th

6 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory
and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materialsthth
The 6 symposium “Hydrogen & Energy” follows the 5 symposium on 23. – 28. January 2011 inStoos with more than 80 participants. It serves as an information platform of the fundamental
science and technology and the frontiers of research on hydrogen and energy.

The symposium consists of invited keynote lectures reviewing the key elements of the hydrogen
cycle, i.e. the hydrogen production, hydrogen storage and hydrogen combustion and fuel cells.
Furthermore, contributions on the conversion of renewable energy in general and energy carriers
beside and beyond hydrogen are very welcome. The world leading experts present the current
research challenges and most important results in invited and contributing talks. Early stage andexperienced researchers present their newest results and the open questions on posters as well as
in a one slide presentation.
The conference will take place in the conference and wellness hotel Stoos in the beautiful small
village Stoos on 1'270 m above see level. The village is free of traffic on a alp above Schwyz incentral Switzerland.
The number of participants is limited to 80.

22. - 27. January 2012
Seminar- und Wellnesshotel Stoos
Ringstrasse 10
CH-6433 Stoos
Tel.: +41 (0)41 817 44 44
Fax.: +41 (0)41 817 44 45
info@hotel-stoos.ch
http://www.hotel-stoos

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6th Hydrogen & Energy Symposium

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CONTENTS
Timetable
Abstracts
Sunday17:00 - 18:00

Chair: Andreas ZÜTTEL
Mogens Bjerg MOGENSEN, 'Electrolysis and Recycling of CO2 into
CO2-neutral Fuels'

MONDAY morning
08:30 - 09:30

Chair: Ping CHENMin ZHU, 'Tuning DE/Hydrogenation Kinetics and Thermodynamics
of Magnesium Based Alloys'
Zhirong ZHAO-KARGER, 'Nanoconfined Metal Hydrides for Energy
Storage'
Arndt REMHOF, 'Hydrogen Dynamics in Nanoconfined
Lithiumborohydride'
Renato CAMPESI, 'SANS and TEM Characterization of MgH2-NaBH4
Nanoparticles Confined in Silica based Mesoporous Scaffold SBA-15'
Philippe MAURON, 'Hydrogen absorption in Na intercalated C60'
Nicholas STADIE, 'Zeolite-Templated Carbon Materials for High
Pressure Hydrogen Storage'

09:30 - 10:00
10:00 - 10:30
11:00 - 11:30
11:30 . 12:00
12:00 - 12:30
MONDAY afternoon
14:00 - 15:00
15:00 - 15:30
16:00 - 16:30
16:30 - 17:00
17:00 - 17:30

Chair: Min ZHUHongge PAN, 'Improved Hydrogen Storage in Li-Mg-N-H Combined
System 'Chaoling WU, 'Development of Low Cost Vanadium-based Hydrogen
Storage Alloys in Sichuan University'
Alondra TORRES, 'Hydrogen Semi-Clathrate Hydrate Formation fromTBAB aqueous solution: Kinetics and Evolution of Hydrate-Phase
Composition by in situ Raman Spectroscopy.'
Timmy RAMIREZ-CUESTA, 'Determining the Energetics of molecularhydrogen adsorption using Inleastic Neutron Scattering Spectroscopy'
Elsa CALLINI, 'Catalysis by Metathesis'

POSTER SESSIONSMONDAY evening

PROCEEDINGS

Chair: Andreas BORGSCHULTE, Philippe MAURON
Shunsuke KATO, 'Hydrogenation of CO2 on the hydride surface of
Mg2NiH4'
Peipei YUAN, 'LiBH4-based composites with metal hydrides andfluorides for hydrogen storage'
Shin-ichi ORIMO, 'Synthesis and Characterizations of Complex
Hydride YMn2H6'
Liga GRINBERGA and Andris SIVARS, 'Activated SiO2 basedmaterials for hydrogen storage.'
Wiebke LOHSTROH, 'Gas Release from (H,D) Isotope Labeled
2LiBH4/MgH2 Composites'
Michal GORBAR, 'ESEM and Raman Mapping of Polyphenylene
Sulphide / Polysulfone / Olivine Diaphragms'
Yuen AU, 'Improved hydrogen sorption kinetics in supported Mg2Cunano-particles'36th Hydrogen & Energy Symposium

Stoos, Switzerland 2012

Renato CAMPESI, 'Hydrogenation of Carbon Monoxide overNanostructured Systems: Mechanochemical Approach'Andreas ZÜTTEL, 'The Energy Density of Hydrogen Storage Systems'
Riccardo SUTER, 'Sorption Enhanced Methanation of CO2'
Ioseb RATISHVILI, 'Hydrogen-Metal Complexes in Metal-Hydrogen
Intersittial Alloys. Description of Heat Capacity Anomalies'
TUESDAY morning
08:30 - 09:30
09:30 - 10:00
10:00 - 10:30
11:00 - 11:30
11:30 . 12:00
12:00 - 12:30

Chair: Hongge PAN
Ping CHEN, 'Catalytic modification of Mg(NH2)2-2LiH system'
Daniele PONTIROLI, 'Superionic conductivity in fullerene polymers'
Ebrahim HAZRATI, 'A first-principles study of defects in LiNH2 andnano-sized LiBH4 clusters'
Haiwen LI, 'Hydrogen Pressure Dependence of Li2B12H12 Formation
During Dehydrogenation of LiBH4-MgH2 Composite'
Inge LINDEMANN, 'Study of the Decomposition Path of Al-LiBorohydride'
Wan Si TANG, 'Theoretical and Experimental Investigations of KSIH3
as a Reversible Hydrogen Storage Material'

POSTER SESSIONSTUESDAY evening

PROCEEDINGS

Chair: Arndt REMHOF, Michael BIELMANN
Mauro RICCÒ, 'Muons probe strong hydrogen interactions withdefective graphene'
Yongfeng LIU, 'Hydrogen Storage Properties of LiBH4 Destabilized byin-situ Formation of MgH2 and LaH3'
Mingxia GAO, 'The Destabilization of Mg(BH4)2-2NaAlH4 Combination
System Doped with Titanium Fluorides'
MOHAMMAD CHOUCAIR, 'Graphene Composites for Next
Generation Lithium Ion Batteries'
Ji Woo KIM, 'Corrosion Behaviour of Steel Interconnects and Coating
Materials in Solid Oxide Electrolysis Cell (SOEC)'
Arndt REMHOF, 'Solvent-free Synthesis and Decompostion ofY(BH4)3'
Andreas BLIERSBACH, ‘How to Watch Hydrogen Diffuse in any
Absorbing Material’
Ulrich ULMER, 'Preparation, testing and scale-up of doped, nanoscaleamide systems for hydrogen storage 'Marius VAN DEN BERG, 'Modelling the melting temperature ofcomplex hydrides'
Michael BIELMANN, 'Market Potential for Hydrogen in Off-Grid
Energy Systems'
Klaus TAUBE, 'Hydrogen Sorption Properties of the MgB2 based CaH2
and CaH2-CaF2 Reactive Hydride Composites'
Ulrich VOGT, 'Self Ignitting Catalytic Hydrogen Burner with Zero
Immission'
Pascal MARTELLI, 'Solid Acid Fuel cells'

46th Hydrogen & Energy Symposium

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WEDNESDAY morning Chair: Michael Felderhoff
08:30 - 09:30
John IRVINE, 'Solid State Electrochemical Conversion of Clean
Electrons to Fuels'
09:30 - 10:00
Andreas BORGSCHULTE, 'Sorption Enhanced Reactions for
Renewable Synfuels'
10:00 - 10:30
Gabor LAURENCZY, 'Hydrogen storage and delivery'
11:00 - 11:30
Jinbao GAO, 'Reversibility of H2 Sorption in Nanoconfined Sodium
Alanate'11:30 . 12:00
Abdelazim OMAR, 'Development Of Alkylation Toluene With Methanol
for fuel On Modified ZSM-5 Zeolites By Amphoteric surfactant'
12:00 - 12:30
Christoph LANGHAMMER, 'Optical Nanoantennas Shine Light On
Single Nanoparticles'
THURSDAY morning
08:30 - 09:30
09:30 - 10:00
10:00 - 10:30
11:00 - 11:30
11:30 . 12:00
12:00 - 12:30

Chair: Klaus FUNKE
Werner SITTE, 'Long-term Stability of SOFC Cathodes'
Ivo TRAJKOVIC, 'Electrochemical characterisation of a small-scale
alkaline electrolyzer and novel membranes'
Motoaki MATSUO, 'Fast-Ionic Conduction in Complex Hydrides'
Yigang YAN, 'Controlling the decomposition of LiBH4'
Christiaan BOELSMA, 'Verification of the Enthalpy-entropy
Compensation Effect in Metal Hydrides'
Samir BARMAN, 'Functionalized Metal-organic Frameworks for
Chemical Hydrogen Storage'

THURSDAY afternoon Chair: Maximilian Fichtner
14:00 - 15:00
Torben R. JENSEN, 'New Materials for Hydrogen Storage'
15:00 - 15:30
Georgios KALANTZOPOULOS, 'Mechanochemical Reaction of
Sodium Borohydride with Transition Metal Fluorides'
16:00 - 16:30
Marc LINDER, 'Metal Hydride based Preheater for HT-PEM Fuel
Cells'
16:30 - 17:30
Michael FELDERHOFF, 'Towards understanding the molecularrearrangements in complex hydrides'
FRIDAY morning
08:30 - 09:30
09:30 - 10:00
10:00 - 10:30
11:00 - 11:30
11:30 . 12:30

Chair: Torben R. JENSEN
Klaus FUNKE, 'First and second universalities - phenomena andmodelling'
Hans HAGEMANN, 'New experimental and theoretical studies ofborohydrides involving divalent metal ions'
Monica TRINCADO, '"New catalytic approach for the dehydrogenationof amine boranes and organosilanes"'
Petra DE JONGH, 'Reversible Hydrogen Release and Uptake in
NaBH4 Confined in Nanoporous Carbon Material'
Maximilian FICHTNER, 'Perspectives of H Storage andElectrochemical Storage Methods'

Guest
Matteo ARAMINI
Heinz BERKE
Urs FRISCHKNECHT
Mattia GABOARDI
Jiri MULLER
Denis SHEPTYAKOVPROCEEDINGS

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD
List of Participants
Information
Notes

PROCEEDINGS

66th Hydrogen & Energy Symposium

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Timetable

PROCEEDINGS

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6th Hydrogen & Energy Symposium

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Abstracts

PROCEEDINGS

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ELECTROLYSIS AND RECYCLING OF CO2 INTO CO2-NEUTRAL FUELS
Mogens Mogensen
Risø National Laboratory for Sustainable Energy, Technical University of Denmark (DTU), Frederiksborgvej 399, DK4000 Roskilde, Denmark.
It is desirable to change our energy supply into 100 % sustainable energy. We in Denmark believe that this is possible.
The presentation gives first a brief discussion of how this may be doable. Next the potential of synthetic fuels is
explained, and finally the possibility of making synthetic CO2 neutral and affordable hydrocarbon using electrolysis tomake synthesis gas is described. A viable CO2 source is, in the long term, recycling of CO2 originating from combustionof biomass derived fuels.

Introduction

Electrolysis and fuel synthesis

There is a great incentive for the industrializedcountries to become less dependent on fossil fuels.
Denmark's aim is to become independent of coal, oil andgas by 2050 [1]. It is natural to look at biomass as toreplace fossil fuel, but there will not be enough biomass
available [2]. Fortunately, more than enough renewableenergy is potentially available. The annual global influx of24
energy from the sun to the earth is about 3 - 410 J,
while the marketed energy consumption is ca. 51020 J,
i.e. the earth receives ca. 6 - 8,000 times more energy
from the sun than we need. Thus, if we use 0.2 % of the2earth’s area (ca. 1 mill. km or 15 % of Australia) andhave a collection efficiency of 10 %, we get the energythat we need. Besides solar, including wind and hydro,
we also have geothermal and nuclear (fusion and fission)
potential energy sources.

Many types of electrolysers exist with operation
temperatures from room temperature up to 1000 C. The
pros, cons and potentials of the various types will bepresented. In particular, the high temperature (600 - 1000
C) solid oxide electrolyser cell (SOEC) has beenreported practical for co-electrolysis of H2O and CO2 eventhough it is not yet commercialized. Electrolysis of H2O +CO2 into H2 + CO (syngas) and O2 using SOEC isadvantageous, because electrolysis is a heat consuming
process. The Joule heat contributes to the splitting of thewater and CO2 molecules. Thus, the higher thetemperature, the less electrical energy is need for the
splitting. The SOEC may be operated self cooling if theoperation voltage is equal to the thermoneutral voltage.

Thus, the relevant question is: how we can make enoughaffordable energy available?

Storage of sustainable electricity
There are several ways of storing sustainable energy.
They can be roughly divided into physical and chemical
methods. The physical storage types are e.g. pumping
water to high altitude reservoirs, compression of air,flywheel, magnetic storage and super capacitors. They
are generally characterized with relatively low energy
density. Chemical storage types are e.g. biomass,
synthetic fuels and batteries. Great advantages ofsynthetic hydrocarbon fuels are their high energy density
and that existing infrastructure can be used without major
modifications.

From syngas most hydrocarbon fuels can be synthesisedusing well established catalytic conversion technologies.
The simplest and cheapest synthetic hydrocarbon is CH4,
also called substitute natural gas (SNG), which may betransported in the existing NG pipelines. Compounds like
CH3OH and dimethyl ether (DME = (CH3)2O) are moresuitable for the transport sector (trucks, air planes, cars).

