec (2003) 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Advanced Underground Vehicle Power and Control Fuel Cell Mine Locomotive 

David L. Barnes (Primary Contact), Arnold R. Miller 

Vehicle Projects, LLC 

621 Seventeenth Street, Suite 2131 

Denver, Colorado 80293-2101 

Phone: (303) 296-4218; Fax: (303) 296-4219; E-mail: david.barnes@vehicleprojects.com 

DOE Program Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-1637; E-mail: Sigmund.Gronich@ee.doe.gov 

Subcontractors: 

Canada Center for Mineral and Energy Technology, Ottawa, Ontario, Canada 

Hatch Associates Ltd, Sudbury, Ontario, Canada 

Kappes, Cassiday & Associates, Reno, Nevada 

Placer Dome Technical Services, Vancouver, British Columbia, Canada 

Sandia National Laboratory, Livermore, California 

University of Nevada, Reno, Nevada 

Objectives 

• Develop a zero-emissions, fuel cell powered metal-mining locomotive 

• Evaluate its safety and performance, primarily in surface tests 

• Evaluate its productivity in an underground mine in Canada 

Technical Barriers 

This project addresses the following technical barriers from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• A. Vehicles 

• B. Storage 

Approach 

• Design 14 kW fuel cell powerplant 

• Design metal-hydride storage 

• Integrate powerplant and hydride storage onto locomotive base vehicle 

• Conduct preliminary tests and evaluate 

• Refine final design 

• Perform safety and risk analysis and complete documentation to meet regulatory approval 

• Evaluate productivity performance in an underground metal mine 

Accomplishments 

• Designed 17 kW fuel cell powerplant and metal-hydride storage 

• Integrated powerplant and metal-hydride storage onto locomotive base vehicle 

• Performed preliminary testing and evaluation in Nevada 

• Completed safety and risk assessment 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

• Completed documentation for regulatory approval 

• Tested and evaluated productivity performance in an underground metal mine 

Future Directions 

• Project successfully completed and closed out January 2003 

Introduction 

Underground mining is the most promising 

application in which fuel cell vehicles can compete 

strictly on economic merit (1). The mining industry, 

one of the most regulated, faces economic losses 

resulting from the health and safety deficiencies of 

conventional underground traction power. 

Conventional power technologies - tethered (including 

trolley), diesel, and battery - are not simultaneously 

clean, safe, and productive. Solution of this problem 

by fuel cells would provide powerful cost offsets to 

their current high capital cost. Lower recurring costs, 

reduced ventilation costs, and higher vehicle 

productivity could make the fuel cell vehicle costcompetitive several years before surface applications. 

The fuel cell locomotive is shown in Figure 1. 

Approach 

A joint venture between the Fuelcell Propulsion 

Institute (a nonprofit consortium of industry 

participants) and Vehicle Projects LLC (project 

management) provided the basis for the 2-phase 

project. In Phase 1, Sandia National Laboratories 

was tasked with the design of the fuel cell powerplant 

and the metal-hydride storage, as well as system 

Figure 1. Fuel Cell Mine Locomotive 

safety and risk assessment, and underground testing 

in a production environment. 

To ensure the locomotive was designed with 

industry in mind, various industry participants were 

involved to assess the design for risk and 

functionality. When the locomotive was tested 

underground, all regulatory requirements were met. 

Results 

The locomotive's fuel cell power system uses 

proton exchange membrane (PEM) fuel cells. No 

traction battery is employed, and the vehicle is thus a 

pure fuel cell vehicle. Two stacks in electrical series 

provide 126 V and 135 A at the continuous rated 

power of 17 kW gross. Parasitic losses are less than 

10%, a very good performance result. Waste heat 

from the stacks provides the heat to desorb hydrogen 

from the metal-hydride bed. A heat exchanger links 

the two isolated thermal systems: (a) the hydride-bed 

heating/cooling loop and (b) the stack cooling loop. 

Figure 2 depicts the schematic layout of the 

powerplant and metal-hydride storage. 

Specifications of the fuel cell and battery versions of 

the locomotive are compared in Table 1. 

Figure 2. Schematic Layout of the Fuel Cell Powerplan 

and Metal-Hydride Storage 

integration. Phase 2 included system evaluation, 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Table 1. Battery and Fuelcell Specifications Table 2. Average Recorded Sound Levels 

Comparison of Battery and Fuelcell Locomotives 

Parameter Battery Fuelcell 

Power, rated continuous 7.1 kW 

(gross) 

17 kW 

(gross) 

Current, rated continuous 76 A 135 A 

Voltage at continuous

rating 

94 V 

(estimated) 

126 V 

Energy capacity, electrical 43 kWh 53 kWh 

Operating time 6 h 

(available) 

7.5 h 

Recharge time 8 h (min) 1 h (max) 

Vehicle weight 3,600 kg 2,500 (without ballast) 

The hydride storage system stores 3 kg of 

hydrogen, sufficient for eight hours of locomotive 

operation at the predicted 6 kW average power of its 

duty cycle. Hydride subsystem design allows for 

rapid change-out (swapping) of a discharged bed 

with a freshly charged unit. Recharging will utilize 

gaseous hydrogen and has been measured at 

approximately one hour. 

The Mine Safety and Health Administration 

(MSHA) focused on possible hazards of hydrogen 

underground, including detailed review of process 

piping and electrical routing. The assessment 

indicated a few changes required to meet existing 

standards and helped to establish new standards for 

hydrogen-fueled underground mine vehicles. 

MSHA measured noise levels (Table 2) of the 

locomotive under a number of operating conditions, 

including acceleration (2). Unlike some fuel cell 

vehicles, our locomotive is very quiet under all 

conditions. It emanates a pleasant, low frequency 

purring, and normal conversation can easily be 

carried out while standing beside the operating 

powerplant. Consequently the steel-wheel-to-steeltrack generated noise will be the most prevalent. 

The locomotive was successfully tested and 

evaluated in two underground mines, one an 

experimental mine, the other a gold production mine 

(27 level, 4,000 feet underground). Pulling upwards 

of 20 tons, the locomotive performed flawlessly 

logging over 60 hours of runtime. Prior to 

Average Sound Levels for the Locomotive 

Location / Condition dBA* Linear** 

Operator Position/Traveling For- ward, Run #1 (Full Throttle) 

75.3 80.1 

Operator Position/Traveling For- ward, Run #2 76.6 85.1 

Operator Position/Traveling in

Reverse, Run #1 (Full Throttle) 

76.6 85.2 

Operator Position/Traveling in

Reverse, Run #2 

76.2 82.2 

Operator Position/Idle 74.4 81.2 

6 Inches from Blower on Right

Side/Idle 

78.9 85.3 

6 Inches from Top Vent on Right 

Side/Idle 

80.8 84.3 

6 Inches from Control Panel on 

Left Side/Idle 

79.5 84.0 

1 Foot in Front of Locomotive/Idle 75.3 81.9 

Background Near Area of Tests 73.4 78.3

 * Sound Level using an "A-weighted" network

** Sound Level using an unweighted network (flat response) 

underground testing a complete documentation 

package was approved including an extensive risk 

assessment and site-specific safety evaluations. A 

large portion of this regulatory approval will set the 

basis for future fuel cell-powered underground 

mining vehicle specifications. 

Conclusions 

The problems of vehicle emissions and noise have 

negative economic consequences for underground 

vehicle applications. Fuel cells coupled with 

reversible metal-hydride storage, by solving these 

problems, offer cost offsets - higher productivity and 

lower operating costs - that can make underground 

fuel cell-vehicles cost-competitive sooner than surface 

applications. Our hydride-fuel cell locomotive, like 

the battery version, is a zero-emissions vehicle. 

However, the fuel cell locomotive has greater net 

power, greater energy storage, higher gravimetric 

energy and power density, higher volumetric power 

density, and substantially faster recharging. Because 

weight is not an issue, safe and compact metal-hydride 

storage is an ideal storage technology for underground 

locomotive applications. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

References 

1. A. R. Miller, Tunneling and Mining Applications 

of Fuel Cell Vehicles. Fuel Cells Bulletin, July 

2000, pp. 5-9. 

2. Special Acoustical Field Investigation, Hydrogen 

Fuel Cell Powered Locomotive. Investigative 

Report PP-025-02O, Mine Safety and Health 

Administration, Pittsburgh, PA, 17 May 2002. 

Presentations 

1. R. Sage, “Fuelcell Mine Loader and Prototype 

Locomotive”, Canadian Institute of Mining 

Annual Conference & Exhibition, Vancouver, 

British Columbia (2002) 

2. A. Miller, “Fuelcell Locomotives”, European Fuel 

Cell Forum, Lucerne, Switzerland (2002) 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

UNIGEN® Regenerative Fuel Cell For Uninterruptible Power Supply 

Stephen Porter 

Proton Energy Systems 

10 Technology Drive 

Wallingford, CT 

Phone: (203) 678-2305; Fax: (203) 949-8078; E-mail: sporter@protonenergy.com 

DOE Technology Development Manager: Chris Bordeaux 

Phone: (202) 586-3070; Fax: (202) 586-9811; E-mail: Christopher.Bordeaux@ee.doe.gov 

Objectives 

Demonstrate hydrogen fuel cell based uninterruptible power supply with 

•	 Economic viability 

•	 Real world applications 

•	 Regulatory code compliance 

Achieve performance goals: 

•	 Power output 3+kW 

•	 Run time of <240 hours per year typical 

•	 Storage capacity of 50 hours 

•	 Instantaneous operation upon grid failure 

•	 Maintain digital equipment with continuous electrical supply 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Technology Validation 

•	 I. Hydrogen and Electricity Coproduction 

Education 

•	 B. Lack of Demonstrations or Examples of Real World Use 

Hydrogen Codes and Standards 

•	 O. Insurance Companies Recognize Current Standards 

Approach 

• Fabricate UNIGEN 	 ® Regenerative Fuel Cell (RFC) Uninterruptible Power Supply (UPS) using 

modular components allowing flexibility in power output, run time, and recharge time 

•	 Demonstrate technology performing useful work in a high visibility location with access to decision 

makers that are key to realizing the common usage of hydrogen based systems 

•	 Obtain permits for siting and operation of the UNIGEN® RFC UPS unit through co-authoring of new 

code with local authority 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Completed development tests and preliminary design of UNIGEN® RFC UPS 

•	 Established the Mohegan Energy, Environmental, Economics Education Center as the demonstration site 

•	 Established working agreement with local authorities at Mohegan Sun to co-author codes for siting 

and operation at their facility 

Future Directions 

•	 Complete final design of 3-kW RFC UPS and fabricate 

•	 Co-author a code to be adopted by the Mohegan Tribe for UNIGEN® RFC UPS 

•	 Perform full system validation test at Proton 

•	 Install UNIGEN® RFC UPS at Mohegan Energy, Environmental, Economics Education Center 

Introduction 

The UNIGEN® Regenerative Fuel Cell (RFC) 

for Uninterruptible Power Supply (UPS) project was 

initiated in October of 2002 as part of the U.S. 

Department of Energy State Energy Program (DOE/ 

SEP). The objective of the project is to demonstrate 

a fuel cell based UPS with economic viability. The 

UPS is required to provide 1-kW to 5-kW of high 

quality electrical power to digital equipment without 

interruption in case of a power outage in a real world 

application. The UNIGEN® RFC UPS being 

fabricated by Proton Energy Systems as part of the 

project provides 3 kW of electrical power without 

interruption during a loss of grid power using a 

proton exchange membrane (PEM) fuel cell that 

utilizes pure hydrogen for power generation and a 

PEM electrolyzer for refilling the hydrogen storage 

system after the grid has returned to normal. 

A significant aspect of the demonstration phase 

is the permitting process for siting the unit. As there 

is no one inclusive regulation that applies to an RFC 

UPS, one needs to be developed as part of the 

project. The generation of the regulation is a 

collaborative effort between Proton Energy Systems 

and the Public Safety Office of the Mohegan Tribe. 

Once completed, the Mohegan Tribe will adopt the 

regulation just as existing National Fire Protection 

Association (NFPA) regulations for mature 

technologies are recognized today. 

Approach 

The project has three separate goals, each 

requiring its own approach. The goals and the 

approach taken to meet each of them are given in the 

following paragraphs. 

Economic Viability. There are three main attributes 

to the regenerative fuel cell power system as it is 

used in a back-up power scenario. These are power 

output, run time, and recharge rate. The power 

output is determined by the size of the fuel cell. The 

runtime is determined by the capacity of the 

hydrogen storage portion of the system. The 

recharge rate is determined by the output rate of the 

electrolyzer used to generate the hydrogen. The 

approach of the Proton UNIGEN® system is to 

separate these attributes into modular components. 

The modular system components allow flexibility in 

meeting the particular needs of future end users by 

easily accommodating different output powers, backup times, and recharge times. Modular component 

systems are fitted to the customer's need in a building 

block approach, enabling a "buy as you need" 

scenario. Modular components also allow capability 

for future expansion with maximum reuse of 

hardware, avoiding the need for total system 

reconfiguration. Modular components greatly 

simplify maintenance, as field repairs become a 

simple module swap. 

2 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Real World Application. One of the significant 

challenges facing the common use of hydrogenbased technology is the general reluctance to adopt 

new technologies based on a lack of understanding 

and negative safety perception of hydrogen. 

Demonstrations outside the laboratories where the 

technologies are performing useful work in 

approachable atmospheres are key to breaking down 

these barriers. The approach to this aspect of the 

project is to site the RFC UPS where the potential for 

educational impact is greatest. The Mohegan 

Energy, Environmental, Economics Education 

Center provides a unique opportunity for showcasing 

the technology in a real world application. The 

Center receives about 1,000 visitors annually, with 

the majority being professionals, government 

representatives, and academics involved in the use, 

research, and industrial deployment of alternative 

energy technologies. Educating these decision 

makers is the first step in realizing the hydrogen 

economy future. 

Regulatory Code Compliance. As with any new 

technology, one of the significant challenges is the 

acceptance by local officials who are chartered with 

ensuring safety of the general public. This is also the 

case with the UNIGEN® Regenerative Fuel Cell 

UPS. Local safety and fire officials are familiar with 

the regulations outlined in documents published by 

the NFPA. They use these guidelines when assessing 

the installation and operation of equipment at their 

facilities. Since hydrogen technology based 

equipment is relatively new, the current regulations 

do not provide the required guidance in all areas. 

The approach used in this project is to co-author a 

regulation with the local safety and fire officials, 

pulling applicable pieces from established 

regulations as they apply to the UNIGEN® RFC 

UPS. Having the demonstration at the Mohegan Sun 

facility offers a unique opportunity to accomplish 

this. The Mohegan Tribe is a recognized sovereign 

nation with its own governing body. As such, there is 

the ability to generate a new regulation that will be 

applicable to their facilities. The number of agencies 

and cognizant parties is small, so the authoring and 

adoption process has a shorter cycle time versus 

regulations covering the state or national levels. 

Results 

The UNIGEN® Regenerative Fuel Cell for 

Uninterruptible Power Supply demonstration project 

is making groundbreaking progress in all three of the 

key areas identified. The design and development of 

the modular components, establishment of a real 

world application for demonstration, and regulatory 

code generation are on a clear path leading to success 

of the project. 

The modular system design has progressed 

through the preliminary phase by meeting the goal of 

a truly configurable system that will serve the needs 

of a variety of end users. The design of the system 

complies with the regulatory codes as they apply to 

each aspect of the technology. Development testing 

in the area of power transfer has resulted in a 

seamless transition from grid to fuel cell generated 

electrical power suitable for digital equipment. 

The real world application in a high visibility 

location has been established. Agreement has been 

reached with the Mohegan Energy, Environmental, 

Economics Education Center Administrator that the 

UNIGEN® RFC UPS will provide needed back-up 

power to the Center's twin 200-kW PC25 fuel cells' 

monitoring and safety systems. Without these 

systems, the PC25s are required to shut down during 

a power outage. The UNIGEN® RFC UPS gets its 

power to recharge the hydrogen storage system from 

the PC25s as well. The notion of a fuel cell based 

UPS keeping a fuel cell based power plant online 

during conventional grid failures is one that will 

create a lasting impact on visitors to the Center. 

The regulatory codes, as they apply to all types 

of hydrogen based equipment and codes pertaining to 

the design and installation of industrial equipment, 

have been reviewed for applicability to the 

UNIGEN® RFC UPS. A subset of these codes has 

been identified in draft form, and a preliminary siting 

plan has been developed. The Mohegan Sun Public 

Safety Official and the Fire Marshall have affirmed 

their support of the project and the generation of the 

new regulation. Once the regulation is complete and 

accepted by the Mohegan Tribal Government, it can 

be used as an example for other national associations 

in generation of standards for similar equipment. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

The UNIGEN® Regenerative Fuel Cell for 

Uninterruptible Power Supply project is well on its 

way towards successful completion in September of 

2004. Progress towards each of the three objectives 

has been positive, with results building upon one 

another. Development testing has yielded a design 

that will meet the performance objectives of the 

 FY 2003 Progress Report 

project. The modular component concept will enable 

economic viability in the future and has been 

designed for fuel cell based UPS system with power 

output in the 1 kW to 5 kW range. The barriers 

commonly associated with the public perception of 

hydrogen technology safety have been broken down 

through mutual cooperation and understanding of 

both the technology and the responsibility of the 

local authorities in keeping the public safe. 

4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Codes and Standards Analysis 

Dr. Michael R. Swain 

University of Miami 

P.O. Box 248294 

Coral Gables, Florida 33124 

Phone: (305) 284-3321; Fax: (305) 284-2580; E-mail: mswain@miami.edu 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811, E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

•	 Quantify ignitability of hydrogen-air mixtures in motion. 

Technical Barriers 

This project addresses the following technical barriers from the Hydrogen, Fuel Cells and Infrastructure 

Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Safety 

•	 C. Validation of Historical Data 

Hydrogen Codes and Standards 

•	 B. Competition between ICC and NFPA 

Approach 

•	 Design: generate apparatus to produce repeatable hydrogen leaks into the interior of a 5000 squarefoot warehouse. Produce experimentally verified computer model of hydrogen cloud formed by leak 

apparatus. 

•	 Test: locate the boundaries of ignitable cloud formed by hydrogen leak with electrical spark. 

•	 Analyze: compare boundaries of experimentally determined combustible cloud to boundaries of 

clouds defined by upper propagating lean limit of combustion (4.0% concentration hydrogen) and 

downward propagating lean limit of combustion (10.0% concentration hydrogen). Determine 

explanation for observed behavior. 

•	 Design: generate apparatus to produce homogeneous hydrogen-air mixture flows in exhaust ducts. 

•	 Test: test the ignitability of lean homogeneous hydrogen-air mixtures in exhaust ducts. 

•	 Analyze: determine the ignitability of homogeneous hydrogen-air mixtures in exhaust ducts as a 

function of Reynolds number. 

Accomplishments 

•	 Modeling: completed experimentally verified computer model of 20 SCFM hydrogen leak. Leak was 

directed horizontally and 4 feet above the floor (see Figure 1). 

•	 Design: completed design of sonic throttle experimental apparatus to accurately leak 20 SCFM 

hydrogen through 0.372 inch diameter orifice in center of 8 foot by 8 foot wall (Figures 2 and 3). 

•	 Examination: examined ignition characteristics of hydrogen cloud formed by 20 SCFM leak (Figure 4). 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

• Evaluate data taken to date and compare with published data. 

• Analyze published data to determine applicability to this research effort. 

• Conduct more ignitability tests with hydrogen leaks and flows of hydrogen-air mixtures in ducts. 

Figure 1. Model Results for 20 SCFM Hydrogen Leak 

Figure 3. Leak Test Apparatus 

Figure 2. Test Wall for Leaks 

Figure 4. Ignitability of 20 SCFM Hydrogen Cloud 

Introduction 

Four percent (4.0%) is a commonly quoted value 

for the lean limit of combustion (references 1-3). 

This value is then used as an indicator of ignitability 

in the determination of separation distances and 

electrical environment classification. Four percent 

concentration represents the upward propagating lean 

limit of hydrogen in a quiescent environment. Ten 

percent concentration represents the downward 

propagating lean limit of hydrogen in a quiescent 

environment. The values of lean limit that apply for 

a moving gas mixture (hydrogen leaks, flow in 

exhaust ducts) is somewhere between 4.0% and 10%. 

This work intends to determine what concentrations 

of hydrogen in air are ignitable under these 

conditions. 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Approach 

The approach is to produce a variety of hydrogen 

leaks and flows of hydrogen-air mixtures in ducts 

and test their ignitability. Parameters can then be 

developed to determine how close an ignition source 

can be to a hydrogen leak and what concentration of 

hydrogen is ignitable in an exhaust duct. 

Results 

The first set of test results are depicted in Figure 

4. The experimentally verified computer model of a 

20 SCFM hydrogen leak shows 4.0% concentration 

at a distance of 76 inches horizontally from the leak 

source in the wall. Using the commonly quoted 

value for the lean limit of combustion, this location 

should be ignitable. In actuality, the cloud could not 

be ignited unless the ignition source was 55 inches 

from the wall. This was true even though the ignition 

source was 110 millijoules (minimum ignition energy 

is three millijoules). The ignition source was 

required to be 47 inches from the wall to ignite the 

cloud with a single arc. At 55 inches, hundreds of 

arcs were required to produce ignition. 

 FY 2003 Progress Report 

Conclusions 

The separation distance defined by 4.0% 

hydrogen concentration is 38% greater than the 

separation distance defined by the actual ignitability 

of a 20 SCFM hydrogen leak. 

References 

1. Strehlow, R.A., 1968, Fundamentals of 

Combustion, International Textbook Company, 

Scranton, Pennsylvania 

2. Lewis, B., and von Elbe, G., 1987, Combustion, 

Flames and Explosions of Gases, Academic 

Press Inc., Orlando, Florida 

3. Glassman, I., 1987, Combustion, Academic 

Press Inc., Orlando, Florida 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Codes and Standards 

Jim Ohi (Primary Contact), Russ Hewett, Cathy Gregoire Padró 

National Renewable Energy Laboratory 

1617 Cole Boulevard 

Golden, CO 80401 

Phone: (303) 275-3706; Fax: (303) 275-3886; E-mail: jim_ohi@nrel.gov 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Subcontractors: 

Compressed Gas Association, Chantilly, VA 

Clean Vehicle Education Foundation, Washington, DC 

CSA America, Inc., Cleveland, OH 

LCC, Ltd., Clementon, NJ 

National Hydrogen Association, Washington, DC 

Robert L. Mauro, Serverna Park, MD 

Ron I. Sims, Saline, MI 

Objectives 

•	 Facilitate creation and adoption of model building codes and equipment standards for hydrogen 

systems in commercial, residential, and transportation applications. 

•	 Provide technical resources to harmonize development of international standards among the 

International Organization for Standardization (ISO), International Electrotechnical Commission 

(IEC), and Working Party on Pollution and Energy (GRPE). 

Technical Barriers 

This project addresses the following technical barriers from the Codes and Standards section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Limited Government Influence on Model Codes 

•	 B. Competition between ICC and NFPA 

•	 C. Limited State Funds for New Codes 

•	 D. Large Number of Local Government Jurisdictions (approximately 44,000) 

•	 E. Officials Training Differences 

•	 F. Limited DOE Role in the Development of ISO Standards 

•	 G. Inadequate Representation by Government and Industry at International Forums. 

•	 H. International Competitiveness 

•	 I. Strategic Conflicts between Domestic and International Standards Objectives 

•	 J. Consensus National Agenda on Codes and Standards 

•	 K. Lack of Domestic Industry Support at International Technical Committees 

•	 L. Competitiveness in Copyright of Published Standards 

•	 M. MNFPA 55 has not yet been completed, but is currently in progress 

•	 N. Lack of Technical Data to Revise NFPA 55 Standard (for underground and aboveground storage) 

•	 P. Current Large Footprint Requirements for Hydrogen Fueling Stations 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Approach 

•	 Support and facilitate the timely and efficient incorporation of hydrogen safety issues into existing and 

proposed codes and/or standards promulgated by organizations such as the International Code Council 

(ICC), National Fire Protection Association (NFPA), Society of Automotive Engineers (SAE), and ISO. 

•	 Support and encourage technical and operational consistency among and across the codes and 

standards developed by different organizations. 

•	 Disseminate and share information on development of codes and standards. 

•	 Identify critical gaps and deficiencies in codes and standards and formulate recommendations for 

addressing them. 

•	 Familiarize building code officials, fire safety officials, local/state/federal policymakers, and other 

strategic stakeholders (e.g., homebuilders, architects, transportation regulators) with hydrogen 

technologies and the related codes and standards. 

•	 Create "national template" to harmonize standards, codes, and regulations. 

•	 Develop generic licensing agreement for web-based access to standards. 

•	 Develop training modules and conduct workshops with ICC and NFPA. 

•	 Develop unified national agenda and support consistent representation of technical experts from 

industry and government at key global venues. 

•	 Develop comprehensive R&D plan and program for validation of codes and standards. 

•	 Actively seek opportunities to work collaboratively with other DOE programs and non-federal 

organizations involved in hydrogen-related codes and standards efforts to streamline codes and 

standards development and minimize duplication of efforts. 

Accomplishments 

•	 Hydrogen safety incorporated in 2003 edition of ICC model codes. 

•	 Developed draft template for national standards, codes, and regulations for hydrogen vehicles, fueling/ 

service/parking facilities, vehicle/facility interface, and on-site hydrogen generation, and for stationary 

and portable fuel cells. 

•	 Testing underway to establish technical basis for separation distances for safe bulk storage of 

hydrogen. 

•	 Draft performance-based regulations for compressed and liquid hydrogen storage for vehicles 

completed by United Nations-European Economic Council Working Party on Pollution and Energy 

(UN-ECE/GRPE) informal group on Hydrogen/Fuel Cells. 