References[1]

Energy strategy 2050 - from coal, oil and gas togreen energy, The Danish Government, 2011,
http://www.ens.dk/Documents/Netboghandel%20%20publikationer/2011/Energy_Strategy_2050.pdf[2]

H. Wenzel, “Breaking the biomass bottleneck of thefossil free society”, Sep. 22nd, 2010, CONCITO,
http://www.concito.info/en/udgivelser.php

Research Professor, Fuel Cells and Solid State Chemistry Division, Risø National Laboratory for
Sustainable Energy, DTU; 38 years in electrochemistry; M.Sc. in 1973 and Ph.D. in 1976 from the
Department of Metallurgy, DTU; Manager of numerous projects and now of Strategic Electrochemistry
Research Center (SERC); 180 peer reviewed journal papers (cited more than 5000 times) and 17
patents/applications; h-index 36. Received the Christian Friedrich Schönbein Medal of Honor at The
8th European Fuel Cell Forum, 2008.

M. Mogensen
Corresponding author: Mogens Mogensen, momo@risoe.dtu.dk, Tel. +45 2132 6622

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TUNING DE/HYDROGENATION KINETICS AND THERMODYNAMICS OFMAGNESIUM BASED ALLOYS
M. Zhu, L. Z. Ouyang and H. Wang
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P. R. China
Abstract By in-situ forming nanocomposite, the de/hydrogenation kinetics can be greatly improved in a Mg-Ce-Ni alloy-1with dehydrogenation activation energy reducing to 63 KJ(mol H2) . Based on that, a Mg-Ce-Ni alloy has beendeveloped, which has initial capacity of 4 wt. %, fast kinetics and excellent cycleabilty. By forming solid solution in Mg
based binary and ternary alloys, the thermodynamics can be adjusted with fully reversible de/hydriding. For Mg90In10 and
Mg85In5Al10 solid solutions, the enthalpy of dehydrogenation reaction is altered to -65 KJ/mol and -63 KJ/mol respectively.

Introduction

Reversible hydriding of Solid solution

Mg based hydrides are potential candidates that satisfy
the requirement for the future hydrogen energy.
However, too high thermodynamic and kinetic barrier isstill big obstacle for utilization. Substantial kinetics
improvement has been achieved by nanoscaling,
catalyzing and alloying, but little progress in tuning thethermodynamics unless the Mg is refined to several
nanometers. Changing reaction path has tuned thethermodynamics in Mg-Si system but the reaction is notreversible[1]. We present here a fully reversible
de/hydriding in Mg based solid solution with alteredreaction enthalpy, and a kinetic improvement by in-situ
forming nanocomposite.

The MgH2/Si system showed reduced desorption
enthalpy of 36.4 kJ (mol H2)-1, which is attributed to theformation of Mg2Si. However, this system suffers frompoor reversibility and large capacity loss [1]. We havedeveloped a reversible de/hydriding reaction in Mg basedsolid solution[3]. By mechanical alloying, Mg(In) solid
solution can be obtained. In the hydriding reaction, Mg(In)transforms to MgH2 and MgIn( phase), while in thedehydriding reaction, MgH2 and MgIn can fully reversiblytransformed to Mg(In). The enthalpy of this reaction is
obviously reduced and plateau pressure is significantly
increased. The reduction of desorption enthalpy is related
to In content in Mg(In) solid solution and it changes from 78 KJ/mol for pure Mg to -65 KJ/mol for Mg90In10 withhydrogen storage capacity of more than 4.0 wt. %. This
concept can be extended to other systems. We also
prepared solid solution in Mg-In-Al ternary system. A fully
reversible hydriding is also realized and the enthalpy canbe further reduced to -62 KJ(mol H2)-1 for Mg85In5Al10 withreversible hydrogen storage capacity of more than 4.0
wt. %. The above results provide significantly new way
for tuning the thermodynamics of Mg based hydrides.

In-situ formed nanocomposite
Mg-RE alloys can disproportionate to MgH2 and REH3 inhydriding process and unique nanocomposite structure
can be in-situ formed in some Mg-RE-TM systems by thisreaction [2]. We show that the MgH2-CeH2.73-Ni
nanocomposite has very fine lamella structure withthickness of MgH2 and CeH2.73 less than 30 and 15 nm,
respectively. In addition, Ni nanoparticles exist at theirboundary. The adjoining of extremely fine CeH2.73 and Ni
to Mg/MgH2 enhances de/hydriding. Indeed, a very fast
kinetics was achieved in aMg-Ce-Ni alloy with capacity of
4.0 wt.% and the temperature for fully de/hydrogenation
cycle was significantly decreased to 505 K. The apparent
activation energy (Ea) for the dehydriding of the alloy was
lowered to 63±3 kJ/mol from 158 kJ/mol measured for
MgH2. The above nanocomposite structure also
effectively inhibits phase growth, which leading long cycle
life of more than 500 cycles.

References[1] J. Vajo, F. Mertens, C.C. Ahn, R.C. Bowman, B. Fultz,
J. Phys. Chem. B 108 (2004) 13977.
[2] L. Z. Ouyang, X.S. Yang, H.W. Dong, M. Zhu, Scripta
Materialia, 61 (2009) 339.
[3] H.C. Zhong,H. Wang,J.W. Liu,D.L. Sun and M.
Zhu,Scripta Materialia 65 (2011) 285–287

136th Int. Symposium Hydrogen & Energy

Min Zhu

Stoos, Switzerland 2012

Professor Min Zhu received Ph.D degree from Dalian Univ. of Tech. in 1988. Heworked in TU Berlin as Humboldt Research Fellow from 1993 to 1995, and laterin Tokyo Univ., NIMS, and Univ. of Sydney as visiting scientist. His researchinterests include hydrogen storage materials, lithium ion battery, mechanicalalloying and shape memory alloys. He has published more than 100 papers in peer
reviewed international journals. He received the Outstanding Young Scientist Fundfrom NSFC in 1999, and appointed as “Cheung Kong Professor” in 2002. He is a
Chief Scientist of China’s “973” project on hydrogen storage materials

Corresponding author: Min Zhu, memzhu@scut.edu.cn, 86-20-87113924.

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NANOCONFINED METAL HYDRIDES FOR ENERGY STORAGE
Zhirong Zhao-Karger, Elisa Gil Bardají and Maxmilian Fichtner
Karlsruhe Institute of Technology (KIT), Institute of nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germany
The impacts of nanoconfinement on the hydrogen storage properties of metal hydrides and decomposition reaction
pathways of complex metal hydrides have been investigated. Nanoconfinement within porous carbon scaffolds has
proved to be promising for tuning the thermodynamics and hydrogen sorption kinetics of metal hydrides. As a bottom-up
nanostructuring methodology, nanoconfinement is also of interest for other applications for chemical energy storage inthe future.

Introduction
Many efforts have been devoted to synthesize nanoscaled metal hydrides to improve their hydrogen sorption
properties and make them suitable for hydrogen fuel-cellbased applications. This is because nanostructuring can
improve the kinetics of a solid state reaction by
shortening the diffusion lengths. In addition, at thenanoscale, the thermodynamic stability of metal hydrides
can also be significantly affected by surface energy.[1]Nano-confinement within porous host scaffolds has
proved to be an efficientmethod for preparing
nanoscaled metal hydrides, especially for materials witha particle size below 10 nm.[2] In the present work, thethermodynamics, dehydrogenation kinetics, and reaction
pathways of nanoconfined hydride materials have beenstudied.

Experimental

surface and porosity analysis (BET method), solid state
NMR et al.

Results
All the composites have shown remarkable decreased
desorption temperatures compared to their bulk states.
The activation energies have been lowered fordecomposition reactions of Mg(BH4)2 and MgH2.
In addition to kinetic change, nanoconfined MgH2 has
also shown the change on equilibrium pressures. The
reduced enthalpy and entropy have been determined forthe nanoscaled MgH2 by pressure-composition isotherm(PCI) measurements. In case of nanoconfined metalborohydride, the decomposition reaction pathways
significantly differ from those of bulk materials.

References[1] M. Fichtner Nanotechnol 20: 204009(2009).

Porous carbon materials with pore width below 4 nm
were utilized as size controlling templates for metal
hydrides. Nanoconfined metal hydrides including MgH2,
Mg(BH4)2 and the binary LiBH4/Mg(BH4)2 system havebeen synthesized by wet incipient impregnation or
melting infiltration techniques. Characterization was
performed by means of TEM, N2 physisorption based[2] Zh. Zhao-Karger, J. Hu, A. Roth, et al. Chem.
Commun. 46, 8353(2010) ; S. Sartori, K. D. Knudsen,
Zh. Zhao-Karger et al. J. Phys. Chem. C, 114,

18785(2010)

Born 01. 11. 1970 in Nei Mongol, China. 1996 M.Sc in Chemistry in China, 2006 Dr. rer. nat. at theinstitute of organic chemistry, university of Hannover, Germany, 2007 Postdoc at the Catalytic
Research Laboratory, university of Heidelberg, Germany, 2008 Research staff at the Institute of
Nanotechnology, Karlsruhe Institute of Technology.

Zh.Zhao-Karger
Corresponding author: Zhirong Zhao-Karger, email: Zhirong.Zhao-Karger@kit.edu, Tel.(+49) 721 608 28908

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HYDROGEN DYNAMICS IN NANOCONFINED LITHIUMBOROHYDRIDE
Arndt Remhof1, Andreas Züttel1, Jan Peter Embs2, Peter Ngene3, Petra de Jongh3
1

Empa, Hydrogen and Energy, Dübendorf, Switzerland; 2Laboratory for Neutron Scattering, ETHZ & PSI, Villigen PSI,
3
Switzerland; Inorganic Chemistry and Catalysis, Utrecht University, NL-3584 CA Utrecht, The Netherlands

Nanoconfinement of LiBH4 is a promising way to enhance the hydrogen sorption kinetics and to prevent phasesegregation. Quasielastic and inelastic neutron scattering reveal the stabilization of the high temperature phase at room
temperature. The rotational mobility however, differs from the bulk high temperature phase. The activation energy isenhanced and a substantial number of [BH4] ions do not participate in the fast rotational motion.

Introduction
Lithium borohydride (LiBH4) is an attractive material forsolid state hydrogen storage due to its high hydrogencontent of 18.5wt% [1]. Confinement of LiBH4 in small
pores can increase hydrogen release and uptake kinetics
We performed inelastic and quasielastic neutron
spectroscopy to investigate the hydrogen dynamics inmelt-infiltrated LiBH4 in graphitic porous carbon,
especially the reorientations of the [BH4] ions.

Results
Figure 1 compares the time of flight spectra of bulk LiBH4(top) and nanoconfined LiBH4 (bottom), recorded attemperatures between 300K and 500K.
In bulk LiBH4, the phase transition is clearly seen by thesudden change of the shape of the TOF spectra between
360K and 390K. In case of nanoconfined LiBH4 in carbon(15wt%), no phase transition is seen in the temperature
range between 300K and 500K. The absence of the
pronounced spectral features is a fingerprint of the hightemperature phase [2]. Nanoconfinement stabilizes thehigh temperature phase at room temperature and leads
to a shift of the transition temperature well below room
temperature.
Inthequasielastic
regime,thenanoconfined system shows enhanced rotational
disorder at room temperature as compared to the bulk
material. Up to 430 K the quasielastic broadening follows
Arrhenius behaviour with activation energy of 83meV,which is higher than in the bulk HT phase. Also the time
between two consecutive rotational jumps is increased.
The confinement favours the dynamically disordered HTphase but at the same time reduces the mobility. Above
430 K the quasielastic broadening is almost independentof temperature, probably due to a melting-like process.

Arndt Remhof

Figure 1: (top) Time-of-flight (TOF) spectra for bulk LiBH4
and of nano-confined LiBH4 (bottom)

References[1] A. F. Gross, Jwt al., J. Phys. Chem. C 112, 5651,(2008).
[2] A. Borgschulte, et al., Faraday Discuss. 151, 213,
(2011).

1994
University Diploma with distinction of the University of Kent at Canterbury, UK.
1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France.
1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany.
1999
Guest scientist at the Universidade Sao Francisco in Itatiba, Sao Paulo, Brazil.
2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands.
2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum.
From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.”
2010
Guest scientist at the Tohoku University in Sendai, Japan

Corresponding author: Arndt Remhof, arndt.remhof@empa.ch +41587654369

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SANS AND TEM CHARACTERIZATION OF MGH2-NABH4 NANOPARTICLESCONFINED IN SILICA BASED MESOPOROUS SCAFFOLD SBA-15
Renato Campesi1, Sebastiano Garroni2, Eva Pellicher3, M.Dolors Baró3, Chiara Milanese4,
Alessandro Girella4, Francesco Dolci1, Gabriele Mulas2.
1

JRC-IET, Westernduinweg 3, 1755 ZG Petten, The Netherlands

2

Dipartimento di Chimica, Università di Sassari and INSTM, Via Vienna 2, I-07100 Sassari, Italy

3

Departament de Física, Universitat Autònoma de Barcelona, E-08193 Bellaterra, Spain

4

C.S.G.I. & Dipartimento di Chimica, Sezione di Chimica Fisica, Università di Pavia, Viale Taramelli 16, I-27100 Pavia,
Italy.
Abstract: The confinement via melt infiltration of MgH2 and NaBH4 nanoparticles within the pores of a silica based
mesoporous scaffold (SBA-15) was studied either by small angle neutron scattering (SANS) or by transmission electron
microscopy (TEM). The coupling of SANS and TEM techniques allowed to confirm that the synthesis route adopted forthe preparation of MgH2-NaBH4/SBA15 nanocomposite, enabled the dispersion of the hydride nanoparticles, with a good
extent, within the pores of the SBA-15 scaffold. The nanoparticles dispersion was studied on the as synthesizedmaterials as well after hydrogen des-absorption cycles.
Introduction
Among the several techniques exploited so far in order toimprove hydrogen storage properties of the so called
Reactive Hydride Composites (RHC), nanoconfinementof the hydride phases in porous materials sounds very
interesting [1] . At least in principle the confinement could
hinder the growing of the hydride particle size during thesynthesis process and allows the dispersion of the active
phases in the support material. The resulting benefit
would be reduced particle size which is recognized tohave a great influence in improving the kinetic andthermodynamic as well as to facilitate the interaction
between the hydride phases during the hydrogenation
process. In that respect we synthesized nanocomposite
by melt infiltration of MgH2 and NaBH4 in the pores ofwell ordered silica based porous material (SBA-15). TEM
and SANS techniques showed as the melting process led
to the dispersion of nanoparticles either within (< 5nm) or
outside the SBA-15 pores.
Experimental
SBA-15 were synthesized from TEOS and a co-block
polymer P-123, following a procedure reported inliterature by Zhao et al. [2]. The SBA-15 were then mixed
with MgH2 and NaBH4 and heated up to 450 °C under Ar
atmosphere for 1 h. The structural characterization of thesamples was carried out by TEM (Jeol-JEM 2011, 200
kV, Tecnai F24) and SANS at the ILL-D22 beam line.
The samples were also desorbed and re-absorbed using
a volumetric apparatus (PCT-pro 2000, Setaram)

Results
SANS measurements showed the appearance of a new-1
peak centered at around 2 nm (figure 1a). This newreflection suggested that new ordered scatterers with asize smaller then the pores of the SBA-15 are present in
the MgH2-NaBH4/SBA-15 nanocomposites. Taking into
account that the scaffold displays only three main peaks-1
centered at 0.66, 1.14 and 1.32 nm , respectively; thenew peak could be attributed to MgH2 and NaBH4nanoparticles. It is also interesting to note that thisreflection is present only in the pattern of the desorbed orre-absorbed materials. This means that the hydride
nanoparticles confined within the pores of the SBA-15
maintained their size even after the hydrogen desorption
and desorption process. To further investigate thedispersion of MgH2 and NaBH4 nanoparticles in the SBA15 scaffold, the as synthesized materials as well as thecycled ones were investigated by transmission electron
microscopy (TEM), the image (figure 1b). shows that thenanocomposites are mainly composed by nanoparticles
dispersed inside the pores of the scaffold. STEM-EDX
chemical analysis also confirmed that both MgH2 andNaBH4 were infiltrated in the SBA-15 pores.
References[1] A. F Gros, J. J Vajo, S.L Van Atta, G. L. Olson, S. L.
Skeith, F. Mertens, J. Phys. Chem. C 2008 112 5651
[2] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. Fredrickson,
B. Chmelka, G. Stucky, Science 279 (1998) 548-52.

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Was born in Olbia, Sardegna, Italy on the 15-01-1981
Graduated in Chemistry at the Universita’ di Sassari in 2005
PhD in Engineering Science and Environment, Universite’ de Paris-Est in 2008
Currently working as a researcher at the JRC-IET in Petten, the Netherlands
RenatoCampesiCorresponding author: Renato Campesi, renato.campesi@ec.europa.eu, Tel. +31224565228

a)b)
Figure 1. a) SANS patterns of the SBA-15 and the MgH2-NaBH4/SBA-15 nanocomposites as synthesized ad after
cycling; b) tilted TEM images of the MgH2-NaBH4/SBA-15 nanocomposite, the circle highlights the filled channel.

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HYDROGEN ABSORPTION IN SODIUM INTERCALATED FULLERENES
Philippe Mauron,1 Michael Bielmann,1 Arndt Remhof,1 Andreas Borgschulte,1 Mohammad
Choucair,2 Mattia Gaboardi,2 Daniele Pontiroli,2 Denis Sheptyakov,3 Mauro Riccò,2Andreas Züttel,1
1Empa. Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, CH-8600 Dübendorf,
Switzerland
2

Dipartimento di Fisica, Università di Parma, Via G. Usberti 7/a, 43100 Parma, Italy

3

Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

The hydrogen absorption of sodium intercalated fullerenes (Na10C60) was investigated volumetrically with a pcT system.
Hydrogenation was done at pressures up to 200 bar and at temperatures up to 450°C. 2 mass% of hydrogen can bereversibly stored in Na10C60. The samples were investigated by XRD, Raman spectroscopy and neutron diffraction.

Introduction

Results

Hydrocarbons have a high hydrogen storage capacity
e.g. up to 25.1 mass% for methane and >12.4 mass% foralkanes CnH2n+2. In hydrocarbons the hydrogen iscovalently bond to the carbon and the desorption
temperature is too high for mobile applications. For
physisorbed molecular hydrogen on high surface areacarbon materials the binding energy is too low and liquid
nitrogen temperatures are required. An intermediatebinding energy of 20 – 40 kJ/mol H2 would be needed forpractical applications. This can be obtained by means ofan additional attracting force between hydrogen moleculeand the host material, which could originate from anelectrostatic (dipole or quadrupole) or orbital interaction(e.g. Kubas) [1].

Up to 2 mass% of hydrogen can be reversibly stored in
Na10C60. During hydrogen absorption the crystal lattice of
Na10C60 is expanded and a new phase was formed asshown by XRD (Fig. 1) and neutron diffraction.

Experimental
The Na10C60 samples were synthesised by decomposing
a mixture of sodium azide and C60 [2] pressed into apellet at temperatures between 380 and 450 °C.
Hydrogenation/deuteration was performed at pressures
up to 200/100 bar respectively at temperatures up to
450°C for several hours.
Dehydrogenation was done by applying a temperature
ramp up to 400 °C at 1 bar hydrogen or at constantvolume.

2nd abs (200°C, 200 bar)
1st H2 des (400°C)
1st H2 abs (350°C, 200 bar)
Na10C60

160

Intensity [a.u.]

140
120
100

80
60
40
20
0
10

20

30

40
Angle [2

50

60

70

Fig. 1: XRD patterns of the hydrogen absorption of Na10C60

References[1] G.J. Kubas, R.R. Ryan, B.I. Swanson, Ph.J.
Vergamini, H.J. Wasserman, J. Am. Chem. Soc. 106(1984) 451.
[2] K. Imaeda, I.I. Khairullin, K. Yakushi, M. Nagata, N.
Mizutani, H. Kitagawa, H. Inokuchi, Solid State
Comm. 87 (1993) 375.

1973 born 6. October in Fribourg, Switzerland.
1999 Diploma in experimental physics (solid state physics), University of Fribourg,
Switzerland.
2003 PhD at University of Fribourg, Switzerland.
2005 Postdoc at Vrije Universiteit Amsterdam, The Netherlands.
2007 Project leader at Empa. Swiss Federal Laboratories for Materials Science andTechnology, Dübendorf, Switzerland
Philippe Mauron
Corresponding author: philippe.mauron@empa.ch, Tel. +41 58 765 4099

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6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012ZEOLITE-TEMPLATED CARBON MATERIALS FOR HIGH PRESSURE
HYDROGEN STORAGE
Nicholas P. Stadie1,2, John J. Vajo3, Philippe Mauron2, Andreas Borgschulte2, Andreas Züttel2,
Channing C. Ahn1, Brent Fultz1
1

W. M. Keck Laboratory, California Institute of Technology, Pasadena, California 91125, USA

2

EMPA, Swiss Federal Laboratories for Materials Research and Testing, CH-8600, Dübendorf, Switzerland

3

HRL Laboratories, LLC, Malibu, California 90265, USA

The hydrogen storage capacity reported for zeolite-templated carbon (ZTC) is among the highest for physisorptive
materials (including porous carbons, carbon nanotubes, zeolites, and metal-organic frameworks): 6 wt% at 2 MPa and at
77 K. Measurements at 298 K have been performed to determine the viability of room temperature hydrogen storage by
pure physisorption. At pressures up to 30 MPa, hydrogen uptake is found to be dependent on specific surface area, evenacross numerous different materials, despite earlier reports otherwise.

Zeolite-Templated Carbon

Experiment

These materials are obtained via a templating method; asuitable polymeric carbon precursor is inserted into thechannels of a zeolite by mixing, then polymerized tocreate a solid hydrocarbon with analogous structure to
the zeolite. The polymer/zeolite composite is treated athigh temperature and the polymer is pyrolyzed to carbon.
This replicate carbon, ZTC, is then freed from the zeolite
template by dissolution in HF, yielding porous zeolite-likestructures with extremely high surface areas (>3000
2
1m /g) and large micropore volume.

We prepared high surface area carbons by the ZTC
method; materials with BET surface areas of up to 3800
m2/g were readily produced in multi-gram quantities.
Measurements of N2 and CO2 adsorption were performed
to analyse the difference in pore character between ZTCs
and other carbons. Hydrogen uptake measurements at
77, 87, and 298 K were performed with a gravimetricbalance and a custom, volumetric Sieverts apparatus (to10 MPa). A second, high pressure Sieverts apparatus
was designed and constructed to measure hydrogen
uptake at pressures up to 70 MPa.

Remarkable Hydrogen Storage at 298 K?

It was reported that room temperature hydrogen uptake
in zeolite-templated carbon (ZTC) materials exceeds thatof materials with similar specific surface area, such as2
superactivated carbon MSC-30, by up to 100%. While
this effect was not reported to be observed at standard
measurement pressures (1-10 MPa), it was claimed to beevident in the regime of 20-34 MPa. Few suitableapparatus for measurement at these pressures exist.

N. Stadie

Gibbs excess hydrogen capacity across all materials
measured corresponded to specific surface area, even athigh pressure. The highest measured capacity was ~1
wt% which is well below the target values for a viable
storage material. Physisorbent materials are not suitablefor hydrogen storage at room temperature.

References[1] Yang et al., “Enhanced Hydrogen Storage Capacity ofHigh Surface Area Zeolite-like C Materials,” JACS,
2007.
[2] Kyotani et al., “High-Pressure Hydrogen Storage in
Zeolite-Templated Carbon,” J Phys Chem C, 2009.

Nick was born in 1985 in Calgary, Alberta, Canada. He received a BS in chemistry from ArizonaState University in Tempe, Arizona, USA in 2007, focusing on synthesis of novel metal-organic
framework materials with Prof. Michael O’Keeffe. He now carries out graduate studies and research
at California Institute of Technology in Pasadena, California, USA with Prof. Brent Fultz and Dr.
Channing Ahn. The focus of current research is synthesis and characterisation of high surface areamaterials for hydrogen storage applications. He expects to graduate with a PhD in Materials Sciencein 2012. During 2010, Nick spent 6 months at EMPA in Dübendorf, Switzerland performing CO2
adsorption experiments on porous materials as a technique for the characterisation of extremely
narrow microporosity.

Corresponding author: Nicholas P. Stadie, nstadie@caltech.edu, +1-626-395-2329

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IMPROVED HYDROGEN STORAGE IN LI-MG-N-H COMBINED SYSTEM
Hongge Pan, Yongfeng Liu, Mingxia Gao
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China.

Abstract
Hydrogen is the most ideal fuel in the comprehensive
clean-energy concept. However, hydrogen storage is stilla major technical barrier for its on-board application as atransportation fuel. Recently, metal-N-H systems havebeen attracting significant attention owing to their highgravimetric hydrogen density. Among them, the Li-Mg-NH material is regarded as one of the very promisingsystems due to its good reversibility, comparatively highhydrogen content and favorable thermodynamic
properties. Unfortunately, a relatively high kinetic barrier
retards its practical applications for hydrogen storage. In
this talk, we present our recent work on improving thehydrogen storage thermodynamics and kinetics of the LiMg-N-H combined system by size effect, composition
adjustment and catalyst addition. It is found that thereaction pathways for dehydrogenation/hydrogenation of
the LiNH2-MgH2 (1:1) system depends strongly on the
milling duration due to the presence of two competing
reactions in different stages including ball milling andheating process. This fact explains reasonably thediscrepancies in the experimental results of the LiNH2MgH2 (1:1) system reported previously by several
research groups. Moreover, Li2MgN2H2 was synthesizedby sintering a mixture of Mg(NH2)2-2LiNH2 and its sizedependent hydrogen storage performances were
investigated systematically. A dramatically enhanced
kinetics for hydrogen absorption/desorption was achieved
with a reduction in the particle size. For dehydrogenation

reaction, a three-dimensional diffusion controlled kinetic
mechanism was definitely identified for the first time byanalyzing isothermal hydrogen desorption curves using alinear plot method. In addition, improved hydrogenstorage properties were achieved for the Mg(NH2)2-2LiH
system by introducing various additives, such as NaOH,NaBH4, and so on. The role played by the additives wereanalyzed and discussed.

References[1] P. Chen, Z. Xiong, J. Luo, J. Lin, K. Tan, Nature
2002, 420, 302-304.
[2] Z. Xiong, G. Wu, J. Hu, P. Chen, Adv. Mater. 2004,
16, 1522-1525.
[3] W. Luo, J. Alloys Compd. 2004, 381, 284-287.
[4] Y. Liu, K. Zhong, M. Gao, J. Wang, H. Pan, Q. Wang,
Chem. Mater. 2008, 20 3521-3527.
[5] Y. Liu, K. Zhong, K. Luo, M. Gao, H. Pan, Q. Wang, J.
Am. Chem. Soc. 2009, 131, 1862-1870.
[6] C. Liang, Y. F. Liu, K. Luo, B. Li, M. X. Gao, H. G. Pan
and Q. D.Wang, Chem. Eur. J., 2010, 16, 693-702.
[7] C. Liang, Y. F. Liu, Y. jiang, Z.J. Wei, M. X. Gao, H. G.
Pan and Q. D.Wang, Phys. Chem. Chem. Phys.,
2011, 13, 314-321.

Hongge Pan received his PhD in Materials Science and Engineering from Zhejiang University in
1996 under a joint program between Zhejiang University and Institute of Physics, Chinese
Academy of Science. Later that year he joined Zhejiang University and became a Professor in
1999. He awarded the Chinese 2000 National Excellent Doctoral Dissertation Award. His
research is focused on energy materials for solid-state hydrogen storage and lithium batteries.

Hongge Pan
Corresponding author: Hongge pan, hgpan@zju.edu.cn, honggepan@zju.edu.cn; +86-571-87952615.