•	 Standards under development and on-going coordination with American Society of Mechanical 

Engineers (ASME) Hydrogen Steering Committee; Underwriters Laboratory (UL) Standards 

Technical Panel 2264 Hydrogen Generators; NFPA Hydrogen Coordination Committee; CSA America 

Technical Advisory Group for on-board gaseous hydrogen container standard; International Hydrogen 

Infrastructure Group Codes and Standards Working Group; California Fuel Cell Partnership Codes and 

Standards Working Group; and Working Group for Emergency Response Guide for Fuel Cell Buses, 

U.S. Fuel Cell Council Codes and Standards Working Group. 

•	 Organization agreements among U.S., Canada, and Japan in place for Partnership for Advancing the 

Transition to Hydrogen (PATH). 

Future Directions 

•	 Refine overall codes and standards coordination program. 

•	 Create centralized, publicly accessible web-based data center. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Negotiate DOE license from primary standard and code development organizations. 

•	 Create one-stop technical assistance for hydrogen projects including directory of primary contacts for 

information and technical assistance. 

•	 Convene annual safety, codes, and standards summit meeting. 

•	 Initiate comprehensive R&D plan for validation of standards. 

•	 Develop hydrogen safety training packages for local code officials with NFPA and ICC. 

•	 Identify and fund appropriate experts to fully participate in development of Global Technical 

Regulations for on-board storage and other hydrogen-related regulations under development. 

•	 Develop Global Technical Regulations for hydrogen fuel cell vehicles that include harmonized 

regulations for on-board hydrogen storage and are harmonized with U.S. Federal Motor Vehicle Safety 

Standards. 

•	 Develop harmonized standards for fuel cell power plants. 

Introduction 

The development and promulgation of codes and 

standards are essential if hydrogen is to become a 

significant energy carrier and fuel. Codes and 

standards are critical to establishing a marketreceptive environment for commercializing 

hydrogen-based products and systems. With the help 

of key stakeholders, the Hydrogen, Fuel Cells & 

Infrastructure Technologies Program of the U.S. 

Department of Energy (DOE) and the National 

Renewable Energy Laboratory (NREL) are 

coordinating a collaborative national effort by 

government and industry to prepare, review, and 

promulgate hydrogen codes and standards needed to 

expedite hydrogen infrastructure development. 

DOE has sponsored work in codes and standards 

as a key part of its efforts since 1995. The initial 

efforts included support for the National Hydrogen 

Association (NHA) to conduct national codes and 

standards workshops at least annually to bring 

together experts to address key issues and needs. 

These and other efforts sponsored by DOE have 

encouraged organizations such as the International 

Code Council (ICC), the National Fire Protection 

Association (NFPA), the Society of Automotive 

Engineers (SAE), Underwriters Laboratory (UL), 

and the Compressed Gas Association (CGA) to 

conduct national activities in hydrogen codes and 

standards. Federal agencies such as the Department 

of Transportation (DOT), the National Aeronautics 

and Space Administration (NASA), and the National 

Institute of Standards and Technology (NIST) also 

have regulatory or mission-related interests in 

hydrogen regulations, codes, and standards. Under 

this project, DOE has assumed leadership in 

accelerating the creation and adoption of a 

harmonized set of national and international 

standards, codes, and regulations that are essential 

for the safe use of hydrogen by consumers in the U.S. 

and worldwide. 

Approach 

The federal government has an indirect and 

relatively limited role in the voluntary consensus 

process through which codes and standards are 

developed in the U.S. Because of the importance of 

establishing a harmonized set of standards upon 

which model codes and regulations can be based, 

DOE, primarily through NREL, has devoted 

considerable effort to facilitate and coordinate this 

consensus process. Much of this effort is carried 

forth through the DOE Hydrogen Codes and 

Standards Coordinating Committee (HCSCC). In 

addition to serving as the database repository, 

clearinghouse, and gatekeeper for the codes and 

standards activities being conducted within DOE, the 

HCSCC also collaborates with other national and 

international organizations involved in codes and 

standards activities. The HCSCC conducts monthly 

conference calls to update participants on current 

activities and to discuss key issues and convenes 

quarterly meetings to: 

•	 Coordinate codes and standards development 

efforts and prevent duplication of efforts, 

•	 Identify critical deficiencies and gaps in hydrogen codes and standards development efforts that 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

could adversely impact market acceptance and 

penetration, 

•	 Collaboratively determine a strategy and action 

plan to address critical gaps and deficiencies, and 

•	 Identify specific opportunities for organizations 

to work collaboratively in developing codes and 

standards. 

Once developed, standards are usually 

incorporated into model codes that, in turn, must be 

adopted by state and local jurisdictions to have the 

force of law. In 2001, the model codes of the ICC did 

not include hydrogen as an energy source or fuel 

cells as either power-generating devices or 

appliances. To address this limitation, the ICC 

established an Ad Hoc Committee (AHC) on 

hydrogen technologies, at the request of DOE, to 

reduce the time needed to have the model codes 

amended to include hydrogen technologies. As part 

of a collaborative process, DOE sponsored the 

participation of experts to the AHC to help ensure a 

balanced membership of hydrogen users, producers, 

and regulator interests. This process was successful, 

and the 2003 edition of the ICC model codes contain 

provisions for hydrogen use in and around buildings 

and consumer facilities. 

In addition to sponsoring activities related to ISO 

TC197 and other international standards 

development organizations (SDOs), DOE is helping 

to organize the Partnership for Advancing the 

Transition to Hydrogen (PATH) to link and unify 

hydrogen interests of the U.S., Canada, Japan, 

Argentina, and other countries in the Pacific Rim and 

the Americas. The goals of PATH are to identify and 

build on a community of interest among members by 

addressing common issues and to increase 

knowledge and activities concerning hydrogen, 

particularly safety and codes and standards. PATH 

will also help interested hydrogen parties in nonmember countries to organize hydrogen activities 

and contribute to the strengthening of the 

international hydrogen community. 

Results 

The key results of the domestic codes and 

standards effort were the inclusion of hydrogen 

applications in the 2003 edition of the ICC model 

codes and the creation of "national templates" 

through which DOE, NREL, and the major SDOs 

and model code organizations will coordinate the 

preparation of critical standards and codes for 

hydrogen technologies and applications. Provisions 

for the safe use of hydrogen are now incorporated in 

the ICC's International Building, Residential, Fire, 

Mechanical, and Fuel Gas Codes. Additional work 

to reduce the footprint of hydrogen fueling stations 

will be considered under the ICC's 2003-04 code 

cycle that, if successful, will be incorporated in the 

2006 edition of the ICC model codes. 

The draft template for hydrogen applications on 

vehicles and in fueling, service, and parking facilities 

is shown in Figure 1. The draft template for on-site 

hydrogen generation and for stationary and portable 

fuel cells is shown in Figure 2. The templates 

designate lead and supporting organizations for the 

standards and codes to be developed and were 

prepared in workshops by consensus of the 

organizations shown. This consensus overcomes the 

historic competitiveness among the organizations to 

develop and sell standards and model codes and is a 

Figure 1. Draft Template for Vehicle Systems and 

Refueling Facilities 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2. Draft Template for On-Site Hydrogen
 

Generation and Fuel Cells
 

critical step in creating a collaborative and cooperative 

national agenda for hydrogen codes and standards. 

The key results in international codes and 

standards were the launching of PATH and the 

strengthening of the collaboration among DOE, DOT, 

and the Environmental Protection Agency (EPA) in 

representing the interests of the U.S. government and 

industry at the GRPE. The DOE is now a full 

participant at international forums at which discussion 

and negotiations on global technical regulations 

affecting hydrogen take place. Internationally 

accepted hydrogen standards can facilitate trade 

among nations and lower regulatory trade barriers. If 

hydrogen is to become a major energy carrier, the 

hydrogen interests of key countries must be 

coordinated, and countries new to hydrogen must be 

introduced to its benefits and safe use. 

Conclusions 

DOE has supported a growing and increasingly 

important effort to coordinate the development and 

promulgation of hydrogen codes and standards. In 

addition to supporting specific projects to develop 

codes, such as that of the ICC/AHC, and standards, 

such as that of ISO TC197, the DOE is supporting 

the coordination of many other efforts so that codes 

and standards can be developed and adopted as 

efficiently as possible and so that the lack of codes 

and standards will not be a barrier to the 

commercialization of hydrogen technologies. 

Support of codes and standards efforts will remain an 

important part of the Program for many years to 

come. 

FY 2003 Publications/Presentations 

1. Domestic Codes and Standards: DOE Status 

Report, Fuel Cell Summit VII, College Park, MD, 

May 2003. 

2. Codes and Standards: The International Scene, 

Fuel Cell Summit VII, College Park, MD, May 

2003. 

3. Hydrogen Codes and Standards, Hydrogen, Fuel 

Cells and Infrastructure Technologies Program, 

2003 Merit Review and Peer Evaluation Meeting, 

Berkeley, CA, May 2003. 

4. Domestic Codes and Standards: DOE Status 

Report, International Hydrogen Infrastructure 

Working Group, The Woodlands, TX, May 2003. 

5. Hydrogen Codes and Standards, National 

Hydrogen Association, Codes and Standards 

Workshop, Ft. Worth, TX, October, 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. National Hydrogen Association Meritorious 

Service Award to Guy Tomberlin, Chair, ICC 

Hydrogen Ad Hoc Committee, March 6, 2003 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Carbon Monoxide Sensors For Reformate Powered Fuel Cells 

Rangachary Mukundan (Primary Contact), Eric L. Brosha, and Fernando Garzon 

Los Alamos National Laboratory 

Electronics and Electrochemical Materials and Devices Group 

MS D429, SM-40, TA-3 

Los Alamos, NM 87545 

Phone: (505) 665-8523; Fax: (505) 665-4292; E-mail: mukundan@lanl.gov 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Objectives 

Hydrogen reformate gas powered fuel cell systems require sensors for carbon monoxide level monitoring 

and feedback control. 

•	 Develop a low temperature sensor for measuring 10-100 ppm range concentrations for stack poisoning 

control. 

•	 Develop a high temperature sensor for the measurement of 0.1 to 2% carbon monoxide in the
 

reformate gas for fuel processor control.
 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

Approach 

Two electrochemical sensor types are being investigated for high and low temperature carbon monoxide 

sensing: 

•	 An oxide solid electrolyte device based on the kinetics of the electrode reactions is being developed for 

both the high and low temperature applications. 

- Yttria-doped zirconia and gadolinia-doped ceria oxygen ion conductors and strontium yttrium 

zirconium oxide proton conductor are being investigated as the solid electrolyte. 

- Several metals, including Pt, Pd, Au, Ru and Ni, are being evaluated as the sensing and reference 

electrodes. 

•	 A low temperature amperometric device based on the carbon monoxide inhibition of hydrogen 

oxidation kinetics at the electrodes of a polymer electrolyte membrane (PEM) fuel cell is being 

developed for the low temperature application. 

- Sensors based on perfluorosulfonic acid polymer electrolytes are being evaluated. 

- Different catalyst loadings of carbon supported and un-supported Pt, Ru and Pt/Ru alloys are being 

evaluated as electrodes. 

Accomplishments 

•	 Ceramic electrolyte based sensors that operate at 150-300oC have been developed. These sensors 

respond well to 10-100 ppm carbon monoxide in a simulated reformate stream. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Amperometric low temperature carbon monoxide sensors based on a polymer electrolyte have been 

developed and tested under a variety of conditions. These devices respond well at ambient 

temperature to 10-100 ppm carbon monoxide in hydrogen streams. 

•	 Polymer electrolyte based sensors have been optimized to operate at 70o

C and respond to 100-1000 

ppm of CO in a simulated reformate stream. 

Future Directions 

•	 Analyze the response time of the oxide and polymer electrolyte based sensors. 

•	 Evaluate the performance of the polymer and oxide electrolyte based systems under practical fuel 

reformate conditions. 

•	 Evaluate the stability of the response of the oxide electrolyte based sensors. 

•	 Modify the electrodes of the oxide electrolyte based sensor to enable it to detect higher concentrations 

of CO (0.1-2%) at T > 250o

C. 

•	 Demonstrate a prototype oxide based sensor with a patterned heater incorporated on the sensor 

electrolyte body. 

Introduction 

The detection and measurement of carbon 

monoxide in high temperature reformate streams is 

of vital importance to the successful implementation 

of fuel cells for transportation. Much research is 

being performed to optimize low cost fuel reformer 

systems that convert liquid hydrocarbon fuels to 

hydrogen gas containing fuel streams. This 

hydrogen gas typically feeds a polymer electrolyte 

membrane (PEM) fuel cell utilizing a platinum based 

anode. It is well known that low concentrations (10-

100 ppm) of carbon monoxide impurities in 

hydrogen can severely degrade the performance of 

PEM fuel cell anodes.1

 This performance 

degradation is due to strong adsorption of carbon 

monoxide on the electro-active platinum surface sites 

where hydrogen is normally oxidized to protons.1 

Therefore, the proper design of combined fuel 

cell stack and reformer systems must pay careful 

attention to the minimization of carbon monoxide 

before the processed fuel stream enters the stack. 

Many reformer systems use a secondary preferential 

oxidation (PrOx) reactor that selectively oxidizes the 

carbon monoxide present in the reformate stream. 

The efficiency of this PrOx reactor will depend on 

the accurate and rapid measurement of the inlet (or 

outlet) CO concentration at the reactor. Moreover, 

current fuel cells use air-bleeding methods to reduce 

the carbon monoxide poisoning of the Pt anode. 

Since this method involves the mixing of 2-6% air 

with the fuel stream, it results in a decrease in the 

energy efficiency of the fuel cell system and can 

greatly benefit from the accurate determination of the 

CO content of the fuel stream entering the stack. 

Hence, CO sensors that measure the CO content of 

the fuel stream before and after the PrOx reactor can 

be used for feedback control, thus allowing these 

integrated fuel cell systems to operate at maximum 

energy efficiency. We are designing and developing 

solid-state electrochemical sensors meeting these 

criteria, leading to the demonstration of prototype 

sensors. 

Approach 

High temperature carbon monoxide sensors. Los 

Alamos National Laboratory (LANL) is developing 

high temperature zirconia- and ceria-based 

electrochemical sensors to measure CO in hydrogen 

streams. These sensors would operate at 150-400oC 

and can be used for feedback control either before or 

after the PrOx reactor. We have successfully 

developed novel mixed-potential sensors that are 

capable of measuring ppm levels of CO in air. The 

unique design of these sensors makes them robust, 

stable and reproducible.2,3 In this project, we are 

working on modifying the electrodes of these devices 

to enable them to work in a hydrogen atmosphere. 

2 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

We are also exploring the possibility of using protonconducting electrolytes and using these sensors in an 

amperometric mode. 

Low temperature carbon monoxide sensors. Low 

temperature carbon monoxide sensors based on the 

reversible carbon monoxide adsorptive poisoning of 

precious metal electrodes are also being developed at 

LANL. The addition of metals such as ruthenium to 

the platinum anode catalyst is known to greatly 

improve the hydrogen-oxidation kinetics in the 

presence of CO. An amperometric sensor that senses 

the differential CO inhibition of the hydrogen 

oxidation reaction at 2 electrodes can be fabricated 

from a platinum electrode, a proton conductor and a 

platinum ruthenium alloy electrode. While the 

current density of the platinum electrode will be 

influenced by the surface coverage of carbon 

monoxide, the current density at the Pt/Ru alloy 

electrode should be relatively unaffected. This 

difference in the electrode current density in the 

presence of CO can be used to fabricate a low 

temperature CO sensor. In this project, we are 

optimizing the electrode composition, precious metal 

loading and operating temperature of these 

ampereometric sensors in order to develop a CO 

sensor that will sense 1-100 ppm CO in the inlet fuel 

stream of a fuel cell stack. 

Results 

Oxide electrolyte based sensors were prepared 

by sputtering or brush-painting various metal 

electrodes on to oxygen-ion conducting 

electrolytes. The sensor configuration is shown in 

Figure 1, where the electrolyte used was either 

Zr0.85Y0.15O1.95 (YSZ) or Ce0.8Gd0.2O1.9 (CGO), 

and the electrodes used were selected from Pt, Ru, 

Pd, Au or Ni. The substrate was 0.5 mm thick, and 

the electrodes were 0.5-100 Fm thick. When a 

CGO electrolyte with 1 Fm thick Pt and Ni 

sputtered electrodes was exposed to CO, an 

electromagnetic field (EMF) that was proportional 

to the CO concentration developed across the Pt and 

Ni electrodes. The response of this sensor to 100-

500 ppm CO in a base gas of 68%H2/29%CO2/ 

3%H2O at an operating temperature of 250o

C is 

shown in Figure 2 (circles). The Pt electrode was 

positive with respect to the Ni electrode, indicating 

that CO poisoning lowers the EMF (less negative) 

 FY 2003 Progress Report 

of the Pt electrode. However, the response to CO 

decayed over time, probably due to some 

irreversible poisoning of the Ni electrode. When 

the sensor was operated at a negative bias of 1 

Famp, the stability of the sensor was found to 

improve. This improvement in the stability of the 

sensor, shown in Figure 2 (squares), can be 

Figure 1. Schematic of Sensor Configuration 

Figure 2.	 Response of a Pt/CGO/Ni sensor to 100-500 

ppm CO in a Base Gas of 68%H2/29%CO2/ 

3%H2O at an Operating Temperature of 

250o

C [Bias = 0 μamp (circles); Bias = –1 

μamp (squares).] 

3 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3.	 Response of a Pt/CGO/Ni Sensor to 25-100 

ppm CO in a Base Gas of 68%H2/29%CO2/ 

3%H2O at an Operating Temperature of 

240o

C 

Figure 4.	 Response of a Pd/YSZ/Ni Sensor to 25-100 

ppm CO in a Base Gas of 68%H2/29%CO2/ 

3%H2O at an Operating Temperature of 

185o

C 

attributed to the cleaning of the CO from the surface 

of the Ni electrode. 

The stability of the CGO-electrolyte based 

sensors was found to improve with a decrease in the 

operating temperature and the total exposure to CO 

of the sensor electrodes. This is demonstrated by the 

sensor response to 25-100 ppm CO at 240oC (Figure 

3). A stable sensor response of 6 mV was obtained 

for 100 ppm of CO in a 68%H2/29%CO2/3%H2O 

fuel stream. Moreover, this response was found to be 

largely independent of the H2 and H2O content of the 

fuel stream. However, this sensor did show some 

decay in the response when exposed to 100 ppm CO 

for greater than 1 hour. 

The sensor response to CO was optimized by 

studying various electrode and electrolyte 

combinations, and maximum response was obtained 

for a sensor using a YSZ electrolyte with a sputtered 

Ni electrode and a brush-painted Pd electrode. This 

sensor had a response of 60 mV to 100 ppm CO in a 

base gas of 68%H2/29%CO2/3%H2O at an operating 

temperature of 185o

C, as shown in Figure 4. 

Although this is a 10 fold improvement in the sensor 

sensitivity as compared to the CGO based sensors, 

these sensors showed a similar decay in the sensor 

response when exposed to low concentrations of CO 

for long periods of time or high concentrations of CO 

for short periods. The response time of this sensor 

was less than 1 minute and was limited by the flow 

rates of the gases used in our experiment. This 

sensor also possessed the required sensitivity to 

detect 1-100 ppm of CO in the fuel inlet stream of the 

fuel cell stack and has the potential to be used to as a 

CO sensor for stack control. 

Conclusions 

•	 Developed polymer electrolyte based sensors for 

the monitoring of 10-100 ppm carbon monoxide 

at room temperature and 100-1000 ppm carbon 

monoxide at 70oC. 

•	 Successfully developed oxide electrolyte based 

sensors for the detection of 10-100 ppm CO in 

the fuel inlet of a fuel cell stack. These sensors 

operate and T $ 150oC and have a response time 

less than 1 minute. 

•	 Future work includes the optimization of the 

sensor response time and stability. The 

electrodes of this oxide sensor will be modified 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

to try and develop a CO sensor for reformer 

control that can measure 0.1 to 2% CO. A 

patterned heater will be incorporated in these 

sensors, and prototypes that work in a reformate 

stream will be demonstrated. 

References 

1.	 S. Gottesfeld and T. Zawodzinski in “Advances in 

Electrochemical Science and Engineering”, 5, pp. 

219-225 (1998). 

2. R. Mukundan, E. Brosha, and F. Garzon, Mixed 

Potential Sensors for CO Monitoring in Chemical 

and Biological Sensors and Analytical Methods II, 

PV 2001-18, pp. 464-469, The Electrochemical 

Society Inc. (2001). 

3. Rangachary Mukundan, Eric. L. Brosha and 

Fernando H. Garzon, Electrodes for Solid State 

Gas Sensors, Patent Application Filed, S.N. 10/ 

175,252, June 18, (2002). 

FY 2003 Publications/Presentations 

1. R. Mukundan, E. L. Brosha, and F. H. Garzon, 

“An electrochemical sensor for the detection of 

carbon monoxide in hydrogen containing 

streams”. To be presented at the 204th Meeting of 

the Electrochemical Society, Florida, October 12-

17 (2003). 

2. R. Mukundan, E. L. Brosha, and F. H. Garzon, “A 

low temperature sensor for the detection of carbon 

monoxide in hydrogen”. Presented at the SSI-14 

Conference, California, June 24 (2003). 

3. R. Mukundan, E. L. Brosha, and F. H. Garzon, “A 

low temperature sensor for the detection of carbon 

monoxide in hydrogen”. Submitted to the special 

issue of the Journal of Solid State Ionics, May 

(2003). 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Electrochemical Sensors for Proton Exchange Membrane Fuel Cell Vehicles 

L. Peter Martin (Primary Contact) and Robert S. Glass 

Lawrence Livermore National Laboratory 

P.O. Box 808, L-353 

Livermore, CA 94550 

Phone: (925) 423-9831; Fax: (925) 423-7040; E-mail: martin89@llnl.gov 

DOE Technology Development Managers: 

Nancy Garland, Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Neil Rossmeissl, Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

•	 Develop a hydrogen safety sensor operating below 500°C with 1 second response time and low 

sensitivity to humidity and hydrocarbons 

•	 Develop a hydrogen fuel sensor for reformate fuel monitoring for hydrogen concentrations ranging 

between 10 to 100% 

•	 Develop a CO sensor for reformate fuel monitoring (future) 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

Approach 

Safety sensor 

•	 Utilize proven solid state electrochemical technology comparable to automotive exhaust gas oxygen 

sensors based on oxygen conducting ceramic electrolytes 

•	 Apply novel nanocrystalline electrode materials with high electronic conductivity to reduce response 

time and operating temperature 

•	 Design and build micro-sensor configuration to minimize heater power requirements 

Fuel sensor 

•	 Develop and characterize an amperometric sensor using a known proton conducting oxide electrolyte 

•	 Correlate 'pumping' current with hydrogen concentration in simulated reformate gas 

•	 Reduce operating temperature by applying novel electrode/electrolyte materials to enhance
 

conductivity and surface exchange
 

•	 Ensure electrolyte stability in reformate environment by performing appropriate thermal 

characterization and electrochemical testing
 

Accomplishments 

Safety sensor 

•	 Operating temperature has been reduced to 430 - 460oC 

•	 An integrated, planar heater/sensor design has been established (heated substrates supplied by Ford) 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Preliminary testing indicates no baseline drifting over several hundred hours 

•	 External collaborators interested in testing/commercialization are being explored (Ford is currently 

testing) 

Fuel sensor 

•	 A candidate electrolyte with high stability versus CO2 has been selected 

•	 Preliminary laboratory prototypes have been fabricated and are being tested 

Future Directions 

Safety sensor 

•	 Finalize sensor design 

•	 Locate external collaborator interested in testing/commercialization (Ford has agreed to test sensor) 

Fuel Sensor 

•	 Evaluate various materials, processing techniques, and designs 

•	 Fabricate first prototype 

•	 Seek industrial collaboration 

•	 Develop integrated fuel sensor 

Introduction 

Proton exchange membrane fuel cells (PEMFCs) 

are among the most promising clean power system 

technologies being developed for transportation 

applications. However, the use of hydrogen and 

other combustible gases for automotive applications 

requires new on-board safety sensors and controls to 

prevent fire and explosion hazards. In addition, if 

hydrogen fuel is supplied by an on-board reformer, 

additional control and monitoring devices are needed 

in order to protect and to efficiently operate the 

PEMFCs. 

The purpose of this project is to design, fabricate, 

and demonstrate solid state electrochemical sensors 

for various H2 monitoring applications on PEMFC 

vehicles. The first phase of the project has focused 

on the development of a hydrogen safety sensor 

intended to be deployed at critical locations on the 

vehicle to detect potentially dangerous hydrogen 

leakage. Currently, that portion of the project is 

being completed, and development of a hydrogen 

fuel sensor is being initiated. The fuel sensor is 

intended to monitor the fuel quality (i.e. percent 

hydrogen) in the gas stream supplied from an onboard hydrogen reformer (reformate gas). Reformate 

gas is typically a severe environment containing a 

variable mixture of H2, H2O, N2, CO, CO2, and 

residual hydrocarbons. Both of these sensors are 

being developed by applying novel materials to 

established electrochemical sensor technologies. 

Approach 

Our approach to the hydrogen safety sensor is 

based on established solid-state electrochemical 

sensor technology. The proposed sensor consists of 

two electrodes on an oxygen conducting electrolyte. 

One electrode serves as a reference and the other as a 

sensing electrode. The electrode materials are 

selected so that they have different catalytic activities 

toward the oxidation of hydrogen gas. This causes 

the electrodes to reach some kinetically limited 

potential determined by the concentration of 

hydrogen in a hydrogen/air mixture. The sensor 

operates by measuring the difference between these 

electrode potentials, and the hydrogen concentration 

can be correlated with the magnitude of this potential 

difference. Similar sensors have been proposed in 

the past [1]; however, sensitivity and response speed 

were insufficient for the proposed safety sensor 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

application. We have proposed that by using a higher 

conductivity electrode material, response time can be 

reduced to the point where the sensor becomes 

suitable for the safety application. For that reason, 

the current safety sensor uses a metal oxide (indium 

oxide) doped to promote electronic conductivity. 

The resultant fast response, along with the sensitivity 

of the sensor, will be shown below. 

The hydrogen fuel sensor operates on a very 

different principle whereby the hydrogen is 

electrochemically dissociated and pumped through a 

proton conducting ceramic membrane at high 

temperature. The pumping current (at constant 

applied voltage) can be correlated to the hydrogen 

concentration in the test gas. The approach to 

realizing this sensor will proceed in two parts. The 

first will be to demonstrate the sensing technology 

using a known proton conductor with established 

stability in the reformate environment. However, 

since these materials tend to be comparatively poor 

proton conductors, the operating temperature will be 

required to be fairly high (~600o

C). The second part 

of the developmental effort will be to explore novel 

proton conductors to identify the best candidate 

providing the optimum combination of conductivity 

and stability for the proposed application. Once 

identified, this ‘optimum’ electrolyte will be 

implemented in the sensor technique demonstrated in 

the first part of the project. Progress towards these 

goals will be discussed below. 

Accomplishments 

Safety sensor. During the prior efforts, a safety 

sensor was demonstrated which had good sensitivity 

and response time, but relatively high operating 

temperature (500oC). That sensor consisted of 

electrodes on an unheated substrate, and testing 

required that the sensor be heated using a laboratory 

tube furnace. During FY 2003, the principal goals 

were to modify the sensor to reduce the operating 

temperature below 500oC, and to demonstrate an 

integrated, self-heated design. Figure 1 shows that 

integrated design, where the yttria-stabilized zirconia 

(YSZ) electrolyte is attached to the surface of an 

alumina substrate containing an integrated Pt 

resistive heater [2]. The one-inch scale bar in the 

figure shows the sensor size. Also shown in the 

figure are the electrode size and location. It is worth 

 FY 2003 Progress Report 

noting that the electrodes are misaligned from the 

heating element, causing the power consumption 

(~5.4 W at 440o

C) of this sensor to be ~20% elevated 

for a given temperature. This misalignment is being 

corrected in the next generation design. 

Figure 2 shows the sensor response, at 440o

C, to 

3300 ppm (0.33%) H2 in air containing 10% and 

100% relative humidity. The data show the sensor 

baseline near 0 mV in the absence of H2, and a 

reproducible response of ~225 or 250 mV (10 and 

Figure 1.	 H2 Safety Sensor Prototype Showing 

a) Sensing Electrode, b) Reference Electrodes, 

c) Resistive Heater, and d) Electrical 

Connections; the Scale Bar at the Top Is in 

Inches 

Figure 2.	 Response of the Hydrogen Safety Sensor, 

Operated at 440o

C, to 3300 ppm H2 in Air 

Containing 10% (squares) and 100% (crosses) 

Relative Humidity 

3 
 

 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

100% relative humidity, respectively). It is clear that 

the sensor responds within approximately one second 

(which is the DOE technical target) to the addition of 

the H2. The slight overshoot is a consequence of the 

low operating temperature, and it may be possible to 

reduce this effect by modifying the reference electrode 

to reduce the interfering response there. Long term 

testing indicates that the sensor baseline is stable and 

that the sensor response is reproducible over a period 

of several hundred hours. 

Figure 3 shows the response of the sensor, again 

at 440oC and in 10% and 100% relative humidity, to 

varying H2 and CH4 concentrations in air. The data 

show a slight (~10%) reduction in sensitivity in the 

presence of high relative humidity. This slight crosssensitivity is considered to be acceptable since 

discussions with commercial end-users indicate 

generally severe degradation in performance with 

humidity for the commercially available sensors. 

The data also show that the sensor has a very high 

sensitivity at low H2 concentration. This sensitivity 

is an attractive feature for early leak detection. 

Finally, the selectivity versus CH4 is shown to be 

approximately five to one. 

Fuel sensor. Development of the H2 fuel sensor 

has been initiated, and a preliminary prototype sensor 

has been fabricated from a Sr-zirconate electrolyte 

with known stability in H2O and CO2 gas. Figure 4 

shows the pumping current (i.e. the response) of that 

sensor operated at 600oC as a function of H2 

 FY 2003 Progress Report 

concentration. The test gas was composed of the 

indicated concentration of H2 with 20% H2O and a 

balance of N2. These data clearly demonstrate that 

the device is sensitive to the concentration of H2 in 

the test gas. Further testing is underway to evaluate 

the cross-sensitivity to CO2 and H2O. By 

incorporation of a diffusion-limiting porous barrier 

over one of the electrodes, it should be feasible to 

force the response of the sensor to be linear versus 

the H2 concentration. 

Conclusions and Future Work 

A H2 safety sensor has been demonstrated with 

an integrated, self-heated design operating at 430 - 

460oC. Preliminary testing indicates no baseline 

drifting over several hundred hours. External 

collaborators interested in testing/commercialization 

are being explored. A candidate electrolyte has been 

identified for the H2 fuel sensor with high stability 

versus CO2. Preliminary laboratory prototypes have 

been fabricated and are being tested. Ongoing 

developmental efforts for the fuel sensor include 

evaluation of various materials, processing 

techniques, and designs. In addition, an industrial 

collaboration will be sought to facilitate the eventual 

commercialization of an integrated fuel sensor. 

References 

1. G. Lu, N. Miura and N. Yamazoe, "Hightemperature hydrogen sensor based on stabilized 

Figure 3.	 Response of the Sensor, Operated at 440oC, to 

H2 and CH4 in Air Containing 10% Relative 

Humidity (diamonds) and 100% Relative 

Humidity (squares) 

Figure 4.	 Fuel Sensor Response versus H2 Concentration 

at 600o

C, 20% H2O, Balance N2; Applied Bias 

Is 250 mV 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies

zirconia and a metal oxide electrode," Sensors and 

Act., B35-36, (1996) 130-135. 

2. Supplied by Rick Soltis, Ford Research Center, 

Dearborn, MI. 

Publications 

1. L. P. Martin, Q. Pham, and R. S. Glass, 

"Electrochemical Hydrogen Sensor for Safety 

Monitoring," submitted for publication in Solid 

State Ionics (4/2003). Will be a peer-reviewed, 

special edition serving as Proceedings of The 14th 

International Meeting on Solid State Ionics. 

Presentations 

1. L. P. Martin and R. S. Glass, "Electrochemical 

Sensors for PEMFC Vehicles," presented at the 

DOE Hydrogen, Fuel Cells & Infrastructure 

Technologies Program Review, (Berkeley, CA, 

May 19-22, 2003). 

2. L. P. Martin, Q. Pham, and R. S. Glass, 

"Electrochemical Hydrogen Sensor for Safety 

Monitoring," poster presented at The 14th 

International Meeting on Solid State Ionics, 

(Monterey, CA, June 22-27, 2003). 

3. L. P. Martin, A.-Q. Pham, and R. S. Glass, 

"Hydrogen Sensor Based on Yttria-Stabilized 

Zirconia Electrolyte and Rh-Promoted ITO 

Sensing Electrode," submitted for presentation at 

the 204th Meeting of the Electrochemical Society 

(Orlando, FL, October 12-17, 2003). 

 FY 2003 Progress Report 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Interfacial Stability of Thin Film Sensors 

Roland Pitts (Primary Contact), Dave Smith, Ping Liu, Ed Tracy, Se-Hee Lee, Jim Ohi 

National Renewable Energy Laboratory (NREL) 

1617 Cole Blvd. 

Golden, CO 80401 

Phone: (303) 384-6485; Fax: (303) 384-6655; E-mail: roland_pitts@nrel.gov 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

The goal of this project is to develop safe, low cost, lightweight, reliable hydrogen safety sensors that can 

be used wherever hydrogen is used, stored, or transported. Safety sensors need to satisfy the following 

requirements established by DOE: 

• Measurement range: 0.1–10% H2 in air 

• Operating temperature: -30°C – +80°C 

• Response time: <1 s 

• Accuracy: 5% 

• Gas environment: ambient air, 10–98% relative humidity (RH) range 

• Lifetime: 5 years 

• Selectivity from interference gases, such as hydrocarbons, is needed. 

Technical Barriers 

This project addresses the following technical barriers from the following sections of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

Hydrogen Safety 

• A. Limited Historical Database for Components 

• C. Validation of Historical Data 

• D. Technical and Scientific Understanding of Systems Limits the Value of Protocols 

• F. Liability Issues 

• L. Expense of Data Collection and Maintenance 

• M. Quality of Data 

Hydrogen Delivery 

• D. High Capital Cost of Pipelines 

Fuel Cells 

• B. Sensors 

Technology Validation 

• C. Hydrogen Refueling Infrastructure 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Production 

•	 E. Control and Safety 

Approach 

•	 Investigate the stability of thin films that undergo optical changes in the presence of hydrogen. 

•	 Construct test articles of thin films and subject them to environmental stresses. 

•	 Measure response of hydrogen sensing to environmental stresses and aging. 

•	 Develop improved protective strategies. 

Accomplishments 

•	 Designed optical sensor configurations that meet most DOE criteria for safety sensors. 

•	 Demonstrated sensor lifetimes in excess of 1 year. 

•	 Measured response of test articles to thermal stresses (-20°C to +80°C) and relative humidity (0% to 

100%). 

•	 Analyzed subtle compositional differences in protective coatings that result in dramatic changes in 

performance. 

•	 Supported NREL’s photobiological hydrogen production project by constructing large area sensor 

plates for semi-quantitative evaluation of hydrogen-producing algae. 

Future Directions 

•	 Investigate the fundamental behavior of the protective coatings in order to optimize performance. 

•	 Analyze the response of optical sensors coated with protective polymeric chemical vapor deposition 

(CVD) films when exposed to low temperature and high humidity environments. 

•	 Design a control package for probing the status of the thin film optical sensors. 

•	 Fabricate prototypes for testing. 

Introduction 

Public perception of the hazards of hydrogen fuel 

use, its production, and storage, as well as 

governmental regulation will require extensive safety 

precautions and codes to be in place before hydrogen 

can be incorporated into the energy infrastructure in a 

meaningful way. Currently, commercial hydrogen 

detectors are not useful for widespread use, 

particularly in transportation, because they are too 

bulky, expensive, and dangerous. Work sponsored 

by DOE has developed promising technologies for 

satisfying the future demands. Specific performance 

targets for safety sensors have been proposed: 

•	 Measurement range: 0.1%–10% H2 in air 

•	 Operating temperature: -30°C – +80°C 

•	 Response time: <1 s 

•	 Accuracy: 5% 

•	 Gas environment: ambient air, 10%–98% RH 

range 

•	 Lifetime: 5 years 

•	 Selectivity from interference gases, such as 

hydrocarbons, is needed. 

Sensors that exhibit physical changes when 

exposed to hydrogen have been fabricated and tested, 

and they have the potential to provide inexpensive 

hydrogen detection. For example, there are thick 

film and thin film metallic sensors that exhibit 

conductivity changes when hydrogen adsorbs on the 

surface and is incorporated into the lattice. There are 

thin film sensors that are deposited as a part of a 

field-effect transistor, where accumulation of atomic 

hydrogen at the metal/insulator interface results in a 

2 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

change of response from the circuit. Finally, there the sensors past the one-year mark that had been 

are chemochromic sensors, where reaction of thin accomplished in FY 2002. 

films with hydrogen gas results in an optical change 

that can be sensed by a probe beam of light. All four 

of these configurations have the potential for 

degradation in their performance over time due either 

to mechanisms that are inherent in their construction, 

effects of their cyclic interaction with hydrogen, or 

contamination from impurities in the environments in 

which they will be used. Prior research to study 

these issues has ranked their importance to the 

various sensor concepts and has suggested the 

relevant mechanisms. This work has led, in turn, to 

methods of mitigating these factors. The research 

reported here addresses these issues and is directed 

toward substantially extending the lifetime and utility 

of these sensors, especially in the configuration that 

is based upon the optical response of the sensor 

materials. This concept appears to offer the greatest 

safety by design, and it would appear to meet cost 

goals. 

Approach 

All of the thin film safety sensor designs 

currently use a Pt group metal (usually Pd or an 

alloy) as the hydrogen dissociation catalyst. Atomic 

hydrogen is the species that causes a physical change 

in the sensing material, thereby providing a means to 

detect the presence of hydrogen. In the case of 

multiple layers of thin films forming the detection 

ensemble, the interfaces between layers, including 

the surface of the dissociation catalyst, control the 

response of the sensor. Changes in the interfaces 

most often result in degradation in the performance 

of the device. Consequently, our research and 

development activities deal mainly with the stability 

of the interfaces and the approach to the performance 

goals listed in the objectives. 

Work this year concentrated upon understanding 

the performance of a protective coating, which in 

prior years had shown extraordinary promise to 

prolong the life of the Pd catalyst. The approach was 

to study the influence that various parameters (e.g., 

precursor purity, the details of the synthesis, and 

deposition techniques) played in the performance of 

the film. The objective was to optimize the 

performance of the coating and extend the lifetime of 

A secondary effort was to characterize the 

performance of the sensors over an expanded range 

of temperatures and relative humidities. Specifically, 

the temperature range for characterization was 

extended to -30°C to +80°C, and the relative 

humidity range was extended to 0% to 100%. The 

sensors were tested in the full target range of the 

DOE goals for safety sensors. 

Results 

The results of the studies on the synthesis and 

preparation of the protective coating for the sensor 

films were mixed. Replication of early results 

proved elusive, although it was shown that the 

performances of the protective coatings are sensitive 

to almost every aspect of the preparation. A great 

deal of analytical work has suggested why the results 

of this study were mixed and has pointed to the fact 

that additional fundamental work is needed to fully 

understand the functioning of these films and their 

sensitivity to the details of their preparation. 

The performance of typical tungsten oxide 

sensor elements at various temperatures is illustrated 

in Figures 1 and 2. The data indicate that the 

tungsten oxide sensors operate reasonably well in a 

temperature range from 0°C to +80°C. However, 

excursions to the upper temperature apparently result 

in irreversible changes in the WO3 film that affect 

performance (Figure 1, 19°C after heating). This 

irreversible change does not constitute a fatal flaw in 

the design of these sensors, since the performance is 

Figure 1.	 Optical Sensor Response to 2% Hydrogen in 

Synthetic Air at Temperatures from 19°C to 

80°C 

3 
 

 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

likely adequate (rather than optimum) after the 

material changes. At temperatures below 0°C, the 

performance of the sensors degrades rapidly (Figure 

2). We think that it is likely that the formation of ice 

on the catalyst surface progressively covers the 

hydrogen dissociation sites. This inhibits both the 

response to hydrogen and recovery after exposure. 

At temperatures below –10°C, the response of the 

sensor may be degraded to the point where response 

is deemed unacceptable. There are two approaches 

to mitigate the problem of condensation and ice 

formation at these temperatures. One is to use a 

physical barrier to inhibit the diffusion of water 

through the coating, while allowing hydrogen to 

diffuse at a relatively high rate. The other is to 

periodically pulse the light source to such an 

intensity as to evaporate a substantial amount of the 

ice that fouls the Pd surface. Studies of these 

methods had to be deferred to another year. 

Figure 2.	 Optical Sensor Response to 2% Hydrogen in 

Synthetic Air at Temperatures Ranging from 

–30°C to 19°C 

Figure 3.	 Response of a WO3 Sensor to 0.5% 

Hydrogen in Air at Room Temperature and 

Various Relative Humidities 

 FY 2003 Progress Report 

The response of a typical WO3 based sensor to 

0.5% hydrogen in air is shown in Figure 3. 

Increasing relative humidity slows the response of 

the sensors, which is observed by the change in slope 

of the curves in the inset. The inset is a 

magnification of the “knee” region of the curve 

showing more detail of the sensor response upon 

admission of hydrogen into the gas stream. Another 

observation is that increasing relative humidity 

decreases the depth of coloration at saturation. 

However, neither of these effects represents a fatal 

flaw in the operation of the devices as safety sensors. 

We believe that we can improve the performance of 

these sensors in high humidity by the application of 

polymeric thin films with surface properties designed 

to minimize the interaction with water vapor. 

Preliminary experiments with such films give a good 

indication that they will inhibit the ingress of water 

to the catalyst surface. 

Conclusions 

The performance of optical thin film sensors are 

represented in tabular form as follows: 

•	 Measurement range: 0.02% – 10% H2 in air 

•	 Operating temperature: -20°C – +80°C 

•	 Response time: <1 s 

•	 Accuracy: needs to be determined 

•	 Gas environment: ambient air, 0% – 100% RH 

range 

•	 Lifetime: 1 year 

•	 Interference resistant (e.g., all other gases) 

Significant progress was made this year in 

understanding the sensitivity of our best protective 

coating to variations in the synthesis techniques. 

Furthermore, measurements of the response of the 

sensor under extremes of temperature and relative 

humidity have produced encouraging results. It 

appears that the major remaining criteria to meet, and 

the focus of future work in the area, is the durability 

of the sensor elements in realistic atmospheres. 

FY2003 Publications/Presentations 

1. R. D. Smith, P. Liu, S.-H. Lee, C. E. Tracy, and J. 

R. Pitts, "Low-Cost Fiber Optic Hydrogen 

Sensors," ABSTR PAP AM CHEM S 224: 171­

FUEL Part 1, Aug. 18, 2002. 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

2. E. Ozkan, P. Liu, S.-H. Lee, C. E. Tracy, J. R. 

Pitts, and S. K. Deb, "Preparing Mesoporous 

Tungsten Oxide Thin Films Using Non-Ionic 

Surfactants as the Templates by Sol-Gel 

Deposition Process," Solid State Ionics 

(submitted). 

3. S.-H. Lee, H. M. Cheong, M. J. Seong, P. Liu, C. 

E. Tracy, A. Mascarenhas, J. R. Pitts, and S. K. 

Deb, "Raman Spectroscopic Studies of 

Amorphous Vanadium Oxide Thin Films," Solid 

State Ionics (submitted). 

4. E. Ozkan, S.-H. Lee, C. E. Tracy, F. Z. Tepehan, J. 

R. Pitts, and S. K. Deb, "Comparison of 

Electrochromic Amorphous and Crystalline 

Tungsten Oxide Films," Solar Energy Materials 

and Solar Cells (submitted). 

5. P. Liu, S.-H. Lee, C. E. Tracy, J. A. Turner, J. R. 

Pitts, and S. K. Deb, "Electrochromic and 

Chemochromic Performance of Mesoporous 

Thin-Film Vanadium Oxide," Solid State Ionics 

(submitted). 

6. J. R. Pitts, "Switchable Optical Materials 

Applications in Energy Conservation and 

Hydrogen Infrastructure," invited seminar, 

University of Texas at Arlington, Dept. of 

Chemistry and Biochemistry, Oct. 25, 2002. 

 FY 2003 Progress Report 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Development of Sensors for Automotive Fuel Cell Systems 

Brian A. Knight (Primary Contact), Lei Chen 

United Technologies Research Center 

411 Silver Lane Mail Stop 129-30 

East Hartford, CT 06108 

Phone: (860) 610-7293; Fax: (860) 660-1204; E-mail: knightba@utrc.utc.com 

DOE Technology Development Manager: Nancy Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811, E-mail: Nancy.Garland@ee.doe.gov 

Subcontractors: 

ATMI, Inc., Danbury, CT 

Illinois Institute of Technology, Chicago, IL 

NexTech Materials, LTD, Worthington, OH 

Objectives 

Develop technology and a commercial supplier base capable of supplying physical and chemical sensors 

required to optimize the operation of proton exchange membrane (PEM) fuel cell power plants in 

automotive applications. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

•	 E. Durability 

Approach 

The team assembled for this project will perform the following tasks: 

1.	 Obtain representative samples of physical parameter sensors currently available to meet the targets 

specified in the fuel cells section of the Hydrogen, Fuel Cells and Infrastructure Technologies Program 

(HFCIT) Multi-Year R,D&D Plan (MYP). 

2.	 Design and construct a facility for testing physical and chemical sensors under simulated reformer exit 

conditions. 

3.	 Determine the suitability of state-of-the-art physical parameter sensors for the extreme environment of 

a PEM fuel cell power plant by testing them in a combination of laboratory and simulated fuel cell 

flow stream environments. 

4.	 Assist the sensor manufacturers, where necessary, to modify their sensors to achieve the requisite 

performance and durability goals. 

5.	 Modify baseline chemical sensing technologies to create sensors capable of measuring the gas 

concentrations listed in the HFCIT Multi-Year R,D&D Plan while operating in a PEM fuel cell 

environment. 

6.	 Validate and document the performance and durability of the developed sensors by exposing them to a 

combination of laboratory and simulated fuel cell flow stream environments. 

7.	 Install the developed sensors on a PEM fuel cell at UTC Fuel Cells (UTCFC) for final testing. 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

•	 Designed and constructed physical and chemical sensor test facility for simulated reformer test gas 

stream. 

•	 Developed software for continuous monitoring and operation of the test facility. 

•	 Developed α-prototype H2 safety sensor and began testing. 

•	 Completed physical sensor survey and have obtained candidate sensors for evaluation. 

Future Directions 

•	 Evaluate physical sensors in United Technologies Research Center (UTRC) facility followed by tests 

at UTCFC on the S300 gasoline-fired reformer breadboard facility. 

•	 Obtain electrochemical and micro electromechanical system (MEMS) chemical sensors and evaluate 

in UTRC and Illinois Institute of Technology (IIT) test facilities. 

•	 Optimize sensor performance and reliability. 

•	 Deliver sensor suite for testing at UTCFC gasoline-fueled reformer PEM cell facility. 

Introduction 

The present state-of-the-art in fuel cell power 

plant sensor technology is embodied in the UTC FC 

PAFC PC 25 and PEM S200 power plants. Sensors 

measuring all of the parameters defined in the HFCIT 

Multi-Year R,D&D Plan are utilized in designing and 

setting up these power plants. However, none of the 

chemical sensors and only a very few of the physical 

sensors are "on-board" the power plant, and only 

temperature and stack differential pressure, in the 

S200, are measured continuously for control 

purposes. Production automotive fuel cell power 

plants require all of these sensors to be on-board the 

power plant, and to provide data signals on a 

continuous basis to optimize fuel cell operation and 

protect the cell stack from damage. 

Approach 

UTCFC is, or will be, evaluating the sensors 

described above in the appropriate test facilities by 

supplying a synthesized gas stream of known inlet 

gas composition and determining the response 

accuracy of each sensor at the required operating 

temperature. By controlling the inlet gas 

composition and mass flow, a fixed reference will be 

established to which the sensor response will be 

compared as a function of time. This effort is being 

conducted in UTRC, IIT and UTCFC facilities. 

Baseline sensor technology taken from a 

combination of production PC25, S200 and fuel cell 

development laboratory applications is being 

subjected to a series of performance, durability and 

cost reduction studies. Concurrent with this portion 

of the task, a detailed review of alternate sensors is 

being conducted. New advanced solid state 

electrochemical and MEMS sensors are being 

developed at NexTech, Inc. and Advanced Technical 

Materials Incorporated (ATMI), which include new 

transduction principle development, new sensing 

materials and fabrication development, and sensor 

prototyping. Appropriate sensors will be ranked 

according to the probability of successful test 

outcome. Initial qualification tests will be conducted 

by IIT in the PEM Fuel Cell Benchmark Facility. 

These tests will consist of installation and exposure 

of baseline sensors to precisely controlled 

temperature, humidity, pressure, and gas mixture 

conditions. Sensor response versus these parameters 

will be logged. 

Second level testing will be conducted at 

UTRC. During these tests, the sensors will be 

installed in a chamber through which gases 

simulating an autothermal reformer (ATR) exhaust 

stream (created by mixing gases, heating and 

humidifying as necessary, to obtain the desired 

composition) will flow. The sensors will be 

evaluated for accuracy, speed of response, cross 

sensitivity to non-target parameters and test gas 

parameters. The tests will operate continuously, 

2 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

during which time a computer utilizing National 

Instruments LabView software will control and log 

all test parameters, including gas composition, 

sensor output, and control safety systems. 

It is assumed that repetition of the above testing 

cycle will be required due to non-performance of some 

sensors. If baseline sensors cannot demonstrate 

performance meeting the targets in the HFCIT MultiYear R,D&D Plan, alternates will be selected. 

Results 

A team has been assembled to address the 

development and evaluation of physical and 

chemical sensors meeting the requirements listed 

above. Table 1 shows the breakdown of 

responsibilities for each of the team members. 

UTRC has constructed a physical and chemical 

sensor test facility capable of subjecting candidate 

sensors to gas compositions simulating operation in a 

gasoline/natural gas-fueled reformer-based fuel cell 

system. IIT will be evaluating all sensors developed 

during execution of this project in their PEM fuel cell 

test facility. The facility design is shown in Figure 1; 

Figure 2 is a photograph of the flow controllers, 

steam generator, and condenser. 

UTRC has begun evaluation tests on a hydrogen 

sensor manufactured by H2Scan, Inc. in both dry and 

moisturized gas streams consisting of H2 and N2, 

with CO2 and trace concentrations of methane added. 

Results of these tests are shown in Figures 3a and 3b. 

FY 2003 Progress Report 

Figure 1. UTRC PEM Fuel Cell Gas Stream Simulator 

and Sensor Testing Rig 

Conclusions 

The tests show the H2 sensor has a linear 

response to the concentration of H2 present in the gas 

stream. The sensor indicates no cross-sensitivity to 

methane under the conditions investigated. The 

sensor shows excellent repeatability among the tests 

conducted so far. The sensor response time (t90) in 

dry gas environment is about 30 seconds and the 

response time is extended to 100 to 140 seconds in a 

moisturized gas stream. The sluggish response as a 

result of operation in a humid environment may 

impact the cost-effectiveness of deploying the sensor 

in PEM fuel cells. This aspect of the overall sensor 

performance needs to be improved significantly. 