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DEVELOPMENT OF LOW COST VANADIUM-BASEDSTORAGE ALLOYS IN SICHUAN UNIVERSITYHYDROGEN

1

Chaoling Wu, 2Yigang Yan, 1Fei Yang, 1Linshan Luo, 1Yungui Chen

1

College of Materials Science and Engineering, Sichuan University, Chengdu 610064, China
EMPA, Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland

2

Abstract Vanadium (V)-based hydrogen storage alloys show attractive absorption capacity up to 3.8wt% and goodkinetics at near room temperature. However, the cost of alloy hinders their applications, due to the high price of pure V(25,000 Euro/ton). After several years of efforts, Sichuan University made a big progress in preparing low cost V-based
alloys by using cheap FeV80 master alloy. The cost of alloy was significantly decreased by about 90%. The cyclicstability and the applications of the alloys have been investigated. 2.5 kg V-based alloys prepared from FeV80 were filledin two containers to supply the hydrogen for a fuel cell bicycle, which shows a cruise of around 100 km after one fullcharge.

Establishment of V-Ti-Cr-Fe alloy system
A V-Ti-Cr-Fe quarternary alloy system was developedwith the V content varying from 20~60 mol%. The
optimum compositions among this system show
desorption capacities ≥ 2.1 wt% at room-temperature [1].
The ab/desorption capacities were found to strongly
dependonlatticeparameters
andelectronconcentrations. Based on this system, the addition ofmanganese further improve the desorption capacity to
2.43 wt% at room-temperature and 3.0 wt% at 80 ℃.

Application of V-based hydrogen storage
alloys
2.5 kg of the V-based alloy, prepared by arc-melting
under vacuum, was stored in two containers as thehydrogen supply to a fuel cell bicycle. The bicycle is able
to run 100 km (40 km / kg alloy) after being fully charged.
In comparison, the same bicycle carrying 3 kg of thecommercial alloy (AB5 type) only runs 56.5 km (18.8 km /kg alloy) after one charge.

Cyclic stability of the alloys
Cyclic stability of two alloys of Ti-Cr-(VFe)48 and Ti-Cr(VFe)72 were investigated [2]. The desorption capacity
decreases sharply during the first 10 ab/desorption cycles,
while keeping steady after that. Ti-Cr-(VFe)72 alloyshows better cyclic stability than Ti-Cr-(VFe)48. The
microstrain inside the lattice was found to be strongly
related with the decrease in desorption capacity. On theother hand, the surface poisoning by the impurities in thehydrogen sources was also found to reduce the cyclic life.

贮氢器Container

燃料电池
Fuel
cell

Alloys prepared from FeV80 master alloy
The price of FeV80 master alloy is even lower than 10%of that of pure V metal in current market. We succeededin preparing the V-Ti-Cr-Fe-based alloys from the cheap
FeV80 master alloy, due to their similar V/Fe ratio [3]. For
example, V-Ti-Cr-Fe-Mn prepared from FeV80 shows
almost the same desorption capacity and a slightincrease in plateau pressure from 0.35 to 0.45 MPa.

Wu Chaoling

Figure 1. The fuel cell bicycle carrying 2.5 kg V-basedhydrogen alloys in two containers.

References[1] Y. Yan, et al, J. Alloys Comp. 441, 297 (2007).
[2] C. Wu, et al, Int. J. Hydrogen Energy 35, 8130 (2010).
[3] Y. Yan, et al, J. Power Source 164, 799 (2007).

Born 20th July, 1974 in Chongqing City, China. 1997 bachelor in department of metal materials and heattreatment, Chengdu University of Science and Technology, Chengdu, China. 2000 Master in College ofMaterials Science and Engineering, Sichuan University, Chengdu, China. 2003 Ph.D. in College of Materials
Science and Engineering, Sichuan University. 2003 Lecturer in College of Materials Science and Engineering,
Sichuan University. 2007 Associate professor in College of Materials Science and Engineering, Sichuan
University. 2007 Assistant director in Engineering Research Center of Alternative Energy Materials &Devices, Ministry of Education of China. 2008 Chief Engineer in Sichuan Baosheng New Energy Materials
Co., Ltd. Chengdu, China. Research field: Hydrogen production, hydrogen storage and system, electrodematerials in batteries. 2012 Guest Professor in Prof. Züttel Lab in EMPA Swiss Federal Laboratories forMaterials Science and Technology, Switzerland.

Corresponding author: Chaoling Wu, wuchaoling@scu.edu.cn, 86-28-85466916

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HYDROGEN STORAGE IN TETRA N-BUTYL AMONIUM BROMIDE SEMICLATHRATE HYDRATES: KINETICS AND EVOLUTION OF HYDRATEPHASE COMPOSITION BY IN SITU RAMAN SPECTROSCOPY
Alondra Torres Trueba,1 Ivona Rodovic,1 John F. Zevenbergen,2
Cor J. Peters,1,3,4 Maaike C. Kroon4*
1

Department of Process & Energy, Delft University of Technology, Delft, Netherlands
TNO Defense, Security and Safety, Lange Kleiweg 137, 2288 GJ Rijswijk, Netherlands
3
Chemical Engineering Program, Petroleum Institute, Abu Dhabi, United Arab Emirates
4
Department of Chemical Engineering & Chemistry, Eindhoven University of Technology, Eindhoven, Netherlands
2

In order to elucidate the potential of H2-TBAB semi-clathrate hydrates for H2 storage, kinetic data and in situ Raman
spectroscopy measurements were obtained for two TBAB concentrations (2.6 mol% and 3.7 mol% in the liquid solution)
in a pressure range of 5 – 16 MPa. The influence of pressure, TBAB concentration and formation method (T-cycle
method and T-constant method) on the hydrate nucleation, hydrate growth and H2 storage capacity was determined. The
results showed that kinetics are favored at higher pressures and solute concentrations. Less stochastic nature wasobserved when the T-cycle method was applied. The inclusion of H2 in the semi-hydrate phase was confirmed.

Introduction
Tetrabutylammonium bromide (TBAB) semi-clathrate
hydrates, or TBAB semi-hydrates are crystalline inclusioncompounds formed by H2O molecules and by TBAB
salts. Recently, TBAB semi-hydrates have been
proposed as potential H2 storage materials [1]. In order todevelop semi-hydrate based technology for H2 storage, itis necessary to take into account the optimal kinetics offormation, which depends on the conditions applied.
Therefore, time-dependent experiments were performedin this study in order to determine the optimal formation
kinetics as well as the H2 storage potential of H2-TBAB
semi-hydrates.

Results
The influence of pressure (5-16 MPa), TBAB
concentration (2.6 mol% and 3.7 mol%) and formation
method (T-cycle method and T-constant method) on thehydrate nucleation, hydrate growth and H2 storage
capacity was determined. The results showed thatkinetics are favored at higher pressures and soluteconcentrations. It was also observed that the H2-TBAB
semi-hydrate formation at constant cooling rate (T-cycle
method) exhibited shorter induction times with a lessstochastic nature compared to the T-constant method.
There was not observed any influence of the formation
method on the hydrate growth and amount of H2
consumed.

Additionally, a new apparatus was built and tested to
study the hydrate phase formation and dissociation for asolution of 2.6 mol% of TBAB in situ by using the Raman
spectroscopy technique. The inclusion of H2 in the semihydrate phase was confirmed. Results showed theimportance of H2 mass transfer on the storage capacity of
the H2-TBAB semi-hydrates.

Conclusions
In order to developed semi-clathrate hydrate based
technology for H2 storage, higher pressures and soluteconcentrations should be used to assure optimal kinetics.
The T-cycle method should be applied to reduce thestochastic nature of the semi-hydrate formation. Finally,
to assure optimal H2 storage, the H2 mass transfer
limitations should be eliminated by means of increasing
the contact surface area by the liquid and gas phases or
the hydrate and gas phases.

References[1] Hashimoto S, Murayama S, Sugahara T, Sato H,
Ohgaki K. Thermodynamic and Raman spectroscopic
studies on H2+tetrahydrofuran+water and H2+ tetran-butyl
ammoniumbromide+water
mixturescontaininggas
hydrates.
Chem
Eng
Sci
2006;61(24):7884-8.

M.Sc. Alondra Torres earned her bachelor degree from Universidad Autonoma del Estado de Mexicoand her master degree (cum laude) from Universidad Iberoamericana in Mexico City. Currently
Alondra Torres is appointed as a Ph.D. student at Delft University of Technology in the Netherlands.
During her studies Alondra Torres has been involved in several projects including; heavy metals
removal from waste water with organic material and the formation of polymeric membranes withsupercritical CO2 for gas separation. Her current Ph.D. project involves the study of the potential ofclathrate hydrates for hydrogen storage.
Alondra Torres*

Corresponding author. Cor J. Peters, E-mail: cpeters@pi.ac.ae, Tel.: +31-15-2782660

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STUDYING HYDROGEN ADSORPTION ON MOF FRAMEWORKS
A.J. Ramirez-Cuesta
ISIS Facility, Rutherford Appleton Laboratory, STFC, Chilton, Didcot, OX11 0QX, United Kingdom
The interaction of molecular hydrogen with surfaces and porous materials can be studied with Inelastic Neutron
Scattering Spectroscopy (INS). In particular the rotational line of hydrogen is very sensitive to the interaction of themolecule with the adsorption site. A series of results arising from the interaction of hydrogen with different system ispresented. From the weak interaction of molecular hydrogen with carbon to the stronger interaction with metal organic
frameworks.

Introduction
Inelastic neutron scattering spectroscopy (INS) is
an ideal technique to study hydrogen containing
materials.[1]. Another great advantage of INS isthat allows a more direct comparison between
experimental results and theoretical calculations
than is the case for optical spectroscopies (Raman
and Infra-red). All experiments have been made in
TOSCA, which is the world’s higher resolution
broadband INS spectrometer. It measures a rangeof 3-1000 meV (24-8000 cm-1).
TheoryThe rotational levels for the hydrogen molecule, inthe case of solid hydrogen (negligible interaction
between molecules) are given by:
EJM=J(J+1) Brot

Where J and M are the rotational quantum
numbers. In the case hydrogen, the rotational
constant B is 7.35 meV. With INS, due to the natureof the neutron with matter, we can measure an
extremely sharp line corresponding to the rotationaltransition J(1←0) (para to ortho-hydrogen), that has
an energy of 2B (14.5 meV) [1,2].
When the hydrogen molecule interacts with asurface, the rotational line can experience a shift
and splitting. In the case of graphite, there is a verysmall widening of the rotational line. For carbon
nanotubes, the effect, due to the curvature of thesurface is more pronounced but still small. For
metal oxides, MOF, zeolites etc, the interaction ofmolecular hydrogen is large, so are the rotationalline shifts [5]. For MOFs, a very exquisite
assignment of the adsorption sites can be done.
References[1] PCH Mitchell, SF Parker, AJ Ramirez-Cuesta
and J Tomkinson “Vibrational Spectroscopy with
Neutrons” World Scientific, London, (2005).
[2] Ramirez-Cuesta, AJ;et al; Journal Of Materials
Chemistry, 17: 2533 (2007)[3] Ulivi, L; Celli, M; Giannasi, A; Ramirez-Cuesta,
AJ; Bull, DJ; Zoppi, M, PRB, 76: 161401 (2007)[4] Ramirez-Cuesta, A. J.; Mitchell, P. C. H.
Catalysis Today 2007, 120 (3-4), 368-373.

Fig 1. The INS spectra of hydrogen in HKUST asfunction of loading, 4 different sites are apparent; thepopulation is monitored by the area of each peak.

[5] AJ Ramirez-Cuesta, MO Jones, WIF David,
Materials Today, 12, 2009, 54-61.

AJ (Timmy) Ramirez-Cuesta is Senior Instrument Scientist of the TOSCA spectrometer at the ISIS
Facility, Rutherford Appleton Laboratory in the United Kingdom. He has been working on
computational modeling of experimental data for over 25 years and has been involved in the use ofneutrons for over a decade. Scientific interests are: Lattice Dynamics Calculations. Characterizationof hydrogen storage systems, metal hydrides and porous materials using Inelastic Neutron
Scattering and ab-initio Computational methods. Interactions of molecules with surfaces. Modelingof surface reactions and catalysis using classical and quantum methods.
Timmy
Corresponding author: AJ (Timmy) Ramirez-Cuesta, timmy.ramirez-cuesta@stfc.ac.uk, Tel.+44 1235 446510

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CATALYSIS BY METATHESIS
E. Callini1, A. Borgschulte1, A.J. Ramirez-Cuesta2, B. Probst1, A. Züttel1
12

Empa, Swiss Federal Laboratories for Materials, Testing and Research, CH-8600 Dübendorf, Switzerland
ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, United Kingdom

Understanding complex hydrides decomposition paths is a crucial issue to store hydrogen. Through the information we
can get from such an analysis, tuned and focused attempts to obtain their reversibility can be possible. Here we present
combined thermogramivetric (TG) and infra-red (IR) measurements which shed a new light on the problem. The supportof the computational modelling is complementary to determine the decomposition reaction. The system underinvestigation is Ti(BH4)3 which is an interesting room temperature liquid complex hydride.

Hydrogen in Complex Hydrides
The storage of hydrogen in liquid complex hydrides is an
attractive option, since these materials contain up to 20
wt% of hydrogen [1]. Synthesis and handling thesematerials is not simple. This therefore yields to difficulties
in their characterization and the identification of thedecomposition reactions with particular emphasis on
gaseous products.

Combined TG-IR measurements
The method presented here is an innovative combinationof different techniques and approaches [2]. The weightloss associated with the release of hydrogen is monitored
by a thermogravimetric balance, while the decomposition
gas is detected by an infrared spectrometer, which gives
a quantitative measure of the amount of each gas
component. In this way we provide a real time in situ
composition analysis of the desorption gas.