Table 1. Sensor Development Team Responsibilities 

Team 

Member 

UTC FC 

T 

X 

∆P 

X 

RH

X

 flow 

X

O2

 X 

CO 

X 

UTRC X X X X X X 

ATMI 

IIT X X X X 

NexTech X 

H2

X
 

X
 

X
 

X
 

SO2

X 

X 

X 

X 

X 

H2S 

X 

X 

X 

X 

X 

NH3 

X 

X 

X 

X 

X 

Technological Expertise / 

Responsibility 

Testing on S300 

Breadboard 

Testing in reformate 

simulator 

Develop Using MEMS 

Silicon Microhotplate 

Testing in Benchmark 

Facility 

Develop Using Solid State 

Electrochemical 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2.	 UTRC PEM Fuel Cell Gas Stream Simulator: 

Gas Flow Control System, Steam Generator, 

and Test Chamber 

Figure 3a. Response of H2 Sensor to Hydrogen in Dry 

Gas Stream 

The candidate sensor selected for hydrogen 

detection has demonstrated excellent sensitivity and 

selectivity for H2. The durability of the sensor is 

being tested in the simulated reformate stream. 

Results of the physical sensor survey are 

summarized in Table 2. 

Table 2. Results of Physical Sensor Survey 

Figure 3b. Response of H2 Sensor to Hydrogen in 

Simulated Reformate Gas Stream 

Sensor Meet DOE/FC tech. 

specs 

Further effort Technical 

gap/stretch 

Humidity Yes/Yes Validate new technologies (MEMS sensor) to 

improve the recovery time 

Medium 

Flow rate Yes/No Collaborate with vendors to improve stability High 

Differential 

pressure 

Yes/Yes Collaborate with vendors for size and cost 

reduction 

Medium 

Temperature Yes/Yes Identify inexpensive thermistors for high 

temperature 

Low 

References 

1. DOE Workshop: "Sensor Needs and Requirements 

for Fuel Cells and CIDI/SIDI Engines," Robert S. 

Glass, Ed., published by Lawrence Livermore 

National Laboratory, April, 2000 

2. Hydrogen, Fuel Cells & Infrastructure 

Technologies Program Multi-Year Research, 

Development and Demonstration Plan, June 3, 

2003 

and Development and Analysis for Energy 

Efficient Technologies in Transportation and 

Buildings Applications"; DOE Albuquerque 

Operations Office, November 21, 2000 

FY 2003 Publications/Presentations 

1. DOE Sensor Program 4th Quarter Review, 

submitted March 5, 2003. 

2. DOE Hydrogen & Fuel Cells Annual Program 

Review, May 19-22, 2003 

3. "Solicitation for Financial Assistance 

Applications No. DE-RP04-01AL67057 Research 

4
 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Micro-Machined Thin Film H2 Gas Sensors 

Frank DiMeo, Jr. (Primary Contact), Ing-Shin Chen, Phil Chen, Jeffrey Neuner, Andreas Rohrl, 

Michele Stawaz, and Jim Welch 

ATMI, Inc. 

7 Commerce Drive 

Danbury, Connecticut 06810 

Phone: (203) 794-1100; Fax: (203) 830-2126; E-mail: fdimeo@atmi.com 

DOE Technology Development Manager: Neil Rossmeissel 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

•	 Optimize process conditions, focusing on improving yield and uniformity. 

•	 Investigate the physics and chemistry of the sensing materials and sensing mechanisms. 

•	 Develop improved sensor packaging and electronics system integration. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

Approach 

•	 Introduce new process steps to improve device yield. 

•	 Analyze chemical, electrical, and mechanical aspects of sensor characteristics. 

•	 Survey device packaging possibilities; down-select most appropriate option. 

•	 Develop real-time signal conditioning and processing algorithms and platforms. 

•	 Implement industry-standard control practices and knowledge-based management (KBM). 

Accomplishments 

•	 Improved the post-packaging fabrication yield to greater than 80%. 

•	 Created novel surface treatment methodology for surface micro-machined structures. 

•	 Identified novel piezo-resistive transduction mechanisms. 

•	 Designed a microprocessor-based evaluation kit equipped with on-board signal conditioning and 

processing. 

Future Directions 

•	 Evaluate characteristics of sensors fabricated with new processing steps. 

•	 Explore new piezo-resistive device structures. 

•	 Tailor sensors for specific applications. 

•	 Deploy evaluation kits to test sites. 

1 
 

 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction 

There is a common need in all hydrogen 

applications to detect and quantify the amount of 

hydrogen present. Not only is hydrogen detection 

necessary for life safety reasons, but effective 

hydrogen monitoring is also required for optimal 

process control of hydrogen-based energy systems. 

These needs call for a sensor technology that can 

accommodate many diverse requirements. For 

industrial applications, sensors must be hydrogenselective and immune to impurity gases commonly 

present in hydrogen feedstock. A fast speed of 

response is a critical requirement for life safety 

monitoring and a necessary feature for real-time 

control of processes that run on rapid duty cycles. 

We have developed and characterized novel MicroElectro-Mechanical System (MEMS)-based 

hydrogen sensors to meet this growing need. 

The novel hydrogen sensors developed at ATMI 

are based on a MEMS device platform. The MEMS 

platform, known as a micro-hotplate, is a suspended 

thermal isolation structure with an embedded heater 

element (Semancik, et al., 2001). The new sensors 

employ rare earth metal thin films as the active 

sensing layer and use reversible metal hydrogenation 

as the sensing mechanism. The extent of 

hydrogenation depends on the gas-phase hydrogen 

concentration, and hydrogenation can increase the 

electrical resistance by several orders of magnitude, 

making it a very sensitive transduction mechanism. 

Approach 

Our approach has been to design, fabricate, and 

characterize MEMS-based gas sensors of different 

layouts and film chemistries. The understanding 

gained during characterization is subsequently used 

as feedback to the next design cycle. A schematic of 

the layered structure that makes up the sensor is 

shown in Figure 1. The micro-hotplate layout was 

designed in-house and fabricated by a foundry 

service. A rare earth metal thin film with a 

palladium-based capping layer was subsequently 

deposited onto the micro-hotplate platform and 

serves as the active sensing layer. Substantial effort 

has been devoted to mapping the fabrication process 

flow, which involves 11 steps and over 110 variables. 

Knowledge-based management (Schmidt, et al., 

1999) and other data-driven quality control protocols 

have been applied to identify the issues affecting 

sensor yield and uniformity. 

While the sensor construction is relatively 

straightforward, the sensor characteristics can be 

quite complex due to strong coupling of chemical 

reactions, electrical probing, and mechanical 

movement. For example, hydrogen must first 

adsorb, dissociate, and diffuse through the cap layer. 

Upon reaching the sensing layer, it reacts with the 

sensing material to form hydride of relevant phases. 

When the hotplate temperature is raised above 

ambient to expedite these chemical reactions, it also 

modifies the hydrogen content and electrical 

resistance of the hydride film and causes the microhotplate platform to deflect. The deflection in turn 

modifies the stress state of the sensor stack, changing 

the film properties. We have used a wide variety of 

microscopy techniques as well as electrical 

characterization to study and model sensor 

behaviors. 

Results 

Using KBM techniques such as resistance as a 

function of H2 concentration, temperature, and 

voltage, we identified the contact interface between 

the Al interconnect and the sensing layer as a primary 

candidate for improvement in order to improve yields 

and uniformity. It was further determined that the 

interface layer was affected by both non-planar 

surface topography and the formation of native oxide 

on the surface of the Al interconnect prior to 

deposition of the sensing layer. Process steps were 

Figure 1. Schematic of Functional Layer Stack on a 

Micro-Hotplate Platform 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

added to planarize the structure and clean the contact 

area in situ. A representative result comparing the 

surface topography of a sensor structure, measured 

by stylus profilometry, before and after the 

planarization step is shown in Figure 2. The new 

processing steps help ensure that the sensing layer 

deposited is uniform across the platform surface, and 

that there is good electrical contact to the underlying 

Al interconnects. Addition of these steps to the 

fabrication process improved the pre-packaging yield 

to greater than 80% and reduced intra-die variation, 

as shown in Figure 3. 

In addition to improving the fabrication yield, we 

have made appreciable progress towards 

understanding the chemical, electrical, and 

mechanical aspects of the sensing mechanism. The 

mechanical aspect had been less apparent in the past, 

but its effects are magnified now that additional 

processing steps have improved the electrical 

contact. Additionally, new microscopy techniques 

Figure 2. Representative Result of Surface Planarization 

Figure 3. Yield Improvements as Function of Process 

Improvements vs. Process of Record (POR) 

 FY 2003 Progress Report 

have enabled the visualization of the mechanical 

behavior for the first time. In particular, bending of 

micro-hotplate platform has been observed via a 

confocal microscope, as shown in Figure 4. 

Moreover, as the hydride film absorbs hydrogen, its 

volume expands, and the extent of deflection 

changes. The heater element embedded on the 

micro-hotplate platform, made of a piezo-resistive 

element, changes its electrical resistance when the 

deflection modifies the stress states of the platform. 

It was recognized that this phenomenon can serve as 

the basis for a separate, piezo-resistive mechanism in 

addition to the original chemi-resistive mechanism 

for signal transduction. Chemi- and piezo-resistive 

responses of a representative sensor are shown in 

Figure 5. The two mechanisms together, with no 

modification to sensor construction, provide a unique 

sensor package that has high sensitivity around lower 

explosion level (LEL - 4% H2 in air) and a large 

dynamic range beyond LEL. 

An electronic signal conditioning and processing 

system was developed to provide a simple device for 

collaborators to interface with their detection system. 

The system includes signal conditioning circuitry for 

proper power sourcing and resistance measurement, 

as well as real-time signal processing software 

running on a microprocessor embedded on the 

circuitry. When coupled with a data-logging device 

such as a personal digital assistant, as illustrated in 

Figure 4. Representative Confocal Microscopy Image of 

a Sensor 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 6, the system becomes a stand-alone unit that 

can be easily transferred to test sites to verify sensor 

performance in real-life settings. Systems have been 

deployed at several locations in the U.S. and Europe. 

Conclusions 

•	 Improved fabrication yield and device 

uniformity have been demonstrated. 

•	 The interdependency of chemical, electrical, and 

mechanical properties of the sensor operation has 

been characterized and studied. 

•	 An innovative piezo-resistive transduction 

mechanism was discovered. 

•	 Signal conditioning/processing of sensor 

response was implemented for system 

integration. 

Figure 5. Representative Sensor Responses up to 40% H2 

Figure 6. Photo of an Evaluation Kit with Signal 

Conditioning/Processing Capability 

 FY 2003 Progress Report 

•	 KBM techniques have been applied with 

encouraging feedback for the continuing 

improvement of sensor fabrication. 

References 

1. S. Semancik, R.E. Cavicchi, M.C. Wheeler, J.E. 

Tiffany, G.E. Poirier, R.M. Walton, J.S. Suehle, B. 

Panchapakesan, D.L. DeVoe, Sensors and 

Actuators B 77, 579 (2001). 

2. S.R. Schmidt, M.J. Kiemele, and R.J. Berdine, 

Knowledge Based Management, Air Academy 

Press & Associates, CO, 1999. 

FY 2003 Publications/Presentations 

1. “MEMS based hydrogen gas sensors,” submitted 

to Journal of Electrochemical Society. 

2. “MEMS based hydrogen sensors for emerging 

applications,” presented at Connecticut 

Microelectronics and Optoelectronics Consortium 

Symposium, Storrs, Connecticut (2003). 

Special Recognitions & Awards/Patents 

Issued 

1. G. Bhandari and T.H. Baum, “Hydrogen sensor 

utilizing rare earth metal thin film detection 

element,” U.S. Patent 6,006,582 (1999) 

2. F. DiMeo and G. Bhandari, “Micro-machined thin 

film hydrogen gas sensor, and method of making 

and using the same,” U.S. Patent 6,265,222 (2001) 

3. F. DiMeo and T.H. Baum, “Micro-machined thin 

film sensor arrays for the detection of H2, NH3, 

and sulfur containing gases, and method of 

making and using the same,” U.S. patent 

application 2002/0017126, allowed 

4. F. DiMeo and P. Chen, “Rare earth metal sensor,” 

U.S. patent pending 

5. I.-S. Chen and F. DiMeo, “Chemical sensor 

responsive to change in volume of material 

exposed to target particle,” U.S. patent pending 

4 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Sensor Development for Proton Exchange Membrane Fuel Cell Systems 

Bruce Figi (Primary Contact), Richard Alderman 

Honeywell Sensing and Control 

11 W Spring St 

Freeport, IL 61032 

Phone: (815) 235-6769; Fax: (815) 235-5526; E-mail: bruce.figi@honeywell.com 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Technical Advisor: Dr. Robert D. Sutton 

Phone: (630) 252-4321; Fax: (630) 252-4176; E-mail: sutton@cmt.anl.gov 

Subcontractors: 

Honeywell Advanced Technology Labs, Plymouth, MN 

Micro Substrates Corporation, Tempe, AZ 

Objectives 

•	 Establish the requirements for each physical sensor. 

•	 Develop packaging strategies for the sensors to minimize sensor cost. 

•	 Design and fabricate prototype sensors. 

•	 Test sensors in third party fuel cells. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

Approach 

•	 Task 1. Sensor Requirements: establishes the requirements for each physical sensor and develops 

common packaging strategies. 

•	 Task 2. Sensor Development: development of sensor concepts from Task 1 that culminates in sensor 

design engineering of prototype sensors. 

•	 Task 3. Prototype Build & Test: fabrication and testing of the developed sensors culminating in 

demonstrations of the prototype sensors. 

•	 Task 4. Field Testing: testing of prototype sensors at fuel cell and fuel processor companies. 

Accomplishments 

•	 Interviewed 10 fuel cell development companies. 

•	 Developed customer images diagram. 

•	 Extracted customer requirements from interviews. 

•	 Deployed survey to 60 recipients. 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Finalize sensor requirements and review with DOE. 

•	 Brainstorm the requirements for the top 2-3 solutions for each sensor. 

•	 Prioritize solutions. 

•	 Create Engineering Development Specification (EDS) for top priority concept for each physical 

sensor. 

•	 Obtain DOE review and approval of EDS. 

•	 Begin sensor development. 

Introduction 

The technical approach for this project is to look 

at the fuel cell system and establish the requirements 

for each physical sensor, then develop packaging 

strategies for the sensors to minimize sensor cost. 

Prototype sensors will be designed and fabricated at 

Honeywell and then the sensors will be tested in third 

party fuel cell systems at fuel processor companies. 

Approach 

In the initial phase of the project, the 

requirements provided by DOE in the solicitation for 

the individual physical sensors were investigated 

thoroughly and refined as needed. Honeywell 

interviewed fuel cell and fuel processor companies, 

listed in Figure 1, to attain the requirements of each 

customer. 

A fact-based methodology, Language Analysis, 

that is part of a product definition process, Market 

Driven Product Definition (MDPD®), will be 

employed to glean fact-based information from the 

customer interviews. A final step in the MDPD® 

process is surveying the market with the 

requirements created from the interviews. A Kano 

Survey provides requirement validation from the 

broad market again through a fact-based 

methodology. During this development, it is 

Honeywell’s objective to continuously re-evaluate 

the sensor requirements in light of new developments 

in the field, contracting agency inputs, and our own 

development status. Our goal is a continuous 

improvement in the sensor requirements during the 

initial prototype design and testing phase, leading to 

realistic, achievable requirements by the time final 

prototypes are to be developed and tested. Industry 

inputs will be employed to help define packaging 

requirements and associated common packaging 

methodologies across all the sensor developments. 

Results 

Several customers were interviewed during the 

MDPD® process; the customer group is presented in 

Figure 1. The verbatim transcripts of the interviews 

were scrubbed to find customer images and 

requirements. Metrics were also pulled from the 

interview data during the scrubbing. 

The customer images were reduced onto the 

customer image map shown in Figure 2. These 

images describe the emotion in the customer’s voice. 

It shows that they have a problem that needs to be 

solved. 

The customer requirements were also reduced 

onto a customer requirements map as shown in 

Figure 3. Solutions for these requirements will be 

Figure 1. Interview List 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

3
 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

4
 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

brainstormed by a cross functional team. The 

solutions will be prioritized, and engineering teams 

will work the concepts. 

Metrics were also scrubbed from the transcripts, 

and those metrics were used in the customer survey 

to help define the bounds on the functional and 

environmental conditions for each physical sensor. 

The customer list for the survey is shown in Figure 4. 

Conclusions 

Many of the Task 1 conclusions will come from 

the survey feedback. Many of the preliminary DOE 

requirements for physical sensors line up with the 

metrics from the customer interviews. 

Technical hurdles that have been identified are as 

follows: 

• General 

- Meeting cost targets. 

• Relative Humidity Sensing 

- Stability over application life. 

- Ability to provide feedback in two-phase flow. 

• Flow Sensing 

- Providing a stable, accurate output in noncondensing and condensing environments. 

FY 2003 Publications/Presentations 

1. 2003 Merit Review - Sensor Development for 

PEMFC Systems, Bruce Figi, Honeywell 

Sensing & Controls 

 FY 2003 Progress Report 

Figure 4. Survey Customer List 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Gallium Nitride Integrated Gas/Temperature Sensors for Fuel Cell Systems 

Steve Pyke (Primary Contact) and Larry W. Sadwick 

Fluence 

PO Box 1257 

Sisters, OR 97759 

Phone: (541) 390-9572; Fax: (810) 592-1523; E-mail: stevepyke@direcway.com 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-5860; E-mail: Neil.Rossmeissl@ee.doe.gov 

Subcontractor: Larry W. Sadwick, Innosys, Salt Lake City, Utah 

Objectives 

•	 Fabricate gallium nitride (GaN) field effect transistor (FET) sensors to resolve and detect carbon 

monoxide in a background of varying hydrogen concentration and high water content at T>250°C 

•	 Develop method for resolving CO at 10 ppm from H2 interference 

•	 Validate sensors and analysis in operational reformers 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

•	 K. Emissions and Environmental Issues 

•	 L. Hydrogen Purification/Carbon Monoxide Cleanup 

Approach 

•	 GaN and silicon carbide (SiC) are semiconductors with large band gaps and are an attractive option for 

high temperature electronic applications including gas monitoring 

•	 Catalytic metals such as platinum, rhodium and palladium are good candidates for the gate metal in 

GaN FET sensors for CO detection 

•	 The same metals are well known catalysts in the preferential oxidation (PROX) process for oxidizing 

trace amounts of CO by reaction with oxygen in excess H2 

•	 Test GaN FET sensors in mixtures of H2 and CO for array analysis of CO 

•	 Develop a simple analysis method for extracting CO concentration from background H2 effects 

Accomplishments 

•	 Completed main effect testing of CO (0-80 ppm) and H2 (30-70%) 

•	 Developed quantitative method for reliably detecting CO at 10 ppm in 30-70% H2 

Future Directions 

•	 Determine consistency or reproducibility of calibration results in CO and H2 

•	 Confirm higher fabrication yield by improved gate metal adhesion 

•	 Complete testing of Rh and Zr gate metals 

1 
 

 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Field test working hydrogen reforming processes to validate process control and analysis statistics 

•	 Test in wet and dry hydrogen sources (ca H2O ~ 25%vol) 

•	 PdAg abandoned in favor of Zr due to potential surface segregation of Ag and alloys in general leading 

to sensor drift 

Introduction 

A low-cost sensor capable of resolving CO (1­

100 ppm) in hydrogen (30-75%) and water vapor 

(25%) is needed but technically difficult to achieve. 

Platinum based sensors have been used for CO 

detection, but the cross-sensitivity of CO and 

hydrogen precludes their selective measurement of 

CO. Similar cross-sensitivity is expected for any 

single metal with a catalytic response to CO. A 

method is needed to resolve the CO in a background 

of varying hydrogen concentration. Arrays of 

inexpensive sensors have been proposed as a solution 

for when selectivity of an individual sensor is 

insufficient to reliably detect and measure the gas of 

interest. This project demonstrates how an array can 

be used for resolving the CO and hydrogen 

concentrations using two GaN FET sensors with a Pt 

and Rh gate metal and a two-component calibration 

matrix of 25 pairs of CO and hydrogen 

concentrations. The measurements of gate voltage at 

each of the 25 calibration points are used to compute 

a three-dimensional response surface. The 

intersection of the response surfaces for the different 

gate compositions is used to resolve and measure the 

concentrations of CO and hydrogen. 

Approach 

Recent work on SiC FET sensors using catalytic 

metal gates has been reviewed (1) and suggests SiC 

FETs with metal gates are attractive candidates for 

high temperature gas monitoring. GaN based 

devices and circuits are also an attractive option for 

high temperature applications including gas 

monitoring. The effect of gas on GaN FETs with 

metal gates has been studied and reported (2). 

Catalytic metals such as platinum, rhodium and 

palladium are good candidates for the gate metal in 

GaN devices because they have been shown to form 

good Schottky barriers on n-GaN. These metals are 

also suggested for this application because each has 

shown catalytic activity in the preferential oxidation 

(PROX) process for oxidizing trace amounts of CO 

by reaction with oxygen in excess hydrogen. 

Results 

Device characterization, architecture, control 

electronics, the calibration system and chemical 

analysis of the metal gate GaN FET sensors used in 

this study are described in the DOE reports in 

Reference 2. The time history of responses of the Pt 

sensor is shown in Figure 1. Figures 2 and 3 show 

the response surfaces for a Pt and Rh gate GaN 

MODFET sensor. The contours of constant gate 

voltage were mapped using MathCAD from 

measurements at 25 ppm CO and hydrogen 

concentration pairs in the range required for the 

application above. The plots are a two-dimensional 

representation of a three-dimensional surface. A 

single measurement of gate voltage for either of the 

different sensors could indicate any combination of 

CO and hydrogen along a constant voltage contour. 

CO and hydrogen are resolved by the combined 

measurement using sensors with sufficiently 

different response surfaces. For an unknown blend 

of CO and hydrogen, the gases are resolved and 

concentrations determined from where the contours 

Figure 1.	 Typical Calibration Run (Twenty-five 

calibration pairs of CO and H2 are delivered to 

the sensor in random order pair presentation to 

minimize systematic error. There are three 

source gases: CO in H2 (1000 ppm), H2 and N2, 

with a total flow = 1356 cm3

/min at T = 250oC 

and P = 1 atm. The system limited response 

time = 15 sec to 90% of full scale.) 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 2.	 Pt Response Surface at 250oC (Mapping is a 

fit to the calibration data. Calibration pairs are 

at grid intersections. Contour spacing is 1 

standard deviation.) 

Figure 3.	 Rh Response Surface at 250oC (Closer 

spacings improve precision. 90o crossing 

angles for contours from different sensors 

improve accuracy. Straighter contours improve 

accuracy. Single crossings increase 

confidence.) 

computed for the Pt and Rh sensors intersect. These 

data suggest the detection of CO at 10 ppm is 

possible over most of the range. 

Conclusions 

Laboratory results confirm arrays of GaN FET 

sensors can be used to detect the contamination of as 

little as 10 ppm CO in H2 fuels used in proton 

exchange membrane fuel cells. These sensor arrays 

can operate in temperatures exceeding 250°C, thus 

eliminating the need for water separation before 

analysis. 

References 

1. A.L. Spetz, L Uneus, H. Svenningstorp, P. Tobias, 

L.G. Ekedahl, O. Larsson, A. Goras, S. Savage, C. 

Harris, P. Martensson, R. Wigren, P. Salomonsson, 

B. Haggendahl, P. Ljung, M. Mattsson and I. 

Lundstrom, Physica Stat. Solidi A – Applied 

Research, 185, 15-25 (2001). 

2. Y. Kokubun, T. Seto and S. Nakagomi, Jpn. J. 

Appl. Phys., 40, L663-L665 (2001). J. Schalwig, 

G. Muller, M. Eickhoff, O. Ambacher and M. 

Stutzman, Sensors and Actuators B-Chemical, 87, 

425-430 (2002). B.P. Luther, S.D. Wolter and 

S.E. Mohney, Sensors and Actuators B, 56,164 

(1999). S.C. Pyke and L. Sadwick, DOE Report, 

http://www.eere.energy.gov/hydrogenandfuelcells/ 

pdfs/32405b16.pdf, 2002. S.C. Pyke and L. 

Sadwick, DOE Report, http://www.eere.energy.gov/ 

hydrogenandfuelcells/pdfs/30535ay.pdf, 2001. And 

S.C. Pyke, J-H. Chern, J. Hwu and L. Sadwick, 

DOE Report, http://www.eere.energy.gov/ 

hydrogenandfuelcells/pdfs/28890ii.pdf, 2000. 

Special Recognitions & Awards/Patents 

Issued 

1. Invited paper to be presented at “High Band Gap 

Material FET Chemical Sensors”, IEEE 

Sensors 2003, Toronto, October 21-24, 2003. 

3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Fiber Optic Temperature Sensors for PEM Fuel Cells 

Timothy J. McIntyre (Primary Contact), Steven W. Allison, L. Curt Maxey and Michael R. Cates 

Oak Ridge National Laboratory 

P.O. Box 2008 

Oak Ridge, TN 37831-6004 

Phone: (865) 576-5402; Fax: (865) 574-1249; E-mail: mcintyretj@ornl.gov 

DOE Technology Development Manager: Nancy L. Garland 

Phone: (202) 586-5673; Fax: (202) 586-9811; E-mail: Nancy.Garland@ee.doe.gov 

Subcontractors: 

Translume, Inc., Ann Arbor, MI 

Micro-Materials, Inc., Tampa, FL 

Objectives 

The objective of this research is to develop a low-cost, durable and fast-responding temperature sensor for 

proton exchange membrane (PEM) fuel cells. Temperature and temperature gradients within the fuel cell 

membrane electrode assembly (MEA) are a key indicator of the operational condition of the cell and its 

ability to respond to a required load. The thermal state of a fuel cell stack directly affects its ability to 

deliver energy on start-up or under adverse environmental conditions. Furthermore, localized hot spots 

within the MEA can lead to greatly reduced operational life and even catastrophic failure. Hence, realtime 

feedback of the thermal condition of a cell or stack can be utilized to control the stack, optimize 

performance, and monitor the condition of critical components and sub-components. 

Currently, thermocouplers and thermistors are being used to monitor the thermal condition at a few 

locations in operating fuel cell stacks. After a few months effort and a review of our technology with fuel 

cell developers, the ability to measure temperature at many more locations, with a small, low-cost and 

electrical non-conductive sensor was considered of great interest. Additionally, the fiber optic sensors 

provide a safe way of making temperature measurements within the stack without the possibility of 

electrically shorting the stack to ground as may be the case with a conductive sensor like a thermocouple or 

thermistor. Finally, the ability to make many cost effective temperature measurements with a technology 

that is fast, durable and electrically insulating is of great interest to fuel cell developers. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

•	 C. Thermal Management 

Approach 

•	 Identify and characterize the optimum fluorescent medium (materials and possible binders and or 

matrices) for fast-responding, accurate and robust temperature measurement; 

•	 Demonstrate material compatibility of the sensor with the fuel cell; 

•	 Explore the most appropriate temperature measurement zones and arrays within the membrane and 

stack configuration; 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Explore alternate wave guide approaches to optimize sensor robustness, expand the range or density of 

measurements, and minimize cost of implementation; 

•	 Develop and test probe concepts for cost effective implementation, functionality, durability, and 

performance; 

•	 Develop a low-cost electronics package that readily integrates with fuel cell systems; and 

•	 Study alternate probe configurations that may lead to sensing other critical parameters (e.g. humidity 

or flow measurements). 

Accomplishments 

•	 Appropriate fluorescent transducer materials have been identified and characterized that will provide 

fast-responding (milliseconds) and accurate (<1% of range) temperature information from a fuel cell 

membrane electrode assembly; 

•	 Low-cost probe designs have been tested in the lab that will provide temperature data from operating 

fuel cells; 

•	 Initial field tests show that accurate and reliable temperature information can be gathered from 

operating fuel cells; 

•	 New intellectual property (2 patent disclosures) has been developed in the areas of embedded wave 

guide sensors and spatially resolved temperature sensors that may lead to system designs that were 

previously unattainable; and 

•	 Collaborative relationships are developing with several fuel cell designers and end users to gain 

perspective on designs and facilitate testing and implementation. 

Future Directions 

•	 Probe designs will be evaluated in the lab and prepared for field tests; 

•	 Measurement system design issues will be addressed (signal processing, packaging, etc.); 

•	 Alternate probe concepts will be evaluated that could lead to previously unattainable functionality, 

performance, and cost targets; 

•	 Field tests will be planned to evaluate system compatibility, durability and performance under real 

conditions; and 

•	 Emerging possibilities to sense other important parameters or leverage to other related applications 

will be explored (e.g. humidity and flow, leverage to other fuel cell types, etc.). 

Introduction 

The need for an accurate, reliable and fastresponding temperature sensor has been identified as 

a critical need for advanced fuel cell designs. 

Temperature, thermal gradients, and thermal history 

play a key role in determining the health of a fuel cell 

and its ability to respond to instantaneous power 

demands. Furthermore, real-time thermal diagnostic 

sensors will allow designers to increase stack power 

density by reducing operating margins and quickly 

identifying the development of hot spots that could 

cause catastrophic failure. 

This project is focused on the development of 

an optical fiber based temperature measurement 

probe that utilizes the unique fluorescence 

properties of certain materials to detect temperature. 

The persistence of light emitted (fluorescence) by 

these materials (thermographic phosphors) is 

proportional to their absolute temperature. Thus, 

one can measure the fluorescence lifetime as a 

means of accurately inferring the temperature of a 

material. The fluorescence lifetime, as a rule, gets 

shorter as temperature increases. Other related 

emission characteristics, such as the fluorescence 

amplitude or phase of a modulated fluorescence 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

signal, can also be used to infer temperature. The 

technique can be applied over a wide range of 

temperatures (-270°C to >1700°C) and is 

potentially very accurate and durable. 

In practice, one attaches, grows or dopes a length 

of fiber optic cable with the phosphor material 

included to the end of another fiber optic cable that is 

used to transmit the light signal to and from the 

measurement electronics. This impregnated length 

of fiber is inserted into the temperature measurement 

zone of interest. The impregnated fiber is excited by 

a light emitting diode (LED) or laser source, and the 

fluorescence signal is collected with a photodiode. 

The fluorescence signal is then analyzed, and a 

temperature is determined. Temperatures have been 

determined to better than 0.01°C accuracy in the 

laboratory. 

Thus far, two similar materials (chromium doped 

yttrium aluminum garnet and ruby) have been 

identified that exhibit the appropriate characteristics 

for a fast, accurate and reliable temperature 

measurement over the range of -40°C to 150°C, the 

operating range for automotive fuel cells. Being 

developed now is the fiber optic probe to implement 

the measurement technique in operating fuel cells. 

The fiber optic probe can be very small in profile, 

low mass, low cost and rugged for real world 

applications. It is also electrically insulating, thus 

avoiding the possibility of shorting the fuel cell to 

ground. The measurement electronics can also be 

implemented in a very low-cost and robust manner, 

creating a temperature measurement system that is 

very attractive for commercial system diagnostics 

and control. 

Approach 

The development process for this technology 

was initiated by an in-depth study of fuel cell designs 

and operating conditions. Once a clear picture of the 

measurement need and operating environment was 

gathered, exploratory research was performed to 

identify and characterize candidate fluorescent 

materials for the measurement. These candidate 

materials were studied in the laboratory, and 

optimum materials were selected. These optimum 

materials are now being implemented into various 

probe designs for further laboratory study. Favorable 

 FY 2003 Progress Report 

probe designs will then be installed in actual fuel 

cells to gather information about system 

compatibility, performance and durability. 

Parallel to the exploratory work described above, 

alternate probe design and implementation strategies 

are being conducted with the goal of optimizing 

system performance, reliability and cost. During this 

process, two novel discoveries have been made in 

response to the challenge of creating a measurement 

technique that would be very low cost, reliable and 

yet scalable to many measurements distributed 

throughout the fuel cell. One concept involves the 

development of embedded wave guide sensors within 

the fuel cell, thus minimizing the need for intrusive 

probes inserted into the fuel cell. The other concept 

involves the development of a single fiber optic 

sensor that has the ability to measure temperature at a 

local region anywhere along the length of the fuel 

cell. This technique may facilitate many temperature 

measurements through a fuel cell stack with only a 

single measurement probe. 

Considerable progress has been made on the 

development of initial prototype probes for field 

testing. Also, novel technologies have emerged that 

will potentially lead to highly useful and 

economically viable sensor technologies. 

Furthermore, our discoveries portend the possibility 

of other sensor modalities (humidity and flow) that 

would provide additional needed information about 

the internal performance and condition of operating 

and developmental fuel cells. 

Results 

Several fluorescing materials were successfully 

tested which exhibited all the characteristics required 

and sufficient for an inexpensive temperature 

measurement system. These characteristics are: 

1. Temperature dependence in the desired range; 

2. The ability to be excited to emit using a light 

emitting diode or other low-cost source; 

3. Sufficient excitation efficiency to be detected with 

an inexpensive photodiode or other low-cost 

detector; and 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

4. Adequate brightness for use with small diameter 

optical fiber. 

Both powder (phosphor) and crystalline 

materials were tested. Figure 1 shows how the 

fluorescence decay time decreases as temperature is 

increased for one of the materials tested. At present, 

ruby spheres, items that are inexpensive and 

commercially available, appear to be the most 

appropriate as fluorescent transducers. YAG:Cr and 

Gd2O2S:Eu are potential alternatives. 

Figure 2 shows a portion of the calibration curve 

for the ruby sphere in comparison with a competing 

material, YAG:Cr phosphor. Useable emission is 

Figure 1.	 Example of How Temperature Affects Decay 

Time of a Phosphor (TTL = transistortransistor logic) 

 FY 2003 Progress Report 

expected up to at least 700°C, making it a candidate 

for current PEM fuel cells as well as future designs 

that potentially operate at higher temperatures. 

Figure 3 illustrates a small diameter fiber (50 micron 

core, 110 micron cladding) inserted into a 

demonstrator fuel cell. Shown with the fuel cell is a 

water electrolyzer that generates hydrogen and 

oxygen to power the fuel cell. The cell was operated 

at 200 mW power output, and its performance was 

monitored before and after the temperature sensor 

was inserted. The temperature measurement was 

performed as follows: 1) disassemble the cell and 

place a small spot of phosphor on the polymer 

membrane, 2) position the fiber adjacent to the 

phosphor spot, 3) reassemble the cell and operate, 4) 

transmit light into the cell via the fiber and collect the 

fluorescence signal back through the same fiber, and 

5) process the fluorescence signal to determine 

temperature. 

Temperature measurements were acquired 

without any noticeable change to the operation of the 

fuel cell. Viable fluorescence signal levels have also 

been achieved with an optical fiber pair with core 

diameters of 50 microns. 

Figure 4 depicts various probe configurations 

that are under consideration. Laboratory tests are 

being conducted to optimize the signal-to-noise ratio 

of these probe designs. 

Figure 2. First Calibration Run for Ruby and YAG:Cr 

Phosphor 

Figure 3. Example of Low Profile Fiber Temperature 

Sensor Inserted into Demonstrator Fuel Cell 

4 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 3. Three Probe Designs under Consideration: 

(a) Dual Fiber Probe with Phosphor 

Impregnated Matrix (glass or polymer) Tip; 

(b) Single Fiber Probe with Doped Fiber 

Sensing Element Grown to Tip; and (c) 

Single Fiber Probe with Doped Sphere 

Attached (cemented or epoxied) to Tip 

Conclusions 

•	 Appropriate fluorescent transducer materials 

have been identified and characterized that will 

provide fast-responding and accurate 

temperature information from a fuel cell 

membrane electrode assembly. 

•	 Low-cost probe designs have been studied in the 

lab that will provide temperature data from 

operating fuel cells. 

•	 Initial field tests show that accurate and reliable 

temperature information can be gathered from 

operating fuel cells. 

•	 Long term field testing is needed to verify 

material compatibility between the fuel cell and 

the sensor probes and to characterize probe 

durability. 

References 

1. P. A. Rodnyi, "Progress in fast scintillators," 

Radiation Measurements 33 pp. 605-614, 2001. 

2. S. A. Payne and C. Bibeau, "Picosecond 

nonradiative processes in neodymium-doped 

crystals and glasses: Mechanism for the energy 

gap law," Journal of Luminescence 79 pp. 143­

159, 1998. 

3. T. Sun, Z. Y. Zhang, K. T. V. Grattan, and A. W. 

Palmer, "Determination of local high temperature 

excursion in an intrinsic doped fluorescencebased sensor," Review of Scientific Instruments, 

vol 69(8), p. 2930-2934, 1998. 

4. T. Sun, K. T. V. Grattan, W. M. Sun, S. A. Wade 

and B. D. Powell, "Rare-earth doped optical fiber 

approach to an alarm system for fire and heat 

detection," Review of Scientific Instruments vol 

74(1), pp. 250-255, 2003. 

5. D. N. Messias, M. V. D. Vermelho, and A. S. 

Gouveia-Neto, "All optical integrated 

upconversion fluorescence-based point 

temperature sensing system using Er3+-doped 

silica-on-silica waveguides," Review of Scientific 

Instruments vol 73(2), pp. 476-479, 2002. 

FY 2003 Publications/Presentations 

1. A poster on fluorescence thermometry was 

presented at the U.S. Department of Energy 

Hydrogen, Fuel Cells, and Infrastructure 

Technologies Program Review Meeting in 

Berkeley, CA, May 2003. 

2. A description of progress is planned for the 2003 

Fuel Cell Seminar to be held in Miami Beach, 

November 3-7, 2003. 

3. A paper on spatially resolved temperature 

measurement and embedded wave guide sensors 

is being prepared for submission to Review of 

Scientific Instruments. 

Special Recognitions & Awards/Patents 

Issued 

1. A patent disclosure has been filed on embedded 

wave guide sensors and their fabrication in 

polymer thin films. 

2. A patent disclosure has been filed on spatially 

resolved fiber optic temperature measurement. 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Hydrogen Composite Tank Project 

Reginald M. Penner 

Professor of Chemistry 

Department of Chemistry 

University of California, Irvine 

Irvine, CA 92697-2025 

Phone: (949) 824-8572; Fax: (949) 824-3168; E-mail: rmpenner@uci.edu 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

Develop a palladium nanowire-based hydrogen sensor that has fast response, is resistant to reactive gases, 

operates at room temperature, and it intrinsically safe. 

Technical Barriers 

This project addresses the following technical barrier from the Fuel Cells section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

• B. Sensors 	 

Approach 

We propose to develop a hydrogen gas (H2) 

sensor based on palladium nanowire arrays (PNAs) 

as shown in Figure 1. We discovered these sensors in 

2001 (Favier et al., 293 Science 2227) and 

demonstrated that PNAs exhibit a variety of desirable 

attributes for the detection of hydrogen gas, 

including: 

•	 Fast response (<25 ms baseline to 90% signal for 

5% H2 in N2), 

•	 Room temperature operation, 

•	 Efficient power utilization (10-7 - 10-8 watts), 

and 

•	 Resistance to poisoning by reactive gases 

including O2 and CO. 

Beginning in 2004, we will embark on a threeyear project to improve PNA H2 sensors for use in 

real-world hydrogen sensing applications. The goals 

of this project can be summarized as follows: 

First, the performance of PNA H2 sensors will be 

optimized over a range of environmental parameters 

including humidity and temperature (from –40oC to 

200oC) while in the presence of contaminating gases 

such as CO, O2, and H2S. Sensor parameters to be 

optimized will include the nanowire diameter and 

length and the identity and thickness of the polymer 

support. Second, we shall seek to improve the 

performance of PNA H2 sensors at high temperatures 

(where preliminary experiments show the limit-ofdetection for H2 is much higher than at ambient 

temperature – e.g. >5% at 80o

C). Of particular 

interest is the use of palladium alloys with both 

nickel and silver since such alloys exhibit higher 

hydrogen solubility at elevated temperatures. Third, 

we will investigate the feasibility of several new 

types of H2 sensors based on the PNA design. One 

idea to be explored involves the use of coaxially 

layered bimetallic nanowires in which an ultra-thin 

copper cladding is electrochemically applied to core 

nanowires composed of pure palladium. Because the 

chemisorption of many interfering species (e.g., CO, 

hydrocarbons) is weaker on copper than on 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Figure 1.	 (top) Schematic Diagram of PNA H2 Sensor, 

(bottom) Scanning Electron Microscopy 

(SEM) Image of a PNA H2 Sensor (The total 

width of this SEM image is approximately 

300 μm.) 

palladium, this copper outer layer will filter out these 

contaminants while permitting dihydrogen to 

dissociate and penetrate to the palladium core. A 

second direction will be the development of a sensor 

architecture that can be prepared directly on silicon 

surfaces using conventional silicon microfabrication 

technology. Our first efforts in this direction have 

culminated in a recent publication (Analytical 

Chemistry 75 (2003) 4756). These early results 

already suggest that an exciting new generation of 

microfabricated hydrogen sensors, exploiting a 

sensing mechanism closely related to that responsible 

for the operation of the PNA H2 sensors, are 

possible. 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Education Program Element Planning and Multi-Year R,D&D Plan Development 

DOE Technology Development Manager: Christy Cooper 

Phone: (202) 586-1885; Fax: (202) 586-9811; E-mail: Christy.Cooper@ee.doe.gov 

Contractor: SENTECH, Inc., Bethesda, MD 

Objectives 

•	 Prioritize activities to reach the target audiences critical to realizing the hydrogen economy 

•	 Identify key education actions that DOE should support 

•	 Secure stakeholder involvement in DOE's newly established Hydrogen, Fuel Cells and Infrastructure 

Technologies (HFCIT) Education Program Element 

•	 Begin a serious dialogue with stakeholders on the content of and issues related to an Education 

Program Element about hydrogen and fuel cells 

•	 Develop an education chapter for the HFCIT Multi-Year R,D&D Plan 

Technical Barriers 

This project addresses the following technical barriers from the Education section of the Hydrogen, Fuel 

Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Lack of Awareness 

•	 B. Lack of Demonstrations or Examples of Real World Use 

•	 C. Institutional Barriers and Access to Audiences 

•	 D. Regional Differences 

Approach 

•	 Draft a detailed education plan outline 

•	 Conduct a workshop to obtain stakeholder input to and feedback on draft plan outline 

•	 Publish education workshop proceedings to initiate additional stakeholder feedback 

•	 Develop section 3.8 of the HFCIT Multi-Year R,D&D Plan, incorporating the draft education plan 

elements and iterative stakeholder input 

Accomplishments 

•	 Held successful workshop for stakeholder input to the education plan 

•	 Published draft education workshop proceedings for comment 

•	 Published finalized education workshop proceedings with stakeholder input incorporated 

•	 Completed a draft education section of the HFCIT R,D&D Plan for stakeholder comment 

•	 Completed a revised education section for the R,D&D Plan, with stakeholder input incorporated 

Future Directions 

•	 Finalize the education section of the R,D&D Plan in accordance with recommendations from the 

National Academy of Sciences and stakeholder comments 

•	 Conduct education program activities during FY 2004 consistent with the goals, objectives, tasks, and 

milestones identified in the R,D&D Plan 

1 
 

 

 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Introduction • Identification of factors driving the need for 

educational activities 

The National Energy Policy and the National 

Hydrogen Energy Roadmap (“Roadmap”), two 

guiding documents for DOE hydrogen activities, pay 

special attention to education. The National Energy 

Policy recommends that the Secretary of Energy 

develop an education campaign to communicate the 

benefits of alternative energy technologies, including 

hydrogen. The Roadmap, which lays the foundation 

for a national move toward the use of hydrogen 

energy, also establishes a priority for education 

activities and suggests that education is an 

appropriate activity for the federal government. 

Following the National Energy Policy and 

Roadmap recommendations, the HFCIT Program 

established the Education Program Element to 

accomplish the overall objective of educating target 

audiences about the long-term benefits and near-term 

realities of hydrogen, fuel cell systems and related 

infrastructure. The Education Program Element will 

help audiences to do the following: 

•	 Understand the concept and value of a hydrogen 

economy 

•	 Recognize the near-term realities and 

opportunities of hydrogen and fuel cell 

technologies 

•	 Develop an accurate picture of hydrogen safety 

issues 

•	 Understand, where appropriate, their part in 

facilitating the transition to a hydrogen economy 

Approach 

In order to begin a serious dialogue with 

specialists on the content of, and issues related to, an 

educational program about hydrogen and fuel cells, a 

workshop was convened in Washington, DC, on 

December 4 and 5, 2002. More than 60 individuals 

participated in the meeting representing industry, 

government, non-governmental organizations, 

national laboratories and universities. Specific 

objectives of the meeting were to solicit inputs 

regarding the following: 

•	 Goals and objectives for DOE's hydrogen and 

fuel cell-related education activities 

•	 Identification and prioritization of audiences 

•	 Creative thinking on educational projects and 

activities that DOE could support 

•	 Prioritization of activities to reach the target 

audiences. 

Following the meeting, a proceedings record was 

drafted and circulated among the participants and 

other interested parties for feedback. The comments 

were incorporated into a finalized proceedings record 

that was made publicly available on the HFCIT 

website. 

Subsequent to the workshop, the Education 

Program Element worked with other components of 

the HFCIT Program to develop a Multi-Year R,D&D 

Plan for the period FY 2004 - FY 2010. The outputs 

of the education workshop were considered during 

the development of the education segment of this 

draft plan. The incorporation of stakeholder 

consultations and inputs into the R,D&D Plan 

development process was crucial to establishing a 

dialogue on hydrogen and fuel cell education 

activities, and to securing stakeholder support for 

HFCIT Education Program Element activities. 

Results 

The results of these planning and program 

development activities include the following: 

•	 Development of a comprehensive plan for 

hydrogen and fuel cell education activities for 

FY 2004 through FY 2010 that identifies key 

education activities for DOE involvement and 

prioritizes activities for near-term 

implementation 

•	 Publication of section 3.8 of the HFCIT R,D&D 

Plan, on Education 

•	 Development of a database of more than 60 

hydrogen and fuel cell education groups and 

major stakeholders 

•	 Establishment of a dialogue between and among 

the HFCIT Program, through the Education 

Program Element, and the hydrogen and fuel cell 

community on educational needs and activities 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Conclusions	 information about hydrogen and fuel cells, and 

•	 The Education Program Element will focus 

initially on target audiences that can facilitate 

hydrogen and fuel cell demonstration and 

commercialization: 

- State and local governments 

- Large-scale end-users 

- Safety and code officials 

- Teachers and students 

- Interested public 

•	 Educational activities will be coordinated with 

other HFCIT program element activities, 

particularly those for Technology Validation, 

Safety, and Codes and Standards, as well as with 

other DOE programs to extend the reach of 

educational activities. 

•	 The educational potential of hydrogen and fuel 

cell demonstrations will be realized by 

leveraging existing information/education 

conduits to maximize visibility among the 

general public, state and local decision makers, 

and other target audiences and stakeholders. 

•	 The Education Program Element will focus 

initial efforts to do the following: 

- Develop basic "groundwork" materials that 

provide program background and general 

establish a formal distribution mechanism for 

these materials 

- Enhance the presence of hydrogen and fuel 

cells in K-12 and university education 

- Facilitate educational activities for state and 

local governments and large-scale end-users 

- Facilitate information exchange and 

partnerships among emerging local, state, 

regional, and national hydrogen, fuel cell, and 

clean energy efforts 

FY 2003 Publications/Presentations 

Presentations on the Education Program Element 

and the R,D&D Plan development process were 

made at the following events: 

•	 Hydrogen, Fuel Cells, and Infrastructure 

Technologies Program Forum, October 2002 

•	 HFCIT Education Plan Workshop, December 

2002 

•	 National Hydrogen Association Annual Meeting, 

March 2003 

•	 National Clean Cities Conference, May 2003 

Section 3.8 of the HFCIT R,D&D Plan, on 

Education, was published for comment in draft form 

in June 2003. 

3 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Baseline Knowledge Assessment 

Tykey Truett (Primary Contact), David Greene, Rick Schmoyer, Bob Boundy 

Oak Ridge National Laboratory 

P.O. Box 2008, Building 3156, Bethel Valley Road 

Oak Ridge, TN 37831-6073 

Phone: (865) 574-4225; Fax: (865) 574-3895; E-mail: TruettLF@ornl.gov 

DOE Technology Development Manager: Christy Cooper 

Phone: (202) 586-1885; Fax: (202) 586-9811; E-mail: Christy.Cooper@ee.doe.gov 

Objectives 

•	 Conduct a literature search to identify previous surveys that measure knowledge of hydrogen 

technologies
 

•	 Identify non-survey metrics for assessing the current public visibility of hydrogen technologies 

•	 Develop and implement a plan for conducting national surveys of targeted audiences to determine each 

population's awareness of, knowledge about, and opinions concerning hydrogen and related 

technologies 

•	 Design a survey that assesses the general public's knowledge of hydrogen and related technologies 

Technical Barriers 

This project addresses the following technical barriers from the Education section of the Hydrogen, Fuel 

Cells, and Infrastructure Technologies (HFCIT) Program Multi-Year R,D&D Plan: 

•	 A. Lack of Awareness 

•	 C. Institutional Barriers and Access to Audiences 

•	 D. Regional Differences 

Approach 

•	 Conduct a literature search for previously conducted surveys that are related to the hydrogen economy, 

hydrogen technologies, and fuel cells 

•	 Establish liaison with Office of Management and Budget (OMB) and prepare paperwork for obtaining 

OMB approval for conducting surveys 

•	 Identify specific educational content for the target audiences (general public, students and educators, 

state and local agencies, and large-scale users) to consider when developing survey instruments 

•	 Develop survey instrument for public survey and initiate development of other survey questionnaires 

Accomplishments 

•	 Completed draft literature search and documented results 

•	 Began dialogue with appropriate contacts to obtain OMB approval of surveys 

•	 Submitted draft Federal Register Notice about the information collection to the DOE office of the 

Chief Information Officer 

•	 Completed planning for and design of general public survey, initiated work on surveys for other 

populations, and initiated collection of non-survey metrics 

•	 Initiated survey analysis plan 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Conduct and analyze surveys of the general public, students and educators, state and local government 

agencies, and large-scale users 

•	 Determine and document the baseline knowledge of hydrogen and fuel cells for the four populations 

involved in the surveys 

•	 Identify subject areas where hydrogen knowledge is lacking 

•	 Identify institutional barriers that prevent target audiences from receiving instruction or becoming 

informed about hydrogen technologies and applications 

•	 Use the survey results to identify differences, where appropriate, among audiences, regions, genders, 

and age groups 

•	 Determine the appropriate mechanism for conveying information about hydrogen and hydrogen 

technologies to each of the audiences 

•	 Continue collection and analysis of non-survey metrics 

•	 Document survey and non-survey metrics findings in a report 

Introduction 

The HFCIT Program needs to determine the 

baseline knowledge of hydrogen and fuel cells in the 

United States in order to design an appropriate 

educational program and, in the future, to assess the 

effectiveness of education activities. Baseline 

knowledge of hydrogen and fuel cells will be 

determined through surveys of four distinct population 

groups - the general public, students and educators, 

state and local governments, and potential large-scale 

users and/or agencies that impact large-scale users. 

Each of these populations is very different and 

requires a different approach for assessing knowledge. 

While recognizing that knowledge-assessment surveys 

cannot pinpoint causality of changes in knowledge and 

opinions, subsequent surveys identical in methodology 

to the baseline surveys can measure changes from 

baseline knowledge levels. The effect of the 

educational program will be measured in terms of 

program activities designed to impact baseline 

knowledge levels. 

Approach 

This task was initiated during FY 2003 through 

planning sessions, a literature search, and pilot 

questionnaires to ensure that the surveys were welldefined and that the objectives for both current and 

future surveys would be accomplished. A matrix 

was prepared that mapped each survey audience 

against the primary categories of educational 

information to ensure that the survey questions 

would address the appropriate content. 

Results 

Because this is a new task, there are no results to 

report at this time. 