Ti(BH4)3
One of the most promising materials in the class of theroom temperature liquid complex hydrides is the Ti(BH4)3,
since it can store around the 13 wt% of hydrogen.
We investigated metasynthesis of Ti(BH4)3 by ball milling
powders of TiCl3 and LiBH4 or by adding TiCl4 (liquid) tothe powder of LiBH4. In the case of the liquid-solidsynthesis, the initial emission of diborane and HCl isalmost suppressed by the emission, at around 45 °C, ofTi(BH4)3. In the solid synthesis the emission of Ti(BH4)3starts already at room temperature (see the IR spectra in
the picture) and most likely the detected diborane is aneffect of the decomposition of Ti(BH4)3. The difficulties indetecting the Ti(BH4)3 are due to the fact that we found it
to be an extremely unstable compond: it decomposes
within few hours at RT.

This observation and the computational modelling mayconnect this system to the role of Ti halides frequently
used as additives to enhance desorption kinetics. The
exchange of Ti-ions with Li-ions may catalyse thedesorption of LiBH4 via the intermediate formation ofTi(BH4)3:
nLiBH4 + TiCl3 => Ti(BH4)3 +3LiCl + (n-3)LiBH4 =>3(B+3/2 H2) + Ti(BH4)3 + 3LiH + 3LiCl + (n-6)LiBH4
This reaction cannot be reversed, and thus TiCl3 does not
catalyse effectively for absorption, in good agreementwith empirical data. We demonstrate the required highionic mobility by exchange experiments.

References[1] A. Züttel, A. Borgschulte, L. Schlapbach, (eds.)
Hydrogen as a Future Energy Carrier, Wiley-VCH,
Heidelberg 2008
[2] A. Borgschulte, et al., J. Phys. Chem. C, 2011, 115(34), pp 17220–17226

Born 13.1.1982 in Varese, Italy. In 2011 she graduated in Physics in Bologna, Italy, with Prof. E.
Bonetti. During her studies she collaborates with the Danish Technical University in Copenhagen,Denmark, with Prof. T. Bohr; the Department of Chemistry of the Aarhus University in Denmark, with
Prof. T. R. Jensen and with the California Institute of Technology in Pasadena (CA), with Prof. B.
Fultz and Dr. C. Ahn. Since 2011 she is PostDoc in the Complex Hydrides Group in the Laboratory
Hydrogen & Energy at Empa, Dübendorf, Switzerland.
Elsa Callini
Corresponding author: Elsa Callini, elsa.callini@empa.ch, +41 587654933.

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6th Int. Symposium Hydrogen & Energy

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Hydrogenation of CO2 on the hydride surface of Mg2NiH4

Shunsuke Kato,1 Michael Bielmann,1 Benjamin Probst,1 Riccardo Suter,1 Davide Ferri,2Andreas Borgschulte,1 Andreas Züttel1
1Empa, Laboratory for Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2

Empa, Laboratory for Solid State Chemistry and Catalysis, CH-8600 Dübendorf, Switzerland

This study focuses on a catalytic property of the hydrogen-rich surface of a hydride in the hydrogenation reactions ofCO2. The surface processes on Mg2NiH4 were investigated by in situ X-ray photoelectron spectroscopy (XPS) combinedwith thermal desorption spectroscopy (TDS) and mass spectrometry (MS). The hydrogenation reactions of CO2 on the
hydride surface were analyzed by means of catalytic activity measurement with a flow reactor, a gas chromatograph(GC) and MS. The hydrogen-deuterium exchange measurements evidence the interactions of the gas molecules CO2,CH4 and H2O with the hydride surface. Dissociation of H2 molecules is not the rate controlling step on the hydride
catalyst. From the viewpoint of catalyst preparation, this study implies great potential for reutilization of hydrogen storage
alloys as a CO2-reduction catalyst.

Introduction
The way towards a chemical energy carrier fromrenewable energy may be taken via two strategies: thefirst one develops technologies to make hydrogen fromwater the novel energy carrier; the second is theimplementation of processes for the production of
established fuels such as hydrocarbons from CO2, waterand renewable energy [1,2]. Interestingly, many scientificquestions in hydrogen storage have their counterpart inthe catalytic processes during the synthesis ofhydrocarbons from hydrogen and CO2.[3] In this study
the catalytic interactions of the hydride surface of
Mg2NiH4 with CO2 during the hydrogen desorption wasinvestigated and the surface processes were studied ingreat detail in the view of a novel class of methanation
catalysts on one hand, and to understand the poisoning
processes on surfaces of Mg2Ni when exposed tocontaminated hydrogen on the other.

Surface properties
The formation of surface oxide layers on Mg2NiH4 upon
exposure to CO2 hinders the decomposition of thehydride. The surface oxidation is accompanied bysegregation of Mg oxides and Ni at the disproportionatedsurface on Mg2NiH4X. The active Ni sites at the surface
are associated with the ready dissociation of hydrogenmolecules and subsequentintermetallics Mg2Ni.

hydrogenation

of

the

Hydrogenation reaction of CO2 on Mg2NiH4The In the CO2 hydrogenation process on the hydridesurface, the hydrogen desorption does not determine thereaction rate but the dissociative adsorption of CO2
molecules on the hydride facilitates the rate ofmethanation. The precipitated Ni-clusters on the oxidized
surface are attributed to the catalytic activity of thehydrides surface, i.e. for dissociative adsorption of CO2
molecules and their subsequent hydrogenation. The
continuing disproportionation reaction of the hydride
induces a rough surface structure. As more and more Ni
particles are formed during decomposition, the modified
surface becomes further active in the CO2 methanation.

References[1] A. Züttel, A. Remhof, A. Borgschulte, O. Friedrichs,
Phil. Trans. R. Soc. A, 2010, 368, 3329.
[2] C. Graves, S. D. Ebbesen, M. Mogensen, K. S.
Lackner, Renewable and Sustainable Energy
Reviews, 2011, 15, 1.
[3] W. E. Wallace, Chemtech, 1982, December, 752.

Born 10. 6. 1976 in Ise, Japan. 2005 Master of Engineering in Applied Science, Tokai University,
Japan. Research into gas-solid reactions: reactivity of gases (H2, O2, H2O) with metal surfaces underultrahigh vacuum condition. 2005-2007 NEDO research assistant at Tokai University, Japan,"Advanced metal hydrides with high volume density of hydrogen". Since 2007 PhD student at Empa,
Div. Hydrogen & Energy, and University of Fribourg, Switzerland.

Shunsuke Kato
Corresponding author: Shunsuke Kato, email: mailto:shunsuke.kato@empa.ch, Tel. (+41) (44) 823 4327

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LiBH4-based composites with metal hydrides and fluorides forhydrogen storage
Pei Pei Yuan and Bin Hong Liu
Dept. of Materials Sci. & Eng., Zhejiang University, Hangzhou 310027, P.R. China

Abstract
LiBH4-based reactive composites are promising hydrogen storage materials. In this study,
we developed a new composite based on 6LiBH4+CaF2. It has a theoretical hydrogen capacity of
9.6 wt% and a slightly decreased thermodynamic stability compared with pure LiBH4. The newcomposite demonstrated good reversibility in spite of the hydrogen back pressure during
dehydrogenation. Further comparative studies of four composites 6LiBH4+CaX2 and
2LiBH4+MgX2 (X=H and F) revealed their similarities and differences in hydrogen storage
properties. In general, the composites with fluorides had similar hydrogen storage properties withthose containing corresponding hydrides. However, LiBH4/MgX2 and LiBH4/CaX2 (x=F, H)
demonstrated large differences because the hydrogen storage performance of LiBH4/MgX2 showeda strong dependence on hydrogen back pressure. The structural difference between MgB2 andCaB6 may partially account for the observed phenomena for these LiBH4-based composites.

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INCREASING HYDROGEN DENSITIES OF METAL HYDRIDESBY USING CONTINUOUS TRANSFORMATION INTOCOMPLEX HYDRIDES
Guan-Qiao Li1, Nao Hiyama1, Mika Kano1, Shigeuyki Takagi1, Motoaki Matsuo1,
Satoshi Semboshi1, Kazutoshi Miwa2, Shin-ichi Orimo1
1
2

Institute for Materials Research, Tohoku University, Sendai, 980-8577, Japan
Toyota Central R&D Laboratories, Inc., Nagakute 480-1192, Japan

Recent experimental and computational results on YMn2 hydrides provide us a new guideline for designingadvanced hydrogen storage materials, that is, “increasing hydrogen densities of metal hydrides by using
continuous transformation into complex hydrides”.

Background on YMn2 hydrides
Hydrogenation of YMn2 has been studied
because hydrogen induces strong modifycations in its materials properties. Afterhydrogenation at ambient hydrogen pressures and temperatures, YMn2Hx shows acontinuous increase in the cubic cellparameter up to x = 3.5, a two phase range
with a mixture of cubic and rhombohedralphases for 3.5 < x < 4 and a rhombohedralphase for 4 < x < 4.5 [1-3]. Wang et al. andPaul-Boncour et al. have reported that x
reaches 6 when the hydrogenation is carriedout at a high hydrogen pressure of 170 MPa
at 473 K for 12 h [4,5].

Low-pressure
hydrides [6]synthesis

of

YMn2

First-principles calculations were performed
for a complex hydride YMn2H6 to investigate
its electronic structure and thermodynamic
stability. Based on the enthalpy change of−65 kJ/mol estimated from the calculation,
we experimentally verified a possible lowpressure synthesis of YMn2H6 from a metal
hydride YMn2H4.5. X-ray diffractometry
confirmed the formation of YMn2H6 afterhydrogenation below 5 MPa (at 423 K for 12h).

A new guideline for hydrogen storage
materials [6]Further studies should provide us with uniqueguidelines for designing advanced hydrogenstorage materials; increasing hydrogendensities of metal hydrides by using continuous transformation into complex hydrides.
This research was funded by Funding
Program for Next Generation World-Leading
Researchers (GR008) and the Integrated
Project of ICC-IMR.

References[1] J. Przewoznik et al., JALCOM 225, 436 (1995).
[2] M. Latroche et al., JALCOM 274, 59 (1998).
[3] V. Paul-Boncour et al., Faraday Discuss.
151, 307 (2011).
[4] C.-Y. Wang et al., Solid State Commun. 130,815 (2004).
[5] V. Paul-Boncour et al., J. Solid State Chem.
178, 356 (2005).
[6] M. Matsuo et al., APL 98, 221908 (2011).

Born 11. 2. 1966 in Hiroshima, Japan. 1993-1995 JSPS Research Fellow, 1995
Ph.D. degree, 1995-2002 Research Associate, in/from Hiroshima University.
1998-1999 Guest Researcher in Max-Planck Institute for Metal Researchawarded Alexander von Humboldt Fellowship and MEXT Fellowships. 2002
Associate Professor, Institute for Materials Research (IMR), Tohoku University.
2010 Full-Professor, Head of the Section and Deputy of the Research Center“Integrated Materials Research Center for a Low-Carbon Society (LC-IMR)”.
http://www.hydrogen.imr.tohoku.ac.jp/

Shin-ichi Orimo
Corresponding author: Shin-ichi Orimo, Email: orimo@imr.tohoku.ac.jp, Tel. (+81) (22) 215 2093

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ACTIVATED SiO2-BASED MATERIALS FOR HYDROGEN STORAGE
Liga Grinberga, Andris Sivars, Janis Kleperis
Institute of Solid State Physics, University of Latvia, Kengaraga Street 8, Riga, Latvia
SiO2 based materials (glass, zeolite) under normal conditions are not absorbing hydrogen in notable amounts. We used
extractive-pyrolytic method to activate glass and natural clinoptilolite zeolite with palladium nano-particles. Ion exchange
method was applied to adjust natural clinoptilolite for hydrogen storage. The volumetric and thermogravimetric methods
were used to study hydrogen absorption in samples at room and elevated temperatures and hydrogen pressures up to
10 bars. Different amount of sorbed hydrogen in the investigated samples is observed although it varies by method usedin the experiments.

Experimental
SiO2 based samples in the form of composite materials
used in this research consist of Pyrex glass (PG), SiO2
glass (SiO2), silica gel (SG), zeolite (ZE), and palladium(Pd). Palladium nanoparticles with nominal metal loadingfrom 1.25 to 10 wt% onto carrier powders (PG, SiO2, SG,ZE) were prepared by extractive-pyrolytic method [1].
Hydrogen sorption experiments were performed with
PCTPro-2000 (SETARAM). Initial treatment of thesamples includes vacuuming and annealing at 200°C for
1h and cooling to 26°C. Differential thermogravimetricanalysis was performed on Shimadzu DTA-60. Afterinitial heat treatment the samples were heated up to 200
oor 300 C at the rate 10 deg/min in argon atmosphere,
and cooled down to room temperature in hydrogen
atmosphere at the rate 5 deg/min. Both argon andhydrogen were supplied with flow rate 50 ml/min.

Results
XRD and SEM analysis of silica/Pd based composite
materials showed that not only the pure nanocrystalline
Pd but also PdO are located on the external surfaces ofsilica based material nanoparticles. BET surface analysis
showed that porous silica gel and zeolite has
considerably larger specific surface area than Pyrex and

SiO2 glass. It can be assumed that the material withlarger surface area absorbs more hydrogen due to thegreater amount of potential interaction sites that would be
exposed to hydrogen. However, hydrogen sorption
kinetic measurements with volumetric method showedthat the materials with the less specific surface areaabsorb more hydrogen than the other ones. Potential
explanation is related with the spill-over effect [2]. The
results of thermogravimetric results show that the massof zeolite activated with 1.25 wt% Pd is increasing by 4-5
wt%. This work demonstrates the possibility to use silica
based materials doped with palladium for hydrogenstorage.

Acknowledgements
Authors acknowledge the ERDF Projects No.
2010/0204/2DP/2.1.1.2.0./10/APIA/VIAA/010. and2010/0188/2DP/2.1.1.1.0/10/APIA/VIAA/031.

References[1] V.Serga, M.Maiorov, A.Petrov, A.Krumina (2009),
Integrated Ferroelectrics, No.103 (1), p. 18-24.
[2] L.Grinberga, J.Kleperis, G.Bajars, G.Vaivars, A.Lusis(2008), Solid State Ionics 179, p. 42-45.

A. Sivars is the 3 grade bachelor student of the faculty of Physics and Mathematics, University ofLatvia. Currently works also in the Institute of Solid State Physics, University of Latvia, in the
Laboratory of Hydrogen and energy technology materials. Already is co-author of the 3 conference
thesis and 2 articles.

Andris Sivars
PhD degree in Material Sciences of University of Latvia, works in the in the Institute of Solid State
Physics, University of Latvia, in the Laboratory of Hydrogen and energy technology materials since1999. The scientific research topic has changed from gas sensors and electronic nose to thehydrogen storage materials on 2004. The title of the PhD thesis: ‘New materials for hydrogenstorage’ where the investigated material was composite of AB 5 and glass. She is author and coauthor of more than 20 articles and 1 book chapter.
Liga Grinberga
Corresponding author: Liga Grinberga, email: Liga.Grinberga@cfi.lu.lv, Tel. +371 67262145

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GAS RELEASECOMPOSITESFROMStoos, Switzerland 2012

(H,D)

ISOTOPELABELED

2LiBH4/MgH2

W. Lohstroha,b, N. Boucharatb, E. Gil Bardajib, M. FichtnerbaForschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universität München, 85747 Garching,b
Germany, Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
The decomposition of (H,D) isotope labeled 2LiBD4+MgH2 and 2LiBH4+MgD2 composites has been investigated using
thermogravimetry, differential scanning calorimetry and mass spectrometry. Significant isotope scrambling is observed
once the decomposition process has started. For samples 2LiBD4 + MgH2 the majority gas species is D2 while
2LiBH4+MgD2 predominantly emit HD. The addition of Ti-isopropoxide does not change the ratios.

Introduction
The 2 LiBH4+MgH2 composites are intensely investigatedas hydrogen storage material. Hydrogen release occurs
in a two step reaction:
2LiBH4+MgH2 -> 2LiBH4+Mg + H2 -> 2LiH + MgB2 +4H2
and in total 10.5 wt% H2 are released [1,2]. Additions of
Ti-isopropoxide improve the kinetics of hydrogen releaseand ameliorate reversibility of the system. This
improvement is thought to be due to the formation of TiB2
acting as nucleation site of MgB2 during desorption [3-5].
The formation of MgB2 (instead of amorphous boron) has
been identified as crucial point for the reversibility of thesystem. To further elucidate the rate limiting factors of thedecomposition reaction and the effect of the Tiisopropoxide additive we studied the gas release in
isotopically labelled samples 2LiBD4 + MgH2 and 2 LiBH4+ MgD2.

Experimental and Results
LiBH4 (Sigma-Aldrich, 95%), LiBD4 (KatChem 98%),
MgH2 (Alfa Aesar,98%) and Ti-isopropoxide (Alfa Aesar)
were obtained commercially. MgD2 was produced bycycling commercial MgH2 in a Sieverts’ apparatus under
D2 gas. High energy ball-milling (Retsch PM400 planetarymill) at a 400 rpm rotation speed has been used to
produce the nanocomposites. For the additive freesamples premilled LiB(H,D)4 and Mg(H,D)2 were mixed
and ball milled together for 13 h. Ti-isopropoxide doped
samples have been prepared by mixing premilledMg(D,H)2 powder with 5 at% Ti-isopropoxide for 13h andsubsequently mixing it with premilled LiB(H,D)4 foradditional 5h. The gas release was studied using
thermogravimetry, differential scanning calorimetry andmass spectrometry (Sensys Evo, Setaram, and DSC 204
HP Netzsch), XRD and FTIR were used to study thephase composition.
Significant isotope scrambling is observed once thedecomposition has started: samples 2 LiBH4 + MgD2
release predominantly HD while the majority gas species
for 2LiBD4 + MgH2 is D2. Above T>400°C, the relative
ratio of the gas species D2, HD and H2 remains constant.
For Ti-isopropoxide samples gas release is shifted tolower temperatures but the gas species distribution issimilar compared to the undoped case. The results
indicate that H/D exchange during decomposition iseasily possible and we propose the following model forthe initial step for the decomposition: hydrogen (either H
or H2) released from magnesium hydride gets scrambled
with the more abundant gas species either at the
MgH2/LiBD4 interface or during diffusion through theliquid LiBD4 layer.

References[1] J.J. Vajo et al. Physical Chemistry Letters B 109,
2005, 3719-3722[2] U. Bösenberg et al. Acta Mater. 55 (2007) 3951–3958[3] U. Bösenberg et al Acta Materialia 58 (2010) 3381–
3389[4] E. Deprez et al. Acta Materialia 58 (2010) 5683–5694[5] E. Deprez et al. J. Phys. Chem. C 114 (2010) 3309–
3317

1996 Diploma in Physics, Georg-August Universität Göttingen, Germany 1999 Dr. rer. nat. from thescience faculty Georg-August Universiät Göttingen, Germany 2000 Post Doc at the Clarendon
Laboratory, Condensed Matter Physics, Oxford University 2003 Post Doc at the Department of
Physics and Astronomy, Condensed Matter Physics at the Vrije Universiteit Amsterdam, The
Netherlands 2005 Research Staff at the Institute of Nanotechnology, Karlsruhe Institute ofTechnology
2011
Instrument
ScientistatTechnische
Universität
München,Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM2)
Wiebke Lohstroh
Corresponding author: Wiebke Lohstroh, wiebke.lohstroh@frm2.tum.de, Phone: 49 (0)89 289 14735

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6th Int. Symposium Hydrogen & Energy

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ESEM AND RAMAN MAPPING OF POLYPHENYLENE SULPHIDE/POLYSULFONE / OLIVINE DIAPHRAGMS
Michal Gorbar1,2, Marcus Pohl1,3, Andreas Borgschulte1, Ulrich F. Vogt1,5, Ernest
Burkhalter4 and Andreas Züttel1,2
1

EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland

2

University of Fribourg, Dept. of Physics, Fribourg, Switzerland

3

University of Applied Science, Faculty of Chemical Engineering, Münster, Germany

4

IHT, Monthey, Switzerland

5

Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

PPS-PSU-olivine diaphragms were manufactured and investigated aiming at replacing chrysotile-asbestos diaphragms inalkaline electrolysers. The chemical information was drawn from a mapping of the specific Raman transitions of olivine,
polysulfone and polyphenylene sulphide with a spatial resolution of around 3 mm. The interval between the measured
spots was chosen 5 mm in x- and y-direction. The distribution of the molar fraction of the three components is visualizedusing contour plots calculated from intensities of the integrated areas. Environmental scanning electron microscopy wasapplied to qualitatively investigate the drying effects on the structure of investigated specimens.

Introduction
The efficiency of alkaline electrolysis is highly influenced
by the properties of the diaphragm, responsible forseparating hydrogen and oxygen gases. Traditionallyused asbestos diaphragms fulfill these requirements
thanks to their hydrophilicity, fibrous structure andspecific porosity. This material is undesired because of
the health hazards caused by asbestos. Thus new typesof porous materials are being developed to substituteasbestos fabrics, based on inorganic-organic composites.

Processing
Polyphenylene sulphide (PPS) felts with a thickness of 3
mm were twice infiltrated and impregnated by a mixtureof olivine (Mg,Fe)2SiO4 and (PSU) polysulfone, dissolvedin an aprotic solvent N-methyl-2-pyrrolidone in the ratio of
5:2:48. Subsequently they underwent the phase inversion

Michal Gorbar

process in a non-solvent bath (distilled water) for 72
hours and are kept moist until have been used for theseveral characterisation methods.

Results
The Raman mapping of the diaphragms enables a better
understanding of segregation effects between theindividual compounds within the matrix. The preferredbinding of the PSU/Olivine to the PPS matrix is reducedby the infiltration with olivine water based slurry, leading
to a mechanical instable structure. A repeated
impregnation leads to stable samples, even though aminor segregation is achieved. Environmental SEM
imaging allows to qualitatively indicating the drying effecton the microstructure. The analysis revealed that upon
removal of water, structure deformation occurred as aresult of the segregation of the olivine/polysulfone bodypacking within polyphenylene sulphide matrix.

Born 14. 11. 1982 in Levoca, Slovakia. 2001 – 2007, study of chemistry at the Comenius University
in Bratislava. 2006 - 2007 Master Thesis "TiO2 surface modified ceramic foams for catalytic
applications" at Empa, Dept. of High Performance Ceramics. In 2007 graduated as Master of
Science in inorganic chemistry. 2007 - 2008 employee of Empa, at the Dept. of Internal Combustion
Engines and High Performance Ceramics in Dübendorf, Switzerland. Research focused on
production and development of ceramic foams as a support for catalytic materials. 2008 - 2011, PhD
student at University of Fribourg and in the Laboratory "Hydrogen & Energy" at Empa, Dübendorf.
Involved in the CTI project (NMAE2), BFE & SwissElectric project and EU project ELYGRID until
present.

Corresponding author: Michal Gorbar, Michal.gorbar@empa.ch, Tel. (+41) (58) 765 4301

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IMPROVED HYDROGEN SORPTION KINETICS IN SUPPORTED MG2CU
NANO-PARTICLES
Yuen S. Au, Petra E. de Jongh
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University,
Universiteitweg 99, P.O. Box 80083, 3508 TB Utrecht, The Netherlands
Supported nano-particles of Mg2Cu on different types of carbon were synthesized and the kinetic and thermodynamic
properties for hydrogen sorption were investigated. Smaller crystallites (~50 nm) and better hydrogen desorption kinetics
0were observed by using porous carbon as support material. A temperature shift of 150 C for hydrogen release wasobserved with temperature programmed desorption under Ar-flow. Results from cycling experiments performed
gravimetrically showed that the improved desorption kinetics were maintained.

Introduction

Material and hydrogen sorption properties

Reversible hydrogen storage in metal hydrides isfavorable with regard to safety and volumetric storage
density. The Mg2Cu-H system can reversibly storehydrogenfollowingthereaction:
2 Mg2Cu + 3 H2 ↔ 3 MgH2 + MgCu2. The equilibrium0
temperature for H2-sorption in this system is 240 C at 1bar H2. Nano-sizing and confinement improve the kinetics
and reversibility of hydrogen sorption reactions in lightmetal hydrides [1]. We investigated the hydrogen release
andreversibility
fordifferent
carbon-Mg2Cu
nanocomposites.

The smallest crystallites were obtained with porous
carbon (a) with an average size of 50 nm according to
XRD. SEM, performed in BSE mode, confirmed thepresence of the small crystallites. The sample preparedon graphite (b) yielded significant larger crystallites (>200nm). Sample a prepared on porous carbon releasedhydrogen at much lower temperatures than the othersamples. This is likely due to the decrease in diffusion
distance for hydrogen and/or increased specific surface
area of the Mg-Cu crystallites.

Preparation

Hydrogen Release(a) Mg2Cu with porous carbon

Normalized Flow H2 (ml/min.g)

Mg2Cu species were prepared on porous and non-porousgraphitic carbon supports. We first impregnated thecarbon with a Cu(NO3)2 solution. After decomposition of
the nitrate and reduction, supported metallic Cu particles
were obtained. Mg2Cu was formed by adding MgH2 to the
Cu-carbon composition and heating the mixture to themelting temperature of Mg.

(b) Mg2Cu with non-porous graphite(c) Mg2Cu physical mixture with porous carbon
(b)

(a)

150

200

250

300

350

(c)

400

450

0

Temperature ( C)

Fig. 2: Temperature programma desorption measured under 25
ml/min Ar-flow at 10 0C/min.

Acknowledgements
We acknowledge NWO (Vidi grant 016.072.316) for
financial support.
Fig. 1: SEM image in BSE mode of Mg2Cu particles on porous
carbon (a) and non-porous graphite (b).

References[1] De Jongh, P.E., Adelhelm, P., ChemSusChem, 13321348 (2010)

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Born in The Netherlands. 2007 Bachelor degree in Chemistry (Leiden University). 2009 Master
degree in Chemistry (Leiden University). 2010-present PhD-student in the group of Inorganic
Chemistry and Catalysis, Utrecht University.

Yuen Au
Corresponding author: Yuen Au, email: y.s.au@uu.nl, Tel. (+31) (6) 22736385

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HYDROGENATION OF CARBON MONOXIDE OVER NANOSTRUCTUREDSYSTEMS: MECHANOCHEMICAL APPROACH
Gabriele Mulas1, Renato Campesi2, Sebastiano Garroni1, Francesco Delogu3, Chiara
Milanese4
1

Department of Chemistry, University of Sassari and INSTM, via Vienna 2, I-07100 Sassari, Italy

2

JRC-IET, westerduinweg 3, Petten 1755 ZG, The Netherlands

3

Department of Chemical Engineering and Materials, University of Cagliari, piazza d’Armi, I-09123 Cagliari, Italy

4

C.S.G.I & Department of Chemistry, Physical Chemistry Section, University of Pavia, Viale Taramelli 16, I-27100 Pavia,
Italy

Abstract: In this study we investigated the mechanochemical hydrogenation of carbon monoxide over nanostructured
FeCo- and Mg2Ni-based catalysts. To this aim, powdered materials prepared by mechanical alloying were subjected tomechanical treatment under CO/H2 (1:3) atmosphere. A methodology to evaluate the activity of the solid catalysts on an
absolute basis was developed. Conversion data were, indeed, expressed as turnover frequency, TOF, and related to theoccurrence of ball to powder collision events through the mechanochemical turnover frequency parameter, MTOF.
Differences in the catalytic activity and selectivity were observed for the two FeCo-based studied systems, the solid
solution Fe50Co50 and its dispersion on TiO2 support. As for the Mg2Ni system, we explored the possibility to estimate thespecific role of hydrogen pre-activation step. The catalytic properties of the mechanically alloyed Mg2Ni system werecompared with the conversion data shown by the same system pre-hydrogenated and subsequently milled under CO
atmosphere

Introduction We propose a methodology to describe,
on a quantitative basis, chemical processes at the gas–solid interface promoted by mechanical treatment. The
experimental set up, as well as the developed
procedures, were applied to the study of thehydrogenation process of carbon monoxide (CO), carriedout over multi-component metal alloys and hydrides. This
process, well known as Fischer–Tropsch (FT) synthesis,
has had particular relevance in the industry in the postwar period [1], and nowadays it is receiving increasing
attention for environmental issues and potential
applicative purpose in a clean energy scenario. In aclassical scheme of the FT reaction activated byconventional thermal treatment, hydrogen and carbon
monoxide react over supported transition metal catalysts
to yield saturated hydrocarbons, olefins and oxidized
products. Such consideration prompted us to select, as
catalysts, the cited systems for which recent literature
data are available [2].