Conclusions 

Although surveys have been conducted by 

several organizations concerning alternative fuels, 

and some surveys have been conducted on hydrogen 

and/or fuel cell applications, there has been no 

statistically designed, random survey of the U.S. 

population to determine the baseline knowledge of 

hydrogen and fuel cells. Nor has there been a 

systematic collection and assessment of non-survey 

materials related to the hydrogen economy. This 

type of hard evidence is needed in order to prepare 

the appropriate educational materials for the very 

wide-ranging audiences targeted for the HFCIT 

Program. 

FY 2003 Publications/Presentations 

1. Truett, et al. Literature Review for the Baseline 

Knowledge Assessment of the Hydrogen, Fuel 

Cells, and Infrastructure Technologies Program, 

Draft Final Report, June 2003 

2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Database of Existing Hydrogen and Fuel Cell-related Courses and Research 

Activities at Universities 

Elzbieta Tworek (Primary Contact) 

University of Tennessee 

2360 Cherahala Blvd. 

Knoxville, TN 37932 

Phone: (865) 946-1484; Fax: (865) 946-1314; E-mail: tworeke@ornl.gov 

ORNL Technical Advisor: David Greene 

Phone: (865) 946-1310; Fax: (865) 946-1314; E-mail: dlgreene@ornl.gov 

DOE Technology Development Manager: Christy Cooper 

Phone: (202) 586-1885; Fax: (202) 586-9811; E-mail: Christy.Cooper@ee.doe.gov 

Objectives 

•	 Develop a comprehensive online catalog of college and university programs teaching and conducting 

research in the areas of hydrogen and fuel cell technologies 

•	 Categorize institutions by accreditation status; collect and organize information on institutions: 

location, unit offering program, research and course descriptions; gather data on faculty and their 

research interests 

•	 Verify and maintain the database 

•	 Launch the catalog on the web 

Technical Barriers 

This project addresses the following technical barriers from the Education section of the Hydrogen, Fuel 

Cells, and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Lack of Awareness 

•	 C. Institutional Barriers and Access to Audiences 

Approach 

•	 Search web and review literature to determine if information is already accessible 

•	 Determine accreditation level of programs to be included 

•	 Identify conference and seminar participants as well as authors of specialized books and magazines 

affiliated with schools 

•	 Gather information on faculty and institutions with an interest in hydrogen and fuel cell technology 

•	 Verify credibility and accuracy (via web and personal interviews) of data yielded by research 

•	 Organize information by institution and create a searchable online database of over 70 institutions 

within the scope of this phase 

•	 Develop methods of collecting and verifying upcoming data 

Accomplishments 

•	 Documented current availability of educational opportunities related to hydrogen economy and fuel 

cell technologies 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Described programs and courses 

•	 Collect data on faculty and research members 

Future Directions 

•	 Designed searchable online catalog for use by educators, students, advisors, and government agencies 

•	 Confirm accuracy of data by creating a validation website for ongoing updates 

•	 Launch the catalog on the web 

•	 Increase number of tables linked to the main database, creating connections to individuals and research 

projects to help users refine searches 

•	 Include statistics on Ph.D. graduates from institutions (e.g., number of dissertations on hydrogen and 

fuel cell topics, etc.) 

•	 Include statistics of patent applications from affiliated institutions related to hydrogen and fuel cell 

technologies 

•	 Increase and maintain information in the catalog 

Introduction 

The purpose of the Hydrogen, Fuel Cells and 

Infrastructure Technologies (HFCIT) Education 

Program is to develop and conduct an education and 

training campaign that communicates the long-term 

benefits and near-term realities of hydrogen fuel cell 

systems and related infrastructure. A necessary 

element of this goal is to achieve a level of awareness 

of hydrogen's benefits among educators, other key 

target audiences, and eventually the public, while 

supporting the creation of the skilled and informed 

workforce required for a hydrogen future. As the 

R,D&D Plan for Education notes, initial education 

efforts will focus on teachers and students, state and 

local governments, safety and code officials, and 

large-scale end-users, all of whom are critical to 

sustained education efforts. The catalog resulting 

from this study documents the current availability of 

educational opportunities related to the hydrogen 

economy and fuel cell technologies as an aid to these 

targeted audiences. 

Approach 

This research considered only institutions of 

higher education with engineering programs 

accredited by the Accreditation Board for 

Engineering and Technology (ABET). U.S. 

accreditation is a voluntary, non-governmental 

process of peer review used to assure quality in 

educational institutions and programs. Most of the 

information included in the catalog has been gathered 

by searching university, library, and interest group 

web sites. The study has also identified people 

participating in conferences, seminars, or workshops 

covering hydrogen and fuel cell technology topics. 

Additionally, data has been accumulated by 

searching library databases and reviewing literature 

in the form of books, textbooks, conference 

proceedings, handbooks, industry and researchrelated overviews, government reports, and others. 

Information has also been obtained by phone and 

email contact with researchers and teaching faculty 

as well as authors of books related to hydrogen and 

fuel cells technologies. 

The study includes over 70 institutions, 

describing them on specific levels of detail. 

However, the accuracy of some data is questionable 

since school webmasters and professors often do not 

update their pages frequently. Therefore, in order to 

deliver precise and exact information, the database 

will be validated and will be maintained on an 

ongoing basis by means of a validation web site. 

This kind of interactive web site would give the 

directors of the research programs and faculty 

members the opportunity to express their willingness 

to be included in the catalog as well as to view and 

modify the data presented. 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Results 

A catalog has been developed in the form of a 

searchable database that categorizes detailed 

information about institutions offering research 

programs or courses related to hydrogen or fuel cell 

technologies. The catalog includes the following 

information: institution's name, location, 

organizational units offering related programs 

(academic department, center, and laboratory), types 

and names of courses covering hydrogen economy 

and fuel cell technology topics, descriptions of the 

research programs and courses, and names of faculty 

and research members affiliated with the program. 

This database will be linked to a database containing 

records of over 300 faculty and research members as 

well as their research interests, and full contact 

information like mailing address; email; homepage 

links; affiliated school; and academic department, 

center, or laboratory links. 

The catalog should be useful to many audiences, 

including educators (teaching faculty, counselors and 

advisors) who are looking for new career 

opportunities in research and teaching, students 

(undergraduate and graduate, current and prospective 

students) searching for educational and research 

programs that fit their interests, and business 

 FY 2003 Progress Report 

entrepreneurs seeking new technologies in research 

centers. Stakeholders such as state and local 

governments needing objective and accurate 

information in order to make informed decisions 

about sponsoring certain programs will also find the 

catalog useful. 

Conclusions 

The catalog promises to become an essential 

instrument in the search for hydrogen- and fuel-cellrelated educational opportunities for a broad 

spectrum of users. It may also be a useful tool for 

measuring the current status of hydrogen and fuel 

cell education and may provide a baseline for 

planning to expand hydrogen and fuel cell education 

programs. Government agencies such as DOE could 

use the catalog as a reference point in measuring the 

effectiveness of upcoming efforts to raise awareness 

and public support. 

As hydrogen research and education expands, 

new information about programs, courses, and 

educators involved in activities related to hydrogen 

and fuel cells will be added to the catalog. 

Additional tables will be made available through 

links, making the database more comprehensive for 

educators, students, government agencies, and 

perhaps the general public. 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Reduced Turbine Emissions Using Hydrogen-Enriched Fuels 

Robert Schefer (Primary Contact), Joe Oefelein 

Sandia National Laboratories 

7011 East Ave 

Livermore CA 94550 

Phone: (925) 294-2681; Fax: (925) 294-2595; E-mail: rwscge@sandia.gov 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

•	 Quantify effect of hydrogen addition on gas turbine combustion and emissions. 

•	 Establish a scientific and technological database for lean combustion of hydrogen-enriched fuels in gas 

turbines. 

•	 Establish numerical simulation capabilities that will facilitate design optimization of hydrogen and 

hydrogen-enriched lean gas turbine combustors. 

•	 Develop criteria for use of hydrogen addition as a control knob to eliminate instabilities related to 

varying product gas composition. 

Technical Barriers 

•	 The addition of hydrogen to hydrocarbon fuels affects flame stability, combustor acoustics, pollutant 

emissions and combustor efficiency. Few of these issues are clearly understood. 

•	 Designing a system that can operate over a wide range of fuels while controlling emissions is a 

challenging task. 

Approach 

•	 Design and fabricate a lean premixed swirl burner that simulates the basic features of gas turbine 

combustors. 

•	 Apply advanced experimental diagnostics to understand fluid dynamics, combustion chemistry, and 

pollutant formation. 

•	 Develop a computational model for combustor performance in parallel with the experimental program 

based on next generation Large Eddy Simulation (LES) technique. Use experimental database for 

model validation. 

•	 Identify problem areas in practical gas turbine combustors where hydrogen enrichment of hydrocarbon 

fuels could be beneficial. 

Accomplishments 

•	 Characterized operation of lean premixed swirl burner over a range of conditions. 

•	 Quantified effect of H2 addition on lean flame stability and characterized flame structure. Selected 

target flame conditions for detailed experimental study and model validation. 

•	 Fabricated atmospheric- and high-pressure versions of a lean premixed swirl burner in collaboration 

with National Energy Technology Laboratory (NETL). 

•	 Selected General Electric Aircraft Engines (GEAE) swirlcup injector to evaluate the advantages of H2-

addition in a production fuel injector. Completed hardware for installation of swirlcup injector in test 

stand. 

1 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

•	 Formed new collaboration with Pratt and Whitney to evaluate a production fuel injector for use with 

H2-blended fuels. 

•	 Continued international effort through International Energy Agency (IEA) to address H2-enriched 

hydrocarbon fuels for low emission, high efficiency gas turbine combustion. Defined program 

elements and identified modeling and experimental task areas. 

Future Directions 

•	 Complete detailed mapping of velocity field for model validation in the nonreacting swirl burner. 

Obtain detailed measurements of the velocity, temperature, species concentration fields and exhaust 

emissions under reacting conditions. Quantify effects of H2 addition. 

•	 Establish a representation of flow characteristics in the swirl burner using the LES model approach. 

•	 Establish a framework for modeling hydrogen-enriched lean premixed combustion in the presence of 

acoustically-active flame processes. 

•	 Complete development of test matrix for GEAE swirlcup fuel injector and perform testing. Identify 

areas where hydrogen enrichment could be beneficial. 

•	 Continue the formation of a broad consortium of industrial partners. 

•	 Continue development of international collaborations through the IEA. 

Introduction 

The development of advanced combustion 

capabilities for gaseous hydrogen and hydrogenblended hydrocarbon fuels in gas turbine applications 

is an area of much current interest. Driving this 

interest are several current needs. One need is the 

cost-effective utilization of alternative fuels with a 

wide range of heating values. For example, fuels 

containing significant amounts of hydrogen are often 

produced as a by-product in coal gasification 

combined cycle installations. These product gases 

could provide a significant source of cost-effective 

fuel for gas turbines. A second need is related to the 

recognition that ultra-lean premixed combustion is an 

effective approach to NOx emission reduction from 

gas turbine engines. Hydrogen blended with 

traditional hydrocarbon fuels significantly improves 

flame stability during lean combustion and allows 

stable combustion at the low temperatures needed to 

minimize NOx production. 

A longer-term need is the desire to eliminate 

unburned hydrocarbon (UHC) and CO2 emissions. 

Gas turbines account for 15% of U.S. CO2 emissions, 

which is a significant fraction of the total current 

CO2 emissions. This number will increase to nearly 

30% as natural gas turbines replace older coal-fired 

steam generation plants. The use of hydrogenblended hydrocarbon fuels thus provides both a 

solution to the immediate need for NOx reduction 

and also a transition strategy to a carbon-free energy 

system in the future. 

Approach 

The addition of hydrogen to hydrocarbon fuels 

affects both the chemical and physical processes 

occurring in flames. These changes affect flame 

stability, combustor acoustics, pollutant emissions 

and combustor efficiency. Few of these issues are 

clearly understood. This project will investigate 

issues surrounding the use of hydrogen and 

hydrogen-enriched hydrocarbon fuels in gas turbines. 

Both experimental and modeling approaches are 

being utilized. The experimental data will be 

obtained using an array of advanced laser diagnostic 

techniques that provide information on flame 

structure, fluid dynamics, combustion gas species 

concentrations and temperature. These 

measurements, in addition to providing direct 

insights into the effects of hydrogen enrichment on 

combustion and pollutant emissions, will provide the 

technological database needed for the parallel 

development of a numerical code, based on the LES 

technique, to simulate lean premixed combustion of 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

hydrogen and hydrogen-enriched fuels. Close 

collaborations have been developed with industrial 

partners to provide a mechanism for the transfer of 

this technology to practical applications in stationary 

and aircraft gas turbines. These collaborations will 

facilitate the identification of problematic areas 

related to practical gas turbine design and hardware. 

Areas where hydrogen addition could prove 

beneficial will be identified, and the potential merits 

of hydrogen-enriched hydrocarbon fuels will be 

demonstrated. 

Results 

The lean premixed swirl burner shown in Figure 

1 is representative of land-based industrial 

applications. This burner will be used to study 

combustion of hydrogen and hydrogen-blended 

hydrocarbon fuels. The design emphasizes wellcharacterized flow and boundary conditions to 

facilitate the development of a database for LES 

model validation. Emphasis with regard to LES has 

been placed on providing support calculations for 

Figure 1.	 Lean Premixed Swirl Burner Designed to 

Study Combustion of Hydrogen and 

Hydrogen-Blended Hydrocarbon Fuels 

 FY 2003 Progress Report 

design purposes and establishing an initial baselinemodeling framework for treatment of hydrogenenriched, premixed methane flames. The burner 

design is operationally relevant to industrial devices 

and is optimally tuned for flow and diagnostic 

capabilities at the Sandia Combustion Research 

Facility. 

The stability and burning characteristics of fuellean hydrogen/methane/air flames were characterized 

over a range of operating conditions in the swirl 

burner. Figure 2 shows the effect of hydrogen 

addition on flame stability, where the variable nH2 is 

the fraction of hydrogen in the fuel (nH2=0 

corresponds to pure methane and nH2=1 is pure 

hydrogen). The equivalence ratio, f, is a measure of 

the fuel/air ratio. These measurements were obtained 

by igniting the flame and then decreasing the fuel/air 

ratio until the flame completely extinguished, or 

blew out. The flame typically becomes unstable as 

the blowout condition is approached. Increasing the 

hydrogen content from 0% to 20% results in a 

significant shift in flame blowout conditions to leaner 

fuel/air ratios. Since operation at leaner fuel/air 

ratios results in a lower flame temperature and 

reduced NOx emissions, hydrogen addition will 

allow stable operation at the lean conditions needed 

to limit NOx emissions. 

Figure 2. Effect of Hydrogen Addition on Flame 

Stability in Lean Swirl Burner
 

3 
 

 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

A previous study analyzed the potential of 

controlling NOx emissions with the addition of 

hydrogen [1]. It was found that up to 20% hydrogen 

addition is a competitive alternative to traditional 

NOx control technologies, providing NOx levels of 

about 3 ppm. This study was extended to include the 

potential benefits of reduced CO2 emissions by 

hydrogen addition as well as NOx reduction. Figure 

3 compares the cost of NOx removal using H2 

addition with the costs of conventional selective 

catalytic reduction of NOx (SCONOx) and chemical 

absorption for CO2 removal. While 60-100% 

hydrogen addition is not competitive with SCONOx 

alone, up to 75% hydrogen addition is cost 

competitive when the cost of CO2 removal is 

included. 

Figure 3.	 Cost sensitivity to percent hydrogen in 

natural gas. Estimated NOx emissions are 1 

ppm with high percentage CO2 reduction. 

Credits to the Hydrogen Addition to Midsize Gas 

Turbine Feedstocks,” 14th Annual U.S. Hydrogen 

Conference and Hydrogen Expo USA, March 4-6, 

Washington, D.C. (2003). 

FY 2003 Publications 

1. R. W. Schefer, D. M. Wicksall and A. K. Agrawal: 

“Combustion of Hydrogen-Enriched Methane in a 

Lean Premixed Swirl-Stabilized Burner”, 

Proceedings of the 29th Symposium 

(International) on Combustion, pp. 843-851 

(2002). 

2. R. W. Schefer: “Hydrogen Enrichment for 

Improved Lean Flame Stability”, International 

Journal of Hydrogen Energy, 28/10, pp. 1131-

1141 (2003). 

3. R. W. Schefer, T. D. Smith and C. J. Marek, 

“Evaluation of a Lean Premixed Hydrogen 

Burner”, Combustion Science and Technology 

(submitted), 2003. 

FY 2003 Presentations 

1. Wicksall, D. M., Schefer, R. W., Agrawal, A. K. 

and Keller, J. O., “Simultaneous PIV-OH PLIF 

Measurements in a Lean Premixed SwirlStabilized Burner Operated on H2/CH4/Air”, 

Proceedings of the Third Joint Meeting of the U.S. 

Sections of the Combustion Institute, March 17-

19, Chicago, IL (2003). 

Conclusions 

•	 Hydrogen addition significantly improves flame 

stability and allows stable burner operation at the 

lean fuel/air ratios needed for reduced NOx 

emissions. 

•	 Up to 65% hydrogen addition for NOx reduction 

to the 1 ppm level is cost competitive with 

current control technologies when both NOx 

emissions and the cost of CO2 removal are 

considered. 

References 

1. Towns, B., Skolnik, E., Miller, J., Keller, J. and 

Schefer, R., “Analysis of the Benefits of Carbon 

2. Wicksall, D. M., Schefer, R. W., Agrawal, A. K. 

and Keller, J. O., “Fuel Composition Effects on 

the Velocity Field in a Lean Premixed SwirlStabilized Burner“, Proceedings of ASME Turbo 

Expo 2003: 48th ASME International Gas Turbine 

and Aero Engine Technical Congress and 

Exposition, June 16-19, Atlanta, GA (2003). 

3. Vagelopoulos, C. M., Oefelein, J. C. and Schefer, 

R. W., “Response of Lean Premixed Methane 

Flames to Hydrogen Enrichment”, Proceedings of 

the Third Joint Meeting of the U.S. Sections of the 

Combustion Institute, March 17-19, Chicago, IL 

(2003). 

4. Vagelopoulos, C. M., Oefelein, J. C. and Schefer, 

R. W., “Effects of Hydrogen Enrichment on Lean 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Premixed Methane Flames”, 14th Annual U.S. 

Hydrogen Conference and Hydrogen Expo USA, 

March 4-6, Washington, D.C. (2003). 

5. Towns, B., Skolnik, E., Miller, J., Keller, J. and 

Schefer, R., “Analysis of the Benefits of Carbon 

Credits to the Hydrogen Addition to Midsize Gas 

Turbine Feedstocks”, 14th Annual U.S. Hydrogen 

Conference and Hydrogen Expo USA, March 4-6, 

Washington, D.C. (2003). 

6. Schefer, R.W., “Reduced Turbine Emissions 

Using Hydrogen-Enriched Fuel”, 14th World 

Energy Conference, Montreal, Quebec, Canada, 

June 9-13, 2002. 

7. TerMaath, C., Skolnik, E., Keller, J. O. and 

Schefer, R. W., “Emissions Reduction Benefits 

from H2 Addition to Midsize Gas Turbine 

Feedstocks”, 14th World Energy Conference, 

Montreal, Quebec, Canada, June 9-13, 2002. 

5 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Developing a Thermodynamic Fuel Cell 

Peter Van Blarigan 

Sandia National Laboratories 

MS 9661, PO Box 969 

Livermore, CA 94551 

Phone: (925) 294-3547; Fax: (925) 294-1322; E-mail: pvanbla@sandia.gov 

DOE Technology Development Manager: Neil Rossmeissl 

Phone: (202) 586-8668; Fax: (202) 586-9811; E-mail: Neil.Rossmeissl@ee.doe.gov 

Objectives 

Demonstrate a combustion-based approach to electrical generation, maximizing the thermodynamic cycle 

and thus achieving high efficiency and near-zero emissions, while facilitating a path to hydrogen and 

hydrogen-rich fuels utilization. 

Technical Barriers 

This project addresses the following technical barriers from the Fuel Cell Transportation Systems section 

of the Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 D. Fuel Cell Power System Benchmarking 

Approach 

•	 Analyze significant components of the thermodynamic fuel cell, including homogeneous charge 

compression ignition (HCCI) combustion, linear electrical generation and two-stroke cycle charging, 

employing experimental and computational means. 

•	 Design major sub-systems based on achieving maximum electrical conversion efficiency and minimal 

operating emissions. 

•	 Integrate components into a full-scale prototype with a rated power output of 30 kW. 

•	 Demonstrate the device's operating performance and fuel versatility. 

Accomplishments 

•	 Experimentally established the potential of HCCI combustion using a free piston configuration 

(30-kW, 2-kW sizes) to realize significant improvements in thermal efficiency and NOx emissions. 

•	 Computationally analyzed, designed and constructed a full scale linear alternator. Collaborated with 

Magnequench, Int. to design and manufacture a similar, but significantly different linear alternator at 

no cost to Sandia. 

•	 Reconfigured a 4-cylinder Caterpillar engine to test the performance of the two linear alternator 

designs at full power output. 

•	 Computationally developed an optimized gas transfer system with respect to the thermodynamic fuel 

cell's operating characteristics and two-stroke cycle dynamics. 

•	 Investigated the performance of a hybrid thermodynamic fuel cell/turbine system. 

•	 Completed preliminary designs for a 4-kW free piston gas compressor (Sandia funded). 

1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Future Directions 

•	 Measure and evaluate linear alternator performance. Modify/adjust configurations based on 

dynamic testing. 

•	 Investigate additional scavenging designs incorporating late, port fuel injection for short-circuited 

emissions control. Verify computational results using a free piston, single-stroke scavenging 

experiment. 

•	 Develop control schemes to facilitate nominal operation. 

•	 Integrate components into a full-scale demonstration prototype. 

•	 Form industrial consortium for commercial application. 

Introduction 

High efficiency, low emissions electrical 

generators will lead to a path for renewable 

hydrogen-based fuel utilization. Electrochemical 

fuel cells are generally considered to be ideal devices 

for these applications, where hydrogen or methane is 

used as the fuel. However, the extensive 

development of the internal combustion engine, and 

the existence of repair and maintenance industries 

associated with piston engines, provide strong 

incentives to remain with this technology until 

electrochemical fuel cells are proven reliable and 

cost competitive. 

The thermodynamic fuel cell is based on 

utilizing homogeneous charge compression ignition 

(HCCI) combustion of very lean (φ ~ 0.3) fuel-air 

mixtures to approach ideal Otto cycle performance 

(the most thermodynamically efficient option for 

piston engines). HCCI is extremely rapid (nearly 

constant-volume), with numerous ignition points 

occurring throughout the charge; chemical kinetics 

dominate while there are no flame propagation or 

fuel diffusion requirements [1]. In addition, virtually 

any fuel-air mixture can be used, with NOx emissions 

controlled through sufficient charge dilution and 

rapid expansion of the combustion gases [2]. 

Sandia’s concept, illustrated in Figure 1, employs a 

free piston/linear alternator combination to facilitate 

direct electrical generation, thus enabling electronic 

control of the HCCI process and therefore the 

performance of the fuel cell. Structural integrity (for 

high peak pressures), design simplicity and cost 

issues are addressed with this unique design. 

Figure 1. Thermodynamic Fuel Cell 

Approach 

This research project aims to investigate and 

resolve critical issues involved in developing the 

thermodynamic fuel cell. The end goal is to 

construct a full-scale prototype that can demonstrate 

the device's efficiency and emissions potential, as 

well as its fuel versatility. Major processes of HCCI 

combustion, linear electrical generation and twostroke cycle charge delivery have been investigated 

in previous years using both experimental and 

computational means. The objective has been to 

verify the capabilities of the critical components 

while determining the factors that will affect the 

performance of the integrated configuration. 

During fiscal year 2003, efforts were made to 

continue to design, build and test various 

components, and to further develop industrial 

partnerships; commercial relationships are expected 

to facilitate the rapid transfer of this technology to 

the marketplace after concept demonstration. Work 

this year focused on aspects of the linear alternator 

and the scavenging system, as well as additional 

2 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies

studies investigating the benefits of a combined 

thermodynamic fuel cell / turbine hybrid system. 

Results 

The alternator test rig, illustrated in Figure 2, 

became operational this year, with issues regarding 

the piston’s integrity seemingly resolved. A test 

procedure has been developed and preliminary data 

acquired using the Magnequench constructed 

alternator, without the inclusion of the permanent 

magnets. The magnets will be attached to the piston 

next and tests run under both load and no-load 

conditions. A switching mechanism will need to be 

developed to achieve the rated output for this design 

(as explained in previous FY reports); however, 

comparison with Magsoft FLUX2D software’s 

performance predictions and an evaluation of its 

accuracy should be possible in the coming months. 

Multi-dimensional modeling of the scavenging 

system was employed to analyze and design an 

optimal arrangement; this configuration will be 

fabricated and tested using a single-cycle 

experiment. Figure 3 illustrates an arrangement 

expected to give very good performance (charge 

replacement greater than 90%, with fuel trapping 

capabilities near 100%). In this “stratifiedscavenging” design, an initial charge of fresh air 

 FY 2003 Progress Report 

(yellow) flushes the combustion products from the 

cylinder (orange), while a rich fuel-air mixture (blue) 

is introduced late in the gas transfer process. A late, 

port fuel-injected configuration to be investigated in 

FY 2004 represents a natural progression in this 

component’s development and should improve shortcircuiting controllability. 

Full cycle thermodynamic modeling utilizing 

zero-dimensional representations of the in-cylinder 

processes, the free piston dynamics, and assumed 

efficiencies for a turbocharger/compressor 

combination, was used to conduct a feasibility study 

analyzing a thermodynamic fuel cell/turbine 

combination [3]. Simulations were conducted over a 

range of possible boost pressures, from 1.2 bar 

through 3.0 bar. The results indicated that the 

emissions performance is unchanged for these 

variations; however, the free piston dynamics can be 

significantly altered by an increase in cylinder 

pressure. For the highest boost case, the frequency 

increased 45%. In addition, the combustion 

pressures were also calculated to be sensitive to any 

boost, with the peak pressure increasing to 445 bar 

(from 230 bar) for the 3.0 bar boost case. 

The performance improvements for the hybrid 

system are presented in Figure 4. The changes in 

generating efficiency (87% at 2.5 bar) and power 

density (838% at 3.0 bar) with increasing boost 

pressure are plotted. It can be seen that there is a 

maximum efficiency that can be reached in this 

hybrid arrangement due to the performance limit of 

current turbocharger and compressor technologies. 

The power density, on the other hand, did not seem to 

have a limit for the conditions investigated. 

Figure 2. Alternator Test Rig Figure 3. Calculated Stratified-Scavenging Flows 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Figure 4. Fuel-to-Electricity Conversion Efficiency 

and Power Density vs. Boost Pressure 

Conclusions 

•	 The thermodynamic fuel cell represents a near 

term (2010) option for achieving the DOE's 

Hydrogen, Fuel Cells and Infrastructure 

Technologies Program goals of significantly 

advancing the operating efficiency and emissions 

performance of electrical generating devices, 

while creating a path for renewable hydrogenbased fuel utilization. 

•	 A prototype design is moving forward, with the 

performance of each major sub-system being 

quantified. 

•	 To date, no unsolvable barriers have materialized. 

References 

1. Onishi, S., Jo, S. H., Shoda, K., Jo, P. D. and Kato, 

S., "Active Thermo-Atmospheric Combustion 

(ATAC) - A New Combustion Process for Internal 

Combustion Engines," SAE Paper 790501, 1979. 

2. Van Blarigan, P., Paradiso, N. and Goldsborough, 

S., "Homogeneous Charge Compression Ignition 

with a Free Piston: A New Approach to Ideal Otto 

Cycle Performance," SAE Paper 982484, 1998. 

3. Van Blarigan, P. and Goldsborough, S., "Free 

Piston Generator/Turbine Systems - Advanced 

Hybrid Systems," Proceedings of the 14th Annual 

 FY 2003 Progress Report 

U.S. Hydrogen Meeting: Energy Security through 

Hydrogen, National Hydrogen Association, 

March 4th-6th, Washington, DC, 2003. 

FY 2003 Publications/Presentations 

1. Eisenbies, S. K., Van Blarigan, P. and 

Goldsborough, S. S., "A Feasibility Study of the 

Free Piston Engine Linear Alternator Concept for 

Use as a Distributed Power Source in Aircraft," 

SAND Report 2003-xxxx, Sandia National 

Laboratories. 

2. Goldsborough, S., "Toward the Development of 

an Advanced, Rapid Combustion Electrical 

Generator", Alfred University, April 17th, Alfred, 

NY, 2003. 

3. Goldsborough, S., "Toward the Development of 

an Advanced, Rapid Combustion Electrical 

Generator", Marquette University, March 27th, 

Milwaukee, WI, 2003. 

4. Van Blarigan, P. and Goldsborough, S., "Free 

Piston Generator/Turbine Systems - Advanced 

Hybrid Systems," 14th Annual U.S. Hydrogen 

Meeting: Energy Security through Hydrogen, 

National Hydrogen Association, March 4th-6th, 

Washington, DC, 2003. 

5. Goldsborough, S. S. and Van Blarigan, P., 

"Optimizing the Scavenging System for a TwoStroke Cycle Free Piston Engine for High 

Efficiency and Low Emissions: A Computational 

Approach," SAE Paper 2003-01-0001, March 3rd, 

Detroit, MI, 2003. 

6. Goldsborough, S. S. and Van Blarigan, P., 

"Optimizing the Scavenging System for a TwoStroke Cycle Free Piston Engine for High 

Efficiency and Low Emissions: A Computational 

Approach," International Multidimensional 

Engine Modeling User's Group Meeting at the 

SAE Congress, March 2nd, Detroit, MI, 2003. 

7. Van Blarigan, P. and Goldsborough, S., "Ideal 

Otto Cycle Implementation of HCCI 

Combustion," U.S. Department of Energy HCCI 

Meeting, Sandia National Laboratories, January 

30th, Livermore, CA, 2003. 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

8. Goldsborough, S. S., "Optimizing the 

Scavenging System for High Efficiency and Low 

Emissions: A Computational Approach," PhD 

Dissertation, Colorado State University, Ft. 

Collins, CO, Fall 2002. 

Special Recognitions & Awards/Patents 

Issued 

1. Van Blarigan, P., "Free-Piston Engine," US Patent 

# 6,199,519 B1 

2. Harry L. Horning Memorial Award, Society of 

Automotive Engineers, 1998 

5 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

HCNG Heavy Duty Vehicle Prime Mover 

Kirk Collier (Primary Contact), Neal Mulligan, Ranson Roser 

Collier Technologies, LLC 

681 Edison Way 

Reno, NV 89502 

Phone: (775) 857-1937; Fax: (775) 857-1938; E-mail: kcollier@nrgtech.com 

DOE Technology Development Manager: Sigmund Gronich 

Phone: (202) 586-1623; Fax: (202) 586-9811; E-mail: Sigmund.Gronich@ee.doe.gov 

Objectives 

•	 Develop a low-emissions heavy-duty vehicle engine repowering package that seamlessly replaces 

existing natural gas and diesel engines in today's buses and trucks. 

•	 Exceed DOE's goal of reducing emissions by 75% compared to 1998 emission standards by achieving 

a 99.5% reduction. Corresponding emission levels of carbon monoxide (CO) will be <1 ppm; nonmethane hydrocarbon (NMHC) emissions will be <0.05 g/hp-hr; and oxides of nitrogen (NOx) will be 

<0.15 g/hp-hr. 

•	 Maintain or enhance current vehicle driveability by effective selection, matching, and configuring of 

off-the-shelf components. 

•	 Meet DOE's requirement to maintain thermal efficiency by obtaining an overall thermal efficiency of 

greater than 35%. 

•	 Prove and enhance the engine design through in-service testing. 

•	 Develop a public/private partnership to implement a commercialization plan that will bring new 

business and economic opportunities to Nevada. 

Technical Barriers 

This project addresses the following technical barrier from the Technology Validation section of the 

Hydrogen, Fuel Cells and Infrastructure Technologies Program Multi-Year R,D&D Plan: 

•	 A. Vehicles 

Approach 

•	 Use hydrogen added to natural gas (HCNG) to achieve high charge dilution ratios to create near-zero 

NOx emissions. 

•	 Incorporate an alternative engine design from that of current heavy-duty engines. Engine design 

features include: 

- Nickel silicon carbide cylinder bores 

- Quiescent combustion 

- Higher rpm operation 

- Larger displacement 

- Mass air flow engine control 

1 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Accomplishments 

• Demonstrated 0.14 g/hp-hr simulated driving cycle NOx emissions. 

• Produced equivalent power and torque to natural gas engine. 

• Demonstrated 38% engine efficiency. 

• Bus is currently operating in Las Vegas. 

Future Directions 

• Expand the work to convert five additional City of Las Vegas buses to HCNG. 

• Market HCNG hydrogen technology to other transit districts. 

Introduction 

The use of hydrogen as a fuel additive to extend 

the lean burn limit of conventional fuels has been 

repeatedly demonstrated to be a viable approach to 

achieving near-zero exhaust emissions from internal 

combustion engines. This technology is intended to 

be a near-term application for hydrogen and to 

accelerate hydrogen infrastructure development 

given the current economic climate. Hydrogen fuelrelated problems such as high fuel cost, high prime 

mover costs (fuel cells) and low energy density are 

largely overcome by supplementing an existing, 

higher energy storage density, lower-cost fuel, such 

as natural gas, and implementing a low-cost prime 

mover such as internal combustion engines. 

Demonstrating that this low-cost hydrogen 

technology can improve emissions of oxides of 

nitrogen by a factor of thirty over current 

generation natural gas engines can create the 

incentive by which a hydrogen infrastructure can 

be developed that will be necessary for the 

successful implementation of fuel cells. 

Approach 

Collier Technologies, LLC is using charge 

dilution as the mechanism for controlling harmful 

exhaust emissions. The basic technique employed is 

to combine exhaust gas recirculation (EGR) and lean 

burn. Cooled and dried EGR is used to control NOx 

emissions and lean burn to control CO and NMHC 

emissions. It is anticipated that lean burn will 

achieve approximately 2 to 4% oxygen in the 

exhaust. This will allow an off-the-shelf oxidizing 

catalyst to achieve very high conversion rates for 

both CO and NMHC emissions. Because the exhaust 

gas temperatures will be comparatively very low 

(<1000EF), catalyst lifetime should be extremely 

high (>100,000 miles). 

To achieve near-zero NOx emissions (10 to 20 

ppm) using charge dilution, the engine must operate 

with an overall lambda (air-fuel ratio divided by the 

stoichiometric air-fuel ratio, including EGR) of 

between 1.8 and 2.0. To achieve this value, at least 

30%, by volume, of the fuel must be hydrogen. Any 

less than that will not support sufficiently consistent 

combustion from cylinder to cylinder or from cycle 

to cycle. Any attempts to achieve this through 

mechanical means (high turbulence combustion 

chambers, etc.) will result in loss of engine efficiency 

through increased combustion chamber heat transfer 

rates and increased NOx emissions compared to 

“quiescent” or open combustion chambers and 

hydrogen addition to the fuel. The result is that 

mechanical enhancement (swirl, tumble, etc.) for 

lean burn will require higher values of lambda to 

achieve equivalent NOx emissions to that achieved 

by hydrogen as a fuel enhancement. 

Results 

A 30-ft transit bus was purchased by DOE and 

shipped to Collier Technologies (then called NRG 

Tech) for conversion to HCNG operation. This bus 

came equipped with a Cummins 8.3L natural gas 

engine. The project called for characterizing the 

exhaust emissions from the current configuration so 

2 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

that the benefits of HCNG can be quantitatively 

assessed. Baseline exhaust emissions were taken 

from the engine using a steady state emissions test 

protocol that is designed to simulate the heavy-duty 

driving test procedure. This protocol is as follows: 

Engine rpm at maximum torque value 

Test Point 1100% loadEmissions are 15% of final value 

Test Point 275% loadEmissions are 15% of final value 

Test Point 350% loadEmissions are 15% of final value 

Test Point 410% loadEmissions are 10% of final value 

Engine rpm at maximum power value 

Test Point 5100% powerEmissions are 10% of final value 

Test Point 675% powerEmissions are 10% of final value 

Test Point 750% powerEmissions are 10% of final value 

Test Point 8IdleEmissions are 15% of final value 

The results of testing the Cummins engine that 

was installed in this bus using the protocol listed 

above are shown in Table 1. 

Emissions results for the 8.8L Collier 

Technologies engine using the same testing protocol 

and using a 30/70 mixture of hydrogen and natural 

gas are shown in Table 2. 

Table 1. 8-Mode Steady State Emissions Summary 

Cummins 8.3L Natural Gas Engine (as received) 

Individual Modes NOx 

g/hp-hr 

THC 

g/hp-hr 

NMHC 

(g/hp-hr) 

CO 

g/hp-hr 

Weighting 

Factor 

1400 rpm 

2400 rpm 

800 rpm 

- 100% Load 

- 75% Load 

- 50% Load 

- 10% Load 

- 100% Load 

- 75% Load 

- 50% Load 

- Idle 

7.42 

4.70 

5.67 

5.77 

1.18 

0.80 

0.44 

6.96 

5.21 

2.57 

3.37 

7.70 

2.82 

4.26 

5.56 

107.74 

0.16 

0.08 

0.10 

0.23 

0.08 

0.13 

0.17 

3.23 

0.19 

0.22 

0.25 

0.59 

0.28 

0.32 

0.37 

12.98 

0.15 

0.15 

0.15 

0.10 

0.10 

0.10 

0.10 

0.15 

Weighted 8 Mode (g/hp-hr) 4.60 19.87 0.58 2.20 

Weighted 8 Mode (g/kw-hr) 6.16 26.63 0.78 2.95 

Table 2. 8-Mode Steady State Emissions Summary 

HCNG Bus Engine 

Individual Modes NOx 

g/hp-hr 

THC 

g/hp-hr 

NMHC 

(g/hp-hr) 

CO 

g/hp-hr 

Weighting 

Factor 

1800 rpm 

2800 rpm 

800 rpm 

- 100% Load 

- 75% Load 

- 50% Load 

- 10% Load 

- 100% Load 

- 75% Load 

- 50% Load 

- Idle 

0.15 

0.12 

0.09 

0.13 

0.21 

0.15 

0.10 

0.22 

3.70 

3.86 

4.86 

8.82 

3.31 

3.77 

5.75 

7.21 

0.11 

0.12 

0.15 

0.26 

0.10 

0.11 

0.17 

0.22 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.15 

0.15 

0.15 

0.10 

0.10 

0.10 

0.10 

0.15 

Weighted 8 Mode (g/hp-hr) 0.15 5.11 0.15 0.00 

Weighted 8 Mode (g/kw-hr) 0.20 6.85 0.21 0.00 

3 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Conclusions 

Emissions, power, torque, and efficiency goals 

have been met with our project methodology. NOx 

emissions have been reduced by a factor of 30 when 

compared to the existing engine without a loss of 

power, torque characteristics or fuel efficiency. 

Major milestones for the remainder of the project 

will be to demonstrate drivability in an operating bus 

and verify exhaust emissions in a driving test. 

 FY 2003 Progress Report 

4 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Acronyms and Abbreviations
 

∆spec 

Å 

A/C 

ABET 

AC 

ACR 

AER 

AFC 

Ag 

AGB 

AHC 

AirCred 

Al 

Al2O2 

AlCl3 

ANL 

ANT 

APU 

a-Si 

ASME 

ASR 

ASU 

atm 

ATMI 

ATP 

ATR 

Au 

B 

barg 

bdt 

BNL 

BOP 

BP 

BPSH 

Br 

BSE 

BTU 

C 

o

C 

C2H4 

Ca 

Absorbance-difference kinetic 

spectrophotometry 

Angstrom (one hundred-millionth of 

a centimeter) 

Air Conditioner 

Accreditation Board for Engineering 

and Technology 

Alternating Current 

Autothermal Cyclic Reforming 

Absorption-Enhanced Reforming 

Alkaline Fuel Cell 

Silver 

Anode Gas Burner 

Ad Hoc Committee 

Air Quality Credits 

Aluminum 

Aluminum Oxide 

Aluminum Chloride 

Argonne National Laboratory 

Albany NanoTech 

Auxiliary Power Unit 

Amorphous Silicon 

American Society of Mechanical 

Engineers 

Area Specific Resistance 

Air Separation Unit 

atmosphere 

Advanced Technical Materials 

Incorporated 

Adenosine Triphosphate 

Autothermal Reformer/Reforming/ 

Reactor 

Gold 

Boron 

Bar Gauge 

Bone Dry Ton 

Brookhaven National Laboratory 

Balance of Plant 

British Petroleum 

Biphenyl sulfones 

Bromine 

Back Scattered Electron 

British Thermal Unit 

Carbon 

Degrees Centigrade 

Ethylene 

Calcium 

CaBr2 Calcium Bromide 

CAD Computer Aided Design 

CAE Computer Aided Engineering 

CaO Calcium Oxide 

CARB California Air Resources Board 

CATA Center Area Transport Authority 

CBS Specific Strain of Rubrivivax 

Gelatinosus 

CCH Complex Compound Hydride 

CCHS Complex Compound Hydrogen 

Storage System 

CCM Catalyst Coated Membrane 

Ce Cerium 

CE European Conformity 

CEC California Energy Commission 

CEM Compressor Expander Motor/ 

Continuous Emissions Monitoring 

CERMET Ceramic and Metal 

CESI Catalytic Energy Systems Inc 

CF Capacity Factor 

CFA Community Fuel Appliance 

CFD Computational Fluid Dynamics 

CFR Code of Federal Regulations 

CGA Compressed Gas Association 

CGO Cerium-Gadolinium Oxide 

(Ce0.8Gd0.2O1.9) 

CH2 Compressed Hydrogen Gas 

CH2-ISS Compressed Hydrogen Gas 

Integrated Storage System 

CH4 Methane 

Chl Chlorophyll 

CIGS Copper-Indium-Gallium-Diselenide 

CL&P Connecticut Light and Power 

CLV City of Las Vegas 

cm2 Centimeters Squared 

CMS Crash Management System 

CMWG Carbon Materials Working Group 

CNG Compressed Natural Gas 

CNR Center for Neutron Research 

CO Carbon Monoxide 

CO2 Carbon Dioxide 

COE Cost of Electricity 

COGEN Combined Building Heat and Power 

COS Carbonyl Sulfide 

CPO Catalytic Partial Oxidation 

CPS Chemical Process Simulation 

cpsi cells per square inch 

X - 1 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

CPSS	 Combinatorial Powder Synthesis 

System 

Cr Chromium 

CS Constant Stoichiometry 

CS&D Compression, Storage and 

Dispensing 

CSMP Cabot Superior Micropowders 

CST Compact Stuart Technology 

Cu Copper 

Cu2O Cuprous Oxide 

CVD Chemical Vapor Deposition 

CVI Chemical Vapor Infiltration 

CWRU Case Western Reserve University 

CY Calendar Year 

DBEDT Department of Business, Economic 

Development and Tourism (Hawaii) 

DC Direct Current 

DCF Discounted Cash Flow 

DCM Dichloromethane 

DEP Department of Environmental 

Protection 

DER Distributed Energy Resources 

DFMA Design for Manufacture and 

Assembly 

DG Distributed Generator 

DME Dimethylether 

DMFC Direct Methanol Fuel Cell 

DNA Deoxyribonucleic Acid 

DNS Direct Numerical Simulation 

DOD U.S. Department of Defense 

DOE U.S. Department of Energy 

DOT U.S. Department of Transportation 

DP Differential Pressure 

DRIFTS Diffuse Reflectance mid-Infrared 

Fourier Transform Spectroscopy 

DSC Differential Scanning Calorimetry 

DTI Directed Technologies Inc. 

EB/GDL Electrode Backing/Gas Diffusion 

Layer 

EdNet Educational Network 

EDS Engineering Development 

Specification 

EERE Energy Efficiency and Renewable 

Energy 

EIHP European Integrated Hydrogen 

Project 

ELAT® Registered Trademark of De Nora 

North America, Inc., covers GDLs 

and GDEs 

EMF	 Electromagnetic Field 

EMI 

EMPA 

EPA 

EPR 

EPRI 

ERD 

ESA 

ESR 

ESS 

ETS 

EXAFS 

F 

FASTER 

FC 

FCCP 

FCE 

FCEV 

FCPI 

FCPS 

FCS 

FCTF 

FCV 

Fd 

Fe 

Fe2O3 

Fe3O4 

FeCl3 

FePOx 

FET 

FID 

FIT 

FMEA 

FP1 

FPD 

FPES 

FPS 

FRACAS 

FreedomCAR 

FS-PEEK 

FTA 

Electromagnetic Interference 

Electron Microprobe Analysis 

U.S. Environmental Protection 

Agency 

Electron Paramagnetic Resonance 

Electric Power Research Institute 

Energy Recovery Device 

Electrochemical Surface Area 

Electron Spin Resonance 

Energy Storage System 

Engelhard Titanosilicate 

(commercial membrane material 

name) 

Extended X-ray Absorption Fine 

Structure 

Force 

Feasibility of Acceptable Start Time 

Experimental Reactor 

Fuel Cell 

carbonyl cyanide mchlorophenylhydrazone 

Fuel Cell Energy 

Fuel Cell Electric Vehicle 

Fuel Cell Propulsion Institute 

Fuel Cell Power System 

Fuel Cell System 

Fuel Cell Test Facility (Hawaii) 

Fuel Cell Vehicle 

Ferredoxin 

Iron 

Ferric Oxide 

Magnetic Iron Oxide 

Ferric Chloride 

Iron Phosphate 

Field Effect Transistor 

Flame Ionization Detector 

Florida Institute of Technology 

Failure Mode and Effect Analysis 

Fuel Processor One 

Flame Photometric Detector 

Fluorinated Polyether Sulfone 

Fuel Processing System 

Failure Reporting, Analysis and 

Corrective Action System 

U.S. Department of Energy 

Automotive Research Partnership 

Fluorinated Sulfonated 

Polyetheretherketone 

Federal Transportation 

Administration 

X - 2 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

FTE Full Time Equivalent 

FUDS Federal Urban Driving Schedule 

g Gram 

GA General Atomics Corporation 

gal Gallon 

GaN Gallium Nitride 

GC Gas Chromatograph/Gas 

Chromatography 

GCtool Power system analysis software 

developed by ANL 

Gd2O2S:Eu Gadolinium Oxy-Sulfide doped with 

Europium 

GDATP General Dynamics Armament & 

Technical Products 

GDE Gas Diffusion Electrode 

GDL Gas Diffusion Layer 

GDS Galvanodynamic Scan 

Ge Germanium 

GEAE General Electric Aircraft Engines 

GGA Generalized Gradient 

Approximation 

gge Gasoline Gallon Equivalent 

GHG Green House Gas 

GHSV Gas Hourly Space Velocity 

GJ Gigajoule (109

 joules) 

GREET Greenhouse Gas Energy and 

Emissions in Transportation 

GRPE Working Party on Pollution and 

Energy 

GTI Gas Technology Institute 

∆Ho Heat of Formation 

H2 Hydrogen 

H2O Water 

H2S Hydrogen Sulfide 

HAZOP Hazardous Operations 

HBr Hydrobromic acid 

HBT Hydrogen Burner Technology 

HC Hydrocarbon 

HCCI Homogeneous Charge Compression 

Ignition 

HCl Hydrochloric Acid 

HCN Hydrogen Cyanide 

HCNG Hydrogen Compressed Natural Gas 

HCSCC Hydrogen Codes and Standards 

Coordinating Committee 

HDPE High Density Polyethylene 

HECO Hawaiian Electric Company 

HELCO Hawaii Electric Light Company 

HEV Hybrid Electric Vehicle 

HF Hydrogen Fluoride 

HFCIT 

HHV 

HI 

HiQ 

HNEI 

HPA 

HPE 

H-PEDOT 

HTE 

HTGR 

HTM 

HTS 

HWCVD 

HX 

HydA1 

HYSYS 

I 

ICC 

ICE 

ICEV 

ICR 

IEA 

IEC 

IFSTM 

IIT 

INEEL 

INS 

IOS 

IPA 

Ir 

IR 

ISO 

ISS 

ISURF 

ITM 

ITO 

JHU/APL 

JPL 

K/o

K 

Hydrogen, Fuel Cells, and 

Infrastructure Technologies 

Higher Heating Value 

Hydroiodic Acid 

High-Efficiency, Quick Start Fuel 

Processor 

Hawaii Natural Energy Institute 

Heteropolyacid 

Hybrid Photoelectrode 

Poly-3,4-ethylenedioxythiphene and 

ethylene glycol 

High Temperature Electrolysis 

High Temperature Gas-cooled 

Reactor 

Hydrogen Transport Membrane/ 

High Temperature Membrane 

High Temperature Shift 

Hot Wire Chemical Vapor 

Deposition 

Heat Exchanger 

Algal Hydrogenases 

Aspen Technologies' CPS 

Electrical Current 

International Code Council 

Internal Combustion Engine 

Internal Combustion Engine Vehicle 

Interfacial Contact Resistance 

International Energy Agency 

International Electrotechnical 

Commission 

Interactive Future Simulations 

Illinois Institute of Technology 

Idaho National Engineering and 

Environmental Laboratory 

Inelastic Neutron Scattering 

Intelligent Optical Systems, Inc. 

International Platinum 

Iridium 

Infrared 

International Organization for 

Standardization 

Integrated Storage System 

Iowa State University Research 

Foundation 

Ion Transport Membrane 

Indium Tin Oxide 

Johns Hopkins University Applied 

Physics Laboratory 

Jet Propulsion Laboratory 

Degrees Kelvin 

X - 3 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

K2O Potassium Oxide 

KBM Knowledge Based Management 

KCx Potassium Carbon when used with 

Intercalated Graphites 

kg Kilogram 

KTH Swedish Royal Institute 

kW Kilowatt 

kWe Kilowatt electric 

kWh Kilowatt hour 

kWth Kilowatt Thermal 

La Lanthanum 

La-Ni-Al Lanthanum-Nickel-Aluminum alloy 

LANL Los Alamos National Laboratory 

lb Pound 

LC Lumped Capacitance 

LCHPP Low Cost Hydrogen Production 

Platform 

LDA Local Density Approximation 

LDRD Laboratory Directed Research and 

Development 

LDV Light Duty Vehicle 

LED Light Emitting Diode 

LEL Lower Explosion Level 

LES Large Eddy Simulation 

LH2 Liquid Hydrogen 

LHC Light Harvesting Complex 

LHV Lower Heating Value 

LiAlH4 Lithium Aluminum Hydride 

LiF Lithium Fluoride 

LLNL Lawrence Livermore National 

Laboratory 

LME London Metals Exchange 

LOX Liquid Oxygen 

LP Linear Polarization 

LTS Low Temperature Shift 

LV Level Indicator 

mA MilliAmps 

MC Multicomponent 

MDPD® Market Driven Product Definition 

MEA Membrane Electrode Assembly 

MEMS Micro Electromechanical System 

mg Milligrams 

Mg Magnesium 

MgH2 Magnesium Hydride 

MgO Magnesium Oxide 

MMBtu Million British Thermal Units 

MMD Mass Median Diameters 

Mn Manganese 

Mo Molybdenum 

MOFS Multiplexed, Optical Fiber Sensor 

mole/(m2Pa•s): Mole per Meter Squared Pascal 

Second 

MPa Mega Pascals 

mpeg Miles per Equivalent Gallon 

mpg Miles Per Gallon 

MRI Magnetic Resonance Imaging 

MSE Mercury/mercurous Sulfate 

reference Electrode 

MSHA Mine Safety and Health 

Administration 

MSU Montana State University 

MSW Municipal Solid Waste 

mV MilliVolts 

mW Megawatt 

mWh Megawatt hour 

MWNT Multi-Wall Nanotubes 

N2 Nitrogen 

Na Sodium 

NaAlH4 Sodium Aluminum Hydride 

NaBH4 Sodium Borohydride 

NAFION® Registered Trademark of E.I. 