Experimental
The catalytic properties of different systems, i.e.
Fe50Co50, FeCo supported on TiO2 (FeCo)/(TiO2) andMg2Ni were investigated. All the samples weresynthesized by mechanical treatment: by using acommercial
Spex
mixer/mill
model
8000.
Mechanochemical carbon monoxide hydrogenation runs
were performed over 8 g of catalyst powders.
Experiments were carried out in batch, inside a stainlesssteel cylindrical reactor, with two pressure valves allowing
the inlet and outlet of gases. The reactor was connectedwith an external gas reservoir where the desired gaseous
mixture was prepared. In particular, the powders of all thesystems were exposed to a CO:H2 gaseous mixture in
the molar ratio 1:3. a. Moreover, the reactor temperature
was kept at 300 K and the frequency of reactor

displacement at 14.6 Hz. The conversion rate and theselectivity of the CO hydrogenation were monitored bygas-chromatography (GC). Hydrogen and carbon
monoxide gases were detected using a Fisons 8000
apparatus equipped with a Hot Wire Detector, whereashydrocarbons were analyzed by a Perkin-Elmer 8600
apparatus equipped with a Flame Ionization Detector.

Results The methodology presented in this work
allowstocompareonanabsolutebasis
mechanochemical conversion data with the results ofheterogeneous catalytic tests carried out underconventional thermal activation conditions. Results of CO+ H2 synthesis over FeCo based catalysts indicated thatmechanochemical processes, characterized by mild
conditions (room temperature, and near to atmosphericpressure), displayed conversion data similar or better
than the corresponding thermally activated reactions,performed under severe conditions (400–800 K, 2–5
MPa). Further improvement in conversion data andkinetics was observed in the CO conversion overhydrides. The quantification of such effect allowed to gain
some hints of the reaction mechanism, and may open
some potential perspective for the application of thestudied process in a future hydrogen-based energy
scenario

References[1] R.B. Anderson, The Fischer-Tropsch Synthesis,
Academic Press, Orlando, 1984.
[2] D.J. Duvenhage, N.J. Coville, Appl. Catal. A 153(1997) 43.

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Was born in Olbia, Sardegna, Italy on the 15-01-1981
Graduated in Chemistry at the Universita’ di Sassari in 2005
PhD in Engineering Science and Environment, Universite’ de Paris-Est in 2008
RenatoCampesiCurrently working as a researcher at the JRC-IET in Petten, the Netherlands

Corresponding author: Renato Campesi, renato.campesi@ec.europa.eu, Tel. +31224565228

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6th Int. Symposium Hydrogen & Energy

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THE ENERGY DENSITY OF HYDROGEN STORAGE MATERIALS
Andreas ZÜTTEL
EMPA Materials Science & Technology, Dübendorf, Switzerland
Renewable energy occurs in energy fluxes while fossil fuels are energy carriers with an energy density of 13 kWh/kg and
10’000 kWh/m3. Therefore, a synthetic energy carrier has to be produced in order to store and transport the renewableenergy, i.e. match the conversion with a typical intensity of 100 W/m2 and the demand 20 W/m2 (for heating) to MW/
capita for transport in an airplane. Hydrogen exhibits an energy density of 39 kWh/kg but a very low volumetric energy
density. The goal is to develop a hydrogen storage system with a similar energy density as compared to fossil fuels, e.g.
synthetic hydrocarbons produced from CO2 from the atmosphere and hydrogen from water and renewable energy.

Energy carriers

HydridesThe economy in the industrialised world is mainly basedon open materials cycles, i.e. mining the ore, produce a
product and deposit or burn the wast. This systems notsustainable and needs to be converted into an economy
based on closed cycles. Especially the energy carriers
are produced from renewable energy and used in aclosed cycle, e.g. hydrogen is produced by electrolysis
from water and electricity, stored, used in a fuel cell,
turbine or internal combustion engine and finally releases
water to the atmosphere.

The hydrogen density in hydrogen storage materials is
limited to <25 mass% and <150 kg/m3 [1]. The resulting
energy density is therefore limited to 6 kWh/kg and 5’000
kWh/m3 on a materials basis, without oxidation of thehost material. Furthermore, the application of hydrogenstorage materials requires a tank system, which reduces
the hydrogen density to approx. 50% of the hydrogendensity in the host material itself.

A system using the oxygen from the atmosphere andreleasing the product of the combustion into theatmosphere exhibits a ten times greater energy density
compared to a closed system e.g. battery. Considering
the Carnot efficiency of the combustion (<40%)compared to the Gibbs free enthalpy of an electrochemical system (>80%), the theoretical maximum
energy density of a combustion is still 5 times the energy
density of a battery (1 kWh/kg and 1000 kWh/m3).

Synthetic hydrocarbons
Only few molecules exist in a significant concentration
and are transported in the atmosphere without negative
effects on the living matter, i.e. N2, O2, H2O and CO2.
Therefore the only synthetic energy carriers, with anenergy density comparable to the fossil fuels arehydrocarbons and ammonia as well as compounds ofnitrogen, carbon and hydrogen. These materials lead towater, carbon dioxide and nitrogen upon oxidation. The
main challenge is to efficiently synthesize the energy
carriers from the products in the atmosphere by means ofheat and electricity from renewable sources, i.e. sun,geothermal and tide. The extraction of CO2 from theatmosphere requires thermodynamically very little energy( 0.2 kWh/kg CO2) but with todays technology consumesa significant amount of the energy stored in the form ofcarbon. Furthermore, the co-electrolysis of H2O and CO2
on the same electrode, the electrochemical synthesis ofammonia and the activation of CH4 would open new
efficient pathways for the production of synthetic fuels.

References[1] A. Züttel, A. Remhof, A. Borgschulte and O.
Friedrichs, “Hydrogen: the future energy carrier”, Phil.
Trans. R. Soc. A 368 (2010), pp. 3329-3342
Fig. 1. Energy density of fossil fuels, hydrogen in various
forms, hydrocarbons and batteries.

Andreas ZÜTTEL

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf, Switzerland. Exchange
student Dow Chemical in Terneuzen, Netherlands. 1990 Diploma in Physics from the Unversity of Fribourg(UniFR), Switzerland. 1993 Dr. rer. nat. from the science faculty UniFR. 1994 Post doc AT&T Bell Labs in Murray
Hill, New Jersey, USA. 1996 Head of the Metalhydride Group at the UniFR. 1997 Lecturer at the Physics
Department UniFR. 2003 External professor at the Vrije Universiteit Amsterdam, Netherlands. 2004 Habilitationin experimental physics at the science faculty UniFR. President of the Swiss Hydrogen Association„HYDROPOLE“. 2006 Head of the section “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics department
UniFR. 2009 Guest Professor at IMR, Tohoku University in Sendai, Japan

Corresponding author: Andreas ZÜTTEL, email: andreas.zuettel@empa.ch, Tel. +41 58 765 4038; m: +41 79 484 2553

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6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012

SORPTION ENHANCED METHANATION OF CO2
Riccardo Suter, Andreas Borgschulte, Shunsuke Kato, Benjamin Probst, Andreas Züttel
Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
The reduction of CO2 by hydrogen eventually forming hydrocarbons depends on the interaction of CO2 and H2 with acatalyst surface, i.e. ad- and desorption of hydrogen, CO2 and products [1]. A significant increase of the process
efficiency is possible by the so-called sorption enhanced reaction. The desorption reaction is strongly enhanced by theremoval of water by its absorption in the inner bulk of a sorption catalyst (see picture). As a proof-of-concept, an
improvement of the reaction yield of more than 100% of the Sabatier was realized using Ni-zeolite sorption catalysts.

Sorption enhanced reaction
The Sabatier reaction
CO2 + 4 H2 <=> 2 H2O + CH4
is strongly enhanced by the removal of water by its
absorption in the inner bulk of a sorption catalyst. As aproof-of-concept, an improvement of the reaction yield of
more than 100% of the Sabatier was realized using Nizeolite sorption catalysts [1].

reactor with a diameter of x cm and a length of x cm. At
the outlet nitrogen is added to dissolve the gas tooptimize the signal to noise ratio in the coupled FTIRspectrometer. To avoid water condensation in the IR cella cool trap with ice water was installed before thespectrometer.

Cat Preparation and Characterization
Catalysts were prepared by ion exchange using different
zeolite precursors with Nickel(II)nitrate. The calcination of
the solids were carried out under a nitrogen flow at 450°C for 16 h and further reduction of Nickel oxide withhydrogen at 650 °C for 4 h. The Nickel content wasevaluated using EDX to 14 w%. SEM-EDX mapping
showed homogeneously dispersed Nickel with a small
excess on the border of the zeolite cores.

Sorption studies

Figure 1: Sorption Enhanced Methanation

Reactor design
The reacting gases are lead into the reactor without
preheating or purification. The reactor is a stainless steel

The pore diameters of the zeolites are highly dependent
on the preparation of the zeolites and are commerciallyavailable. Interesting for our purposes were the 3A, 4A
and 5A, who have different characteristics in theadsorption of water and other small molecules such as
H2, CH4, CO and CO2.

References[1] B. T. Carvill, et al. , AIChE J. 1996, 42, 2765.

Riccardo Suter from Freienwil is born in 1988, in Baden Switzerland. 2011 Master in Science
Chemistry ETH Zürich. 2010 Research project on the Synthesis of Tetramethyl-phosphinanone.
2011 Research project on Luminescent Lanthanide Complexes on Silica Nanoparticles. 2011
Master-Thesis in Bristol in the group of Ian Manners on the Heterogeneous Dehydrocoupling ofAmine-Borane Adducts by Skeletal Nickel Catalysts. Since October 2011 working on the Sorption
Enhanced Methanation of CO2 in the Hydrogen & Energy Laboratory at Empa, Dübendorf,
Switzerland.
R. SuterCorresponding author: Riccardo Suter: riccardo.suter@empa.ch, Tel. +41 58 823 4729

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6th Int. Symposium Hydrogen & Energy

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HYDROGEN-METAL COMPLEXES IN METAL-HYDROGEN INTERSTITIAL ALLOYS.
DESCRIPTION OF HEAT CAPACITY ANOMALY
Ioseb Ratishvili*, Natela Namoradze***I.Javakhishvili Tbilisi State University, Andronikashvili Institute of Physics, Tbilisi, Georgia**Georgian Technical University, Chavchanidze Institute of Cybernetics, Tbilisi, Georgia
Abstract
Basing on measurements [1] it was established [2] that the light rare-earth dihydrides LaH2 andCeH2 reveal a sufficiently remarkable qualitative difference in the heat capacity temperaturedependence C(T) (see Fig.1, reproduced from [2]). Description of experimental dependences
C(T)[LaH2] and C(T)[CeH2] using the traditional mathematical methods applicable to interstitial
alloy lattices provides exclusively good coincidences of experimental and calculated C(T)-curves
in both hydrides, except the temperature region 150-300K in LaH2 [2, 3]. In order to describe
this anomaly we have elaborated a tentative model of metal-hydrogen compounds, based on theassumption that the given stoichiometric dihydrides can be considered as consisting of MH2complexes having tetrahedral or octahedral configurations. Within the frames of this model
additional heat capacity at 150-300K in lanthanum dihydride is ascribed to tetra-octa
reorientations of MH2 complexes.

C (T) [cal / m ole K ]

14
12

LaH2

10
8

CeH2

6
4
2
0
0

100

200

300

400

T [K]
References
1. B.Stalinski, Z.Bieganski. Bull. Acad. Pol., Ser. Chem., v. 12, N 5, 331-334 (1964);
Z.Bieganski, D.Gonzalez Alvarez, F.W.Klaijsen Physica (Utrecht), 37, 153-157 (1967)’
Z.Bieganski. Bull. Acad. Pol., Ser. Chem., v. 19, N 9, 581-586 (1971).
2. N.Namoradze, I.Ratishvili. Poster Presentation at GRC “Hydrogen-Metal Systems”, Stonehill,
MA, USA (2011)
3. N.Namoradze, I.Ratishvili. Bullet. Georg. Nat. Acad. Scien., v. 5, N 3, (2011) [in press].

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6th Int. Symposium Hydrogen & Energy

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Muons probe strong hydrogen interactions with defective
graphene
Mauro Riccò¥,*, Daniele Pontiroli¥, Marcello Mazzani¥, Mohammad Choucair&, John A.
Stride&,§, Oleg V. Yazyevç,,
¥Dipartimento di Fisica, Università di Parma, Via G.Usberti 7/a, 43100 Parma, Italy.

&

School of Chemistry, University of New South Wales, Sydney 2052, Australia.

§

Bragg Institute, Australian Nuclear Science and Technology Organisation, PMB 1, Menai, NSW 2234, Australia.

çDepartment of Physics, University of California at Berkeley, Berkeley, CA 94720, USA

Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Institute of Theoretical Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

ABSTRACT: Here, we present the first SR investigation of graphene, focused on chemicallyproduced, gram-scale samples, appropriate to the large muon penetration depth. We have observed
an evident muon spin precession, usually the fingerprint of magnetic order, but here demonstrated
to originate from muon-hydrogen nuclear dipolar interactions. This is attributed to the formation
CHMu (analogous to CH2) groups, stable up to 1250 K where the signal still persists. The relatively
large signal amplitude demonstrates an extraordinary hydrogen capture cross-section of CH units.
These results also rule out the formation of ferromagnetic or antiferromagnetic order in chemicallysynthesized graphene samples.