DuPont de Nemours 

NASA National Aeronautics and Space 

Administration 

Nb Niobium 

NbPOx Niobium phosphate 

NEBS Network Equipment Building 

Standards 

NELHA Natural Energy Laboratory Hawaii 

Authority 

NERI Nuclear Energy Research Initiative 

NETL National Energy Technology 

Laboratory 

NFC Near Frictionless Carbon 

NFPA National Fire Protection Association 

NG Natural Gas 

NGASE Natural Gas Assisted Steam 

Electrolyzer 

NH3 Ammonia 

NHA National Hydrogen Association 

NHE Normal Hydrogen Electrode 

Ni Nickel 

NICC Natural Gas Infrastructure 

Component Cost 

NIF Neutron Imaging Facility 

NiO Nickel Oxide 

NIST National Institute of Standards and 

Technology 

nm Nanometer 

Nm3 Normal Cubic Meter 

X - 4 
 

 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

NMHC 

NMOG 

NMR 

NOx 

NPW 

NREL 

NRL 

NSLS 

2 Ωcm

O 

O&M 

O/C 

O2 

OCP 

OEM 

OH 

Ohm-cm2 

OMB 

OPP 

ORNL 

ORR 

OTM 

OTT 

P 

PADT 

PAFC 

PAMPAS 

PATH 

PBI 

PCR 

PCT 

Pd 

PDPA 

PDU 

PEC 

PEDOT 

PEEK 

PEFC 

PEM 

PEMFC 

PEN 

PFA 

Non-Methane Hydrocarbon 

Non-Methane Organic Gases 

Nuclear Magnetic Resonance 

Nitric Oxides 

Net Present Worth 

National Renewable Energy 

Laboratory 

Naval Research Laboratory 

National Synchrotron Light Source 

Ohm-Centimeter-Squared 

Oxygen 

Operation and Maintenance 

Oxygen to Carbon ratio 

Oxygen 

Open Circuit Potential 

Original Equipment Manufacturer 

Hydroxal Radical 

Ohm-centemeter-squared 

Office of Management and Budget 

Office of Physical Plant 

Oak Ridge National Laboratory 

Oxygen Reduction Reaction 

Oxygen Transport Membrane 

Office of Transportation 

Technologies 

Pressure 

Phoenix Analysis and Design 

Technologies 

Phosphoric Acid Fuel Cell 

Poly 2-acrylamino-2-methyl-1­

propanesulfonic acid-co-styrene 

Partnership for Advancing the 

Transition to Hydrogen 

Polybenzimidazole 

Polymerase Chain Reaction 

Pressure Composition Temperature 

Palladium 

Phase Doppler Particle Analyzer 

Process Development Unit 

Photoelectrochemical 

Poly-3,4-ethylenedioxythiphene 

Polyetheretherketone 

Polymer Electrolyte Membrane Fuel 

Cell 

Proton Exchange Membrane/ 

Polymer Electrolyte Membrane 

Proton Exchange Membrane Fuel 

Cell 

Positive Electrolyte Negative 

Personal Fuel Appliance 

PFCT Porvair Fuel Cell Technology, Inc 

PFD Process Flow Diagram 

PFSA Perfluorinated Sulfonic Acid 

PGM Platinum Group Metal 

pH Power of the Hydrogen Radical 

PHA Preliminary Hazard Analysis 

PI Principal Investigator 

PM Particulate Matter/ Particulate 

Membrane/ Precious Metal 

PNA Palladium Nanowire Arrays 

PNNL Pacific Northwest National 

Laboratory 

POTW Publicly Owned Treatment Works 

POX Partial Oxidation 

PP Polypropylene 

PP1R Power Plant One Reformate 

ppb Parts Per Billion 

ppbv Parts Per Billion by volume 

ppm Parts Per Million 

ppmv Parts Per Million by Volume 

ppmw Parts Per Million by Weight 

PR Progress Ratio 

PROX/PrOx Preferential Oxidation 

PS Photosystem 

PSA Pressure Swing Adsorption 

psi Pounds Per Square Inch 

PSI Paul Scherrer Institute 

psia Pounds Per Square Inch Absolute 

psig Pounds Per Square Inch Gauge 

PSII Photosystem II 

PSU Pennsylvania State University 

Pt Platinum 

Pt-WO3 Platinum-Tungsten Oxide 

PV Photovoltaic 

R&D Research and Development 

RAM Reliability and Maintenance 

RD&D/R,D&D Research, Development & 

Demonstration 

RDE Rotating Disk Electrode 

Re Rhenium 

REI Reaction Engineering International 

RFC Regenerative Fuel Cell 

RFG Reformulated Gasoline 

RH Relative Humidity 

Rh Rhodium 

RHE Real Hydrogen Electrode/ 

Reversible Hydrogen Electrode 

RI Receding Interface 

ROI Record of Invention 

RPI Rensselaer Polytechnic Institute 

X - 5 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

rpm Revolutions per Minute 

RRDE Rotating Ring-disk Electrode 

RTI Research Triangle Institute 

Ru Ruthenium 

Rz Roughness (vertical) 

S Sulfur 

S/C Steam to Carbon ratio 

S/cm Siemens per Centimeter 

S300 Series 300 Fuel Processing and PEM 

Cell System 

S-A Sulfur-Ammonia 

SAE Society of Automotive Engineers 

SC Single Component 

SCAQD South Coast Air Quality District 

Sccm Standard Cubic Centimeters per 

Minute 

SCFD Standard Cubic Feet per Day 

SCFH Standard Cubic Feet per Hour 

SCFM Standard Cubic Feet per Minute 

SCONOx Selective Catalytic Reduction of 

NOx 

SCW Supercritical Water 

SCWO Supercritical Water Oxidation 

SDS-PAGE Sodium-Dodecyl-Sulfate 

Polyacrylamide Gel Electrophoresis 

SDSU San Diego State University 

Se Selenium 

SEM Scanning Electron Microscope 

SEP Subscale Engineering Prototype 

SERC Schatz Energy Research Center 

SF6 Sulfur Hexafluoride 

SGS Subgrid Scale 

SHE Standard Hydrogen Electrode 

SHTC Southeast Hydrogen Technology 

Consortium 

S-I Sulfur-Iodine 

SiC Silicon Carbide 

SLPM Standard Liters Per Minute 

SMP Superior MicroPowders 

SMR Steam Methane Reformer 

SN Tin 

SNG Synthetic Natural Gas 

SNL Sandia National Laboratory 

SNLL Sandia National Laboratory 

Livermore 

SnOx Tin Oxide 

SO2 Sulfur Dioxide 

SOA State-Of-the-Art 

SOEC Solid Oxide Electrolysis Cell 

SOFC Solid Oxide Fuel Cell 

SPC 

SR 

Sr 

SRTC 

STAR 

STEM 

STH 

SULEV 

SUNY 

SUV 

SV 

SVT 

SWNT 

SWPO 

SwRI 

T 

Ta 

TCD 

TCD 

TCWSC 

TEM 

TEOS 

TEX 

TGA 

THC 

Ti 

TiCl3 

TiCl4 

TiO2 

TIVM 

tla 

TMI 

TMY 

tpd 

T-RFLP 

TRU 

TVA 

UAB 

UC 

UGA 

UGCM 

UH 

UHC 

Statistical Process Control 

Steam Reforming/Reformer 

Strontium 

Savannah River Technology Center 

Substrate-based Transportation 

Autothermal Reformer 

Scanning Transmission Electron 

Microscope 

Solar To Hydrogen 

Super Ultra Low Emissions Vehicle 

State University of New York 

Sport Utility Vehicle 

Space Velocity 

Single Vane Test 

Single Wall Nanotubes 

Supercritical Water Partial 

Oxidation 

Southwest Research Institute 

Temperature 

Tantalum 

Thermal Conductivity Detector 

Thermocatalytic Decomposition 

Thermochemical Water-Splitting 

Cycle 

Transmission Electron Microscopy 

Tetraethyl Orthosilicate 

Texas Energy System, LLC 

Thermal Gravimetric Analysis 

Total Hydrocarbons 

Titanium 

Titanium Trichloride 

Titanium Tetrachloride 

Titanium Dioxide 

Torroidal Intersecting Vane Machine 

Truncated Light-Harvesting 

Chlorophyll Antenna 

Technology Management, Inc. 

Typical Meteorological Year 

English tons per day 

Terminal Restriction Fragment 

Length Polymorphism 

Truck Refrigeration Unit 

Thermovolumetric analyzer 

University of Alabama at 

Birmingham 

University of California 

University of Georgia 

Unitary Gas Control Module 

University of Hawaii 

Unburned Hydrocarbons 

X - 6 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

UHM 

UHV 

UK 

UL 

UNIGEN® 

UOP 

UPS 

US DOE 

USC 

UT-3 

UTC 

UTCFC 

UTRC 

UV 

V 

V 

VASP 

VC 

VNT® 

Voc 

University of Hawaii at Manoa Vol.%/Vol% Percent by volume 

Ultrahigh Vacuum w Width 

University of Kentucky W Tungsten 

Underwriters Laboratory We Watts electric, typically refers to the 

A Registered Trademark of Proton output from a PEM fuel cell 

Energy Systems, Inc. WGS Water Gas Shift 

Universal Oil Products WO3 Tungsten Trioxide 

Uninterruptible Power Supply wt Weight 

United States Department of Energy Wt Watts thermal, typically refers to 

University of South Carolina heat transfer duty 

University of Tokyo-3 wt.%/wt% Weight percent 

United Technologies Corporation XRD X-ray diffraction 

United Technologies Corporation Y Yttrium 

Fuel Cells Division YAg:Cr Yttrium Aluminum Garnet doped 

United Technologies Research with Chromium 

Center yr Year 

Ultraviolet YSZ Yttria Stabilized Zirconia 

Volt (Zr0.85Y0.15O1.95) 

Vanadium Z-60 0 to 60 mph Acceleration 

Vienna Ab Initio Simulation ZEV Zero Emission Vehicle 

Package Zn Zinc 

Vulcan Carbon Zr Zirconium 

Variable Nozzle Turbine ZSM Zeolite Type Membranes 

open circuit potential 

X - 7 
Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

X - 8
 
 

Hydrogen, Fuel Cells, and Infrastructure Technologies FY 2003 Progress Report 

Index of Primary Contacts
 

A 

Aaron, Timothy M. . . . . . . . . . . . . . . . . . . . . . . II-18
 

Atanasoski, Radoslav T. . . . . . . . . . . . . . . . . IV-253
 

Atanassova, Paolina. . . . . . . . . . . . . . . . . . . . IV-188
 

Aceves, Salvador M. . . . . . . . . . . . . . . . . . . . III-15
 

Adzic, Radoslav . . . . . . . . . . . . . . . . . . . . . . IV-236
 

Ahluwalia, Rajesh K.. . . . . . . . . . . . . . . . . . . . . IV-3
 

Ahmed, S. . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-103
 

Ahn, Channing . . . . . . . . . . . . . . . . . . . . . . . . III-65
 

Amrani, Ahmed . . . . . . . . . . . . . . . . . . . . . . . IV-58
 

Anton, Donald L. . . . . . . . . . . . . . . . . . . . . . . III-43
 

Anton, Donald L. . . . . . . . . . . . . . . . . . . . . . . III-52
 

Arif, Muhammad . . . . . . . . . . . . . . . . . . . . . IV-267
 

Armstrong, Timothy . . . . . . . . . . . . . . . . . . . IV-133
 

Arps, James . . . . . . . . . . . . . . . . . . . . . . . . . IV-194
 

Aronsson, Robert R. . . . . . . . . . . . . . . . . . . . . . V-41
 

B 

Bailey, Sterling . . . . . . . . . . . . . . . . . . . . . . . . IV-39
 

Barnes, David L. . . . . . . . . . . . . . . . . . . . . . . . VI-27
 

Barnes, David L. . . . . . . . . . . . . . . . . . . . . . . . VI-31
 

Bauman, Jayson W. . . . . . . . . . . . . . . . . . . . IV-262
 

Bellan, Josette . . . . . . . . . . . . . . . . . . . . . . . . . . II-98
 

Berry, David A. . . . . . . . . . . . . . . . . . . . . . . IV-147
 

Besmann, T. M. . . . . . . . . . . . . . . . . . . . . . . IV-202
 

Blom, Douglas A. . . . . . . . . . . . . . . . . . . . . . IV-300
 

Borup, Rod . . . . . . . . . . . . . . . . . . . . . . . . . . IV-142
 

Bowen, David A. . . . . . . . . . . . . . . . . . . . . . . . . II-78
 

Brady, M.P. . . . . . . . . . . . . . . . . . . . . . . . . . IV-206
 

Brown, Robert C. . . . . . . . . . . . . . . . . . . . . . . . II-73
 

C 

Carlson, Eric J. . . . . . . . . . . . . . . . . . . . . . . . . IV-13
 

Carlson, Eric J. . . . . . . . . . . . . . . . . . . . . . . . . IV-17
 

Carlson, Todd . . . . . . . . . . . . . . . . . . . . . . . . . . . V-3
 

Carlson, Todd . . . . . . . . . . . . . . . . . . . . . . . . . . . V-6
 

Chen, Christopher M. . . . . . . . . . . . . . . . . . . . . . II-9
 

Chintawar, Prashant S. . . . . . . . . . . . . . . . . . IV-157
 

Choung, Sara Yu . . . . . . . . . . . . . . . . . . . . . . IV-79
 

Clapper, William L. . . . . . . . . . . . . . . . . . . . . VI-12
 

Clark, Thomas . . . . . . . . . . . . . . . . . . . . . . . . IV-44
 

Collier, Kirk . . . . . . . . . . . . . . . . . . . . . . . . . . IX-13
 

Cooper, Christy . . . . . . . . . . . . . . . . . . . . . . . VIII-3
 

Czernik, Stefan . . . . . . . . . . . . . . . . . . . . . . . . . II-86
 

D 

DaCosta, David H. . . . . . . . . . . . . . . . . . . . . . . V-36
 

De Castro, Emory S. . . . . . . . . . . . . . . . . . . . IV-165
 

Debe, Mark K. . . . . . . . . . . . . . . . . . . . . . . . IV-178
 

Debe, Mark K. . . . . . . . . . . . . . . . . . . . . . . . IV-211
 

DiMeo, Frank Jr. . . . . . . . . . . . . . . . . . . . . . . .VII-30
 

Dalla Betta, Ralph A. . . . . . . . . . . . . . . . . . . . IV-98
 

Dardas, Zissis. . . . . . . . . . . . . . . . . . . . . . . . . . IV-93
 

Davies, Michele R. . . . . . . . . . . . . . . . . . . . . . . V-26
 

E 

Evans, Robert. . . . . . . . . . . . . . . . . . . . . . . . . . . II-82
 

F 

Fairlie, Matthew . . . . . . . . . . . . . . . . . . . . . . . . V-22
 

Fenske, George R. . . . . . . . . . . . . . . . . . . . . IV-271
 

Figi, Bruce . . . . . . . . . . . . . . . . . . . . . . . . . . .VII-34
 

Fouad, Fouad H. . . . . . . . . . . . . . . . . . . . . . . . . V-32
 

Foure, Michel . . . . . . . . . . . . . . . . . . . . . . . . IV-265
 

G 

Gee, Mark K. . . . . . . . . . . . . . . . . . . . . . . . . . IV-35
 

Ghirardi, Maria . . . . . . . . . . . . . . . . . . . . . . . . II-111
 

Gross, Karl J. . . . . . . . . . . . . . . . . . . . . . . . . . III-31
 

Grot, Stephen . . . . . . . . . . . . . . . . . . . . . . . . . IV-31
 

Gruner, George . . . . . . . . . . . . . . . . . . . . . . . . III-75
 

Guro, David E. . . . . . . . . . . . . . . . . . . . . . . . . VI-17
 

H 

Haack, David . . . . . . . . . . . . . . . . . . . . . . . . IV-197
 

Heben, M. J. . . . . . . . . . . . . . . . . . . . . . . . . . . III-54
 

Herring, Stephen J. . . . . . . . . . . . . . . . . . . . . . II-150
 

Heung, Kit . . . . . . . . . . . . . . . . . . . . . . . . . . . . II-23
 

Hicks, Mike T. . . . . . . . . . . . . . . . . . . . . . . . IV-263
 

Ho, W.S. Winston . . . . . . . . . . . . . . . . . . . . . . IV-88
 

Hobbs, Raymond S. . . . . . . . . . . . . . . . . . . . . . . V-44
 

I
 

Inbody, Michael A. . . . . . . . . . . . . . . . . . . . . IV-107
 

Irving, Patricia . . . . . . . . . . . . . . . . . . . . . . . . . . II-3
 

J 

James, Brian D. . . . . . . . . . . . . . . . . . . . . . . . . IV-22
 

Jensen, Craig M. . . . . . . . . . . . . . . . . . . . . . . . III-26
 

K 

Kaya, Maurice . . . . . . . . . . . . . . . . . . . . . . . . . . V-8
 

Khaleel, Mohammad A. . . . . . . . . . . . . . . . . IV-288
 

Killmeyer, Richard . . . . . . . . . . . . . . . . . . . . . . II-45
 

XI - 1 
 

 

 

 

L 

Hydrogen, Fuel Cells, and Infrastructure Technologies

Knight, Brian A. . . . . . . . . . . . . . . . . . . . . . . VII-26
 

Kopasz, John P. . . . . . . . . . . . . . . . . . . . . . . . IV-138
 

Kopasz, John P. . . . . . . . . . . . . . . . . . . . . . . . IV-153
 

Krause, Theodore . . . . . . . . . . . . . . . . . . . . . IV-129
 

Kumar, Ravi . . . . . . . . . . . . . . . . . . . . . . . . . . .II-34
 

LaVen, Arne . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-71
 

Lasher, Stephen . . . . . . . . . . . . . . . . . . . . . . . . .II-39
 

Lasher, Stephen . . . . . . . . . . . . . . . . . . . . . . . IV-279
 

Lasher, Stephen . . . . . . . . . . . . . . . . . . . . . . . . . VI-8
 

Lee, James W. . . . . . . . . . . . . . . . . . . . . . . . . .II-108
 

Lesch, David . . . . . . . . . . . . . . . . . . . . . . . . . . . III-48
 

Lessing, Paul A. . . . . . . . . . . . . . . . . . . . . . . . . III-19
 

Liss, William E. . . . . . . . . . . . . . . . . . . . . . . . . VI-22
 

Liu, Chung . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-257
 

Lutz, Andrew . . . . . . . . . . . . . . . . . . . . . . . . . . IV-18
 

M 

MacQueen, Brent . . . . . . . . . . . . . . . . . . . . . . .II-137
 

Magrini-Bair, Kimberly A. . . . . . . . . . . . . . . . . .II-89
 

Markel, Tony . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-8
 

Martin, Peter L. . . . . . . . . . . . . . . . . . . . . . . . VII-16
 

Martin, Steve W. . . . . . . . . . . . . . . . . . . . . . . . IV-62
 

Mawdsley, Jennifer . . . . . . . . . . . . . . . . . . . . . IV-83
 

McClaine, Andrew W. . . . . . . . . . . . . . . . . . . . III-73
 

McFarland, Eric W. . . . . . . . . . . . . . . . . . . . . .II-130
 

McIntyre, Timothy J. . . . . . . . . . . . . . . . . . . . VII-42
 

McMillan, April D. . . . . . . . . . . . . . . . . . . . . IV-107
 

Melis, Tasios . . . . . . . . . . . . . . . . . . . . . . . . . .II-104
 

Miller, Eric L. . . . . . . . . . . . . . . . . . . . . . . . . .II-124
 

Milliken, Christopher . . . . . . . . . . . . . . . . . . .II-142
 

Motupally, Sathya . . . . . . . . . . . . . . . . . . . . . IV-171
 

Mukundan, Rangachary . . . . . . . . . . . . . . . . . VII-11
 

Muradov, Nazim . . . . . . . . . . . . . . . . . . . . . . .II-155
 

Myers, Deborah . . . . . . . . . . . . . . . . . . . . . . . IV-275
 

Myers, Duane B. . . . . . . . . . . . . . . . . . . . . . . . .II-53
 

N 

Nanji, Noordin . . . . . . . . . . . . . . . . . . . . . . . . IV-261
 

Narayanan, S. R. . . . . . . . . . . . . . . . . . . . . . . IV-248
 

Nelson, Bruce . . . . . . . . . . . . . . . . . . . . . . . . . V-30
 

Nenoff, Tina M. . . . . . . . . . . . . . . . . . . . . . . . . .II-28
 

O 

Ohi, Jim . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII-6
 

Ott, Ronald D.. . . . . . . . . . . . . . . . . . . . . . . . . . IV-54
 

P 

Page, Richard A. . . . . . . . . . . . . . . . . . . . . . . . . III-77
 

Penner, Reginald M. . . . . . . . . . . . . . . . . . . . VII-47
 

 FY 2003 Progress Report 

Pez, Guido P. . . . . . . . . . . . . . . . . . . . . . . . . . . III-69
 

Pitts, J. Roland . . . . . . . . . . . . . . . . . . . . . . . . VII-21
 

Popov, Branko N. . . . . . . . . . . . . . . . . . . . . . IV-255
 

Porter, Stephen . . . . . . . . . . . . . . . . . . . . . . . . . VI-35
 

Pyke, Steve . . . . . . . . . . . . . . . . . . . . . . . . . . VII-39
 

R 

Raman, Venki . . . . . . . . . . . . . . . . . . . . . . . . . . VI-3
 

Regan, Rob . . . . . . . . . . . . . . . . . . . . . . . . . . . . V-14
 

Robertson, Arthur Bruce . . . . . . . . . . . . . . . . . IV-33
 

Ross, Philip N. Jr. . . . . . . . . . . . . . . . . . . . . . IV-226
 

S 

Schefer, Robert . . . . . . . . . . . . . . . . . . . . . . . . . IX-3
 

Schwartz, Joseph. . . . . . . . . . . . . . . . . . . . . . . . II-14
 

Selecman, George E. . . . . . . . . . . . . . . . . . . . . IV-49
 

Sirosh, Neel . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-3
 

Sirosh, Neel . . . . . . . . . . . . . . . . . . . . . . . . . . . III-24
 

Slattery, Darlene K. . . . . . . . . . . . . . . . . . . . . . III-38
 

Slaudt, Rhonda . . . . . . . . . . . . . . . . . . . . . . . . IV-259
 

Spritzer, Michael H. . . . . . . . . . . . . . . . . . . . . . II-68
 

Stevens, Jim . . . . . . . . . . . . . . . . . . . . . . . . . . IV-163
 

Stevenson, Dan . . . . . . . . . . . . . . . . . . . . . . . IV-294
 

Stone, Harry J. . . . . . . . . . . . . . . . . . . . . . . . . . IV-77
 

Sung, Shihwu . . . . . . . . . . . . . . . . . . . . . . . . . . II-57
 

Swain, Michael R. . . . . . . . . . . . . . . . . . . . . . . VII-3
 

Swider-Lyons, Karen . . . . . . . . . . . . . . . . . . . IV-231
 

T 

Talu, Orhan . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-50
 

TeGrotenhuis, Ward E. . . . . . . . . . . . . . . . . . IV-113
 

Thompson, Levi . . . . . . . . . . . . . . . . . . . . . . . IV-124
 

Tosca, Michael . . . . . . . . . . . . . . . . . . . . . . . . . IV-27
 

T-Raissi, Ali . . . . . . . . . . . . . . . . . . . . . . . . . . II-159
 

Truett, Tykey . . . . . . . . . . . . . . . . . . . . . . . . . VIII-6
 

Turner, John A. . . . . . . . . . . . . . . . . . . . . . . . II-119
 

Tworek, Elzbieta . . . . . . . . . . . . . . . . . . . . . . . VIII-8
 

U 

Unnasch, Stefan . . . . . . . . . . . . . . . . . . . . . . . . II-49
 

Unnasch, Stefan . . . . . . . . . . . . . . . . . . . . . . . IV-284
 

Uribe, Francisco . . . . . . . . . . . . . . . . . . . . . . . IV-221
 

V
 

Van Blarigan, Peter . . . . . . . . . . . . . . . . . . . . . . IX-8
 

Vance, Andrew L. . . . . . . . . . . . . . . . . . . . . . II-146
 

Vogel, John . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV-75
 

W 

Weisberg, Andrew . . . . . . . . . . . . . . . . . . . . . . III-11
 

Wheeler, Douglas . . . . . . . . . . . . . . . . . . . . . . .IV-73
 

Whyatt, Greg A. . . . . . . . . . . . . . . . . . . . . . . . IV-107
 

XI - 2 
Hydrogen, Fuel Cells, and Infrastructure Technologies

Whyatt, Greg A. . . . . . . . . . . . . . . . . . . . . . . IV-119
 

Wipke, Keith . . . . . . . . . . . . . . . . . . . . . . . . . . IV-8
 

Wolfrum, Edward J. . . . . . . . . . . . . . . . . . . . . . II-62
 

Wozniak, John . . . . . . . . . . . . . . . . . . . . . . . . . . II-7
 

Wu, Ying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . III-71
 

Y 

Yeboah, Y.D. . . . . . . . . . . . . . . . . . . . . . . . . . . II-93
 

Yuh, Chao-Yi . . . . . . . . . . . . . . . . . . . . . . . . IV-184
 

Z 

Zamansky, Vladimir . . . . . . . . . . . . . . . . . . . . IV-67
 

Zawodzinski, Thomas A. . . . . . . . . . . . . . . . IV-217
 

Zelenay, Piotr . . . . . . . . . . . . . . . . . . . . . . . . IV-241
 

Zidan, Ragaiy . . . . . . . . . . . . . . . . . . . . . . . . . III-61
 

 FY 2003 Progress Report 

XI - 3