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6th Int. Symposium Hydrogen & Energy

CATALYTIC
MATERIAL

Stoos, Switzerland 2012

DEHYDROGENATION

OF

MG(NH2)2-2LIH

COMPOSITE

Jianhui Wang, Zhitao Xiong, Guotao Wu, Ping CHEN
Dalian Institute of Chemical Physics, Dalian, China 116023
Abstract The kinetics of hydrogen desorption from Mg(NH2)2-2LiH can be significantly improved by doping it with 3 mol%KH. Mechanistic investigation reveals that K keeps on changing bonding environment in the dehydrogenation.

Introduction
Hydrogen Storage is one of the challenging technical1barriers in the implementation of hydrogen energy.
Chemicals with high hydrogen content are potential
hydrogen storage materials. A number of promising
candidates have been identified and investigated overthe past decades, among which amide-hydridecomplexes have attracted considerable attention.2-8 It has
been demonstrated that ~ 10.5 wt.% and 5.5 wt.% ofhydrogen can be stored in lithium amide-lithium hydrideand magnesium amide-lithium hydride systems throughreactions (1) and (2), respectively.2, 6
LiNH2 + LiH = Li2NH + H2

(1)

Mg(NH2)2 + 2LiH = Li2Mg(NH)2 + 2 H2(2)However, relatively high operating temperatures due tothermodynamic or kinetic reason place a serious
restriction onto the application of those materials.

Pristine sample

Intensity (a. u.)

K-doped sample

Figure 2 Pressure-Compositional isotherms of the
Mg(NH2)2-2LiH sample w/o K catalyst.
XAFs analyses reveal that K in K-H state graduallytransformed to the K in K-N environment in thedehydrogenation. Interestingly, there is kickpoint at a H
content of ca. 3.5 showing a rapid enrichment of K-Ncontent in the early stage of dehydrogenation revealingthat a part of the KH takes the advantage to react with
Mg(NH2)2 to form the K-N species. It is, therefore, that
KH catalyzes the dehydrogenation through actively
participation in the reactions with reactant(s) and/orintermediates, which is significant different from those oftransition metal catalyzed dehydrogenation of metal
hydrides and alanates.

References
50

100 150 200 250
0Temperature ( C)300

Figure 1 Hydrogen release from the Mg(NH2)2-LiH
samples with/o K.

Results and Discussions
Among all variables that affect the kinetics of aheterogeneous solid state reaction, mass transport andreaction at the surface or interface(s) are the two
common rate-determining processes. It was found thatthe interface reactions between amide-imide and imidehydride are slow steps in the reaction (2). Conventionaltransition metals have limited catalytic effect on thedehydrogenation of those amide-hydride composites.
Interestingly, KH of 3 mol% works well which can reducethe dehydrogenation temperature from ca. 180 C to 107
C (see Figs 1 and 2).8

[1] Schlapbach L. & Zuttel A. Nature 2001, 414, 353[2] Chen P, Xiong ZT, Luo, JZ, Lin JY, Tan K. L. Nature
2002, 420, 302.
[3] Luo WF. J Alloy Compd 2004, 381,284.
[4] Leng HY, Ichikawa T, Hino S, et al. J Phys Chem B
2004, 108, 8763.
[5] Nakamori Y, Orimo S. J Alloy Compd 2004, 370,,71.
[6] Xiong ZT, Wu GT, Hu JJ, Chen P. Adv. Mater. 2004,
16, 1522.
[7] Pinkerton FE, Meisner GP, Meyer MS, Balogh MP, &Kundrat MD J. Phys. Chem. B 2005, 109, 6.
[8] Wang JH, Liu T, et al, Angew Chem Int Ed 2009, 19,
2141

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Ping Chen is a professor at the Dalian Institute of Chemical Physics (DICP, China). Chenreceived a BS degree in 1991 and a PhD degree in 1997 in chemistry from Xiamen University,
China. She was a faculty member in the Faculty of Science at the National University ofSingapore (NUS) before she joined DICP. Her primary research interest includes thedevelopment of chemical and complex hydrides for hydrogen storage, catalysis, and organic
synthesis.

Ping Chen
Corresponding author: Ping Chen, pchen@dicp.ac.cn, 86-411-84379905.

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5th Hydrogen & Energy Symposium

Stoos, Switzerland 2011

SUPERIONIC CONDUCTIVITY IN FULLERENE POLYMERSDaniele Pontiroli, Matteo Aramini, Mattia Gaboardi, Marcello Mazzani and
Mauro Riccò
Dipartimento di Fisica, Università degli Studi di Parma, Via G. Usberti 7/a, 43124 Parma, Italy
Abstract: The successful intercalation of lithium and magnesium in the fullerene C60 lattice leads to theformation of the isostructural two-dimensional polymers Li4C60 and Mg2C60, with an ordered crystalline
structure. Here the small alkali and alkali-earth ions can easily diffuse, even at low temperature. Thesefindings open to the possibility of employing these materials as electrodes in future ion batteries.

Li and Mg doped C60 polymers
Production of energy from renewablesources also requires an effective andpractical way to storage it. For this reason it
is important designing new materials suitablefor increasing the performance of current
batteries.
It is known that carbon nanomaterials likefullerenes are able to intercalate small alkali
metals to form polymerised layered
structures. In particular, our previous study
on Li doped C60 showed that the chargetransfer of 4 electrons from the metal to thefullerene
stabilizesapeculiar
twodimensional polymer structure in the solidstate [1]. Surprisingly, Li4C60 behaves also as
an extraordinary good ionic conductor (seebelow) [2]. More recently, we successfullyintercalated also magnesium in the fullerene
lattice and found that, interestingly, Mg2C60
shows the same polymeric arrangement of
Li4C60 [3].

Ionic conductivityAnextensive
analysis
with
DC/AC
conductivity and solid state 7Li NMR,
supported also by ab-initio DFT calculations,clearly demonstrated that, in polymerised
fullerene Li4C60, Li+ ions diffuse with anextremely high mobility, even at low T. This
could be obtained thanks to the presence of
intrinsic unoccupied interstitial sites in the
crystalline structure, connected by threedimensional
channels(superionic

conductivity). Due to the low activationenergy of the process (∆Ea≈200 meV), theuncorrelated Li+ hopping among these sites
grows up already at 130 K. Then, following
an Arrenius law, conductivity reaches the
exceptional value for the of 10-2 S/cm atroom temperature [2].
Preliminary DC measurements on Mg2C60
indicated a similar behaviour, with the onsetof the Mg2+ diffusion at T=150 K and an evenlower activation energy for the hopping
process (∆Ea≈105 meV); these analyses are
currently in progress. This material appears
promising for the production of the future andstill unexplored Mg ion batteries.

References[1] S. Margadonna, D. Pontiroli, M. Belli, T.
Shiroka, M. Riccò and M. Brunelli, "Li4C60: A
Polymeric Fulleride with a Two-Dimensional
Architecture and Mixed Interfullerene Bonding
Motifs", Journal of the American Chemical
Society, 2004 Volume 126 (46), 15032.
[2] M. Riccò, M. Belli, M. Mazzani, D. Pontiroli, D.
Quintavalle, A. Jánossy and G. Csányi,"Superionic conductivity in the Li4C60 fullerenepolymer", Physical Review Letter, 2009,
Volume 102, 145901.
[3] D. Pontiroli, M. Aramini, M. Gaboardi, M.
Mazzani, A Gorreri, M. Riccò, I. Margiolaki and
D. Sheptyakov, “Two-dimensional
polymerization with mixed bondingarchitecture observed in Mg2C60”, Journal of
the American Chemical Society, submitted.

Corresponding author: Daniele Pontiroli, email: Daniele.Pontiroli@fis.unipr.it, Tel. (+39) 0521 905231

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A first-principles study of defects in LiNH2 and nano-sized LiBH4
clusters
E. Hazrati1, G. Brocks2, R. A. de Groot1 and G. A. de Wijs1
1

Radboud University Nijmegen, Institute for Molecules and Materials, Electronic Structure of Materials, Heyendaalseweg

135, 6525 AJ, Nijmegen, The Netherlands
2Computational Materials Science, Faculty of Science and Technology and MESA+ Institute for Nanotechnology,

University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands

Defects in LiNH2
We present a first-principles study of native point defects
and dopants in LiNH2 using density functional theory. We+
find that Li-related defects (Lii and VLi ) are mostabundant. Having diffusion barriers of 0.3–0.5 eV, theydiffuse rapidly at moderate temperatures. VH , whichcorresponds to the [NH]2 ion, is the dominant species
available for proton transport with a diffusion barrier of+
0.7 eV. The equilibrium concentration of Hi , whichcorresponds to the NH3 molecule, is negligible in bulk
LiNH2. Dopants such as Ti and Sc do not affect theconcentration of intrinsic defects, whereas Mg and Ca
can alter it by a moderate amount [1].

Figure 1. The geometry of 12 formula units LiBH4 cluster.

clusters of LiH and LiB are more strongly destabilized
than the LiBH4 clusters upon decreasing the cluster size.
As a result the desorption energies for LiBH4 clusters
increase as the cluster size decrease (see figure 2).
Finally, we present some of our preliminary NMR
chemical shift results for different LiBH4 surface
terminations.

Figure 2. Calculated desorption energies (without zeropoint energies) of LiBH4.

References
Nano-sized LiBH4 clusters
In the second part we discuss about the geometries (seefigure 1), total energies and different decomposition
pathways of LiBH4 clusters. The calculations show thatdestabilization can only be achieved for very small LiBH 4
clusters up to 12 formula units. We also find that small

EbrahimHazrati[1] Intrinsic defects and dopants in LiNH2: A firstprinciples study, E. Hazrati, G. Brocks, B. Buurman, R. A.
de Groot and G. A. de Wijs; Phys. Chem. Chem. Phys.,
2011, 13, 6043-6052

Born 1983 in Iran. 2000-2004 B.Sc. in Physics, 2005-2007 M.Sc. in Condensed Matter Physics,
Isfahan University of Technology, Isfahan, Iran. Since 2008 Ph.D. student in the Electronic Structureof Materials group at the Radboud University Nijmegen, The Netherlands.

Corresponding author: Ebrahim Hazrati, ehazrati@science.ru.nl, (+31) 24 36 52810.

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HYDROGEN PRESSURE DEPENDENCE OF LI2B12H12 FORMATIONDURING DEHYDROGENATION OF LIBH4-MGH2 COMPOSITE
Hai-Wen Li1,2, Yigang Yan3, Hideki Maekawa4, Etsuo Akiba2,5, Shin-ichi Orimo6
1

International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395, Japan
International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka 819-0395, Japan
3
Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen & Energy, CH-8600
Dübendorf, Switzerland
4
Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
5
Department of Mechanical Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
6
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
2

Intermediate compound containing [B12H12]2- anion formed in the dehydrogenation is regarded to be responsible for the
degradation of reversibility of metal borohydrides, whereas little is known about the formation of Li2B12H12 in the LiBH4MgH2 composite. In this study, we investigated the dehydrogenation process of the LiBH4-MgH2 composite in a heating
run under different hydrogen pressures. Our experimental results demonstrated that Li2B12H12 was formed during
dehydrogenation, whereas depending on hydrogen pressures.

LiBH4-MgH2 Composite
LiBH4-MgH2 composite attracted a great of attention due
to its good reversible de-/rehydrogenation performances
via reaction 1.
2LiBH4 + MgH2 ↔ 2LiH + MgB2 + 4H2 (1)The formation of MgB2, which is considered to be crucial
for the reversibility of reaction 1, however, largely
depends on hydrogen pressures [1].

Li2B12H12 Formation

Formation of intermediate compound Li2B12H12 during thedehydrogenation of LiBH4-MgH2 composite wasinvestigated under hydrogen pressures of 0 - 2.0 MPa ata heating rate of 5 K/min.
Raman and NMR measurement results indicated that
Li2B12H12 was formed from the individual decompositionof LiBH4 when hydrogen pressure below 2.0 MPa,
whereas not formed under 2.0 MPa. Moreover, theformation of Li2B12H12 was found to negatively dependingon the hydrogen pressure, and also influence subsequent
formation of MgB2: the more Li2B12H12 formed, the less
MgB2 obtained (see Fig. 1) [2].
These findings indicate that suppression of the formationof intermediate compound Li2B12H12, such as by using
adequate hydrogen pressures (e.g. 2.0 MPa), is of great
importance for further improvement of hydrogen storage
properties of LiBH4−MgH2 system.

References[1] J. J. Vajo, S. L. Skeith, F. Mertens, J. Phys. Chem. B,
109 (2005) 3719–3722.
Figure 1 Relationship between the formation of the intermediate
compound Li2B12H12 and final product of MgB2 under differentpressure; He atmosphere is regarded as a hydrogen pressure of
0 MPa. The relative amounts of Li2B12H12 and MgB2 are roughly
calculated from Raman spectra areas and diffraction peak areas,
respectively.

[2] Y. Yan, H.-W. Li, H. Maekawa, K. Miwa, S. Towata,
S. Orimo, J. Phys. Chem. C, 115 (2011) 1941919423.

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6th Int. Symposium Hydrogen & Energy

Hai-Wen LI

Stoos, Switzerland 2012

Born 1976 in Zunhua, China. 1998 Bachelor in Chemical Engineering, Wuhan, China. 2000
Exchange student in Kitami, Japan. 2001 Master in Chemical Engineering from Wuhan University of
Science and Technology, China. 2005 Ph.D in Materials Engineering from Kitami Institute ofTechnology. 2005 Post doc Orimo Lab in Institute for Materials Research (IMR), Tohoku University
in Sendai, Japan. 2006 Japan Society for the Promotion of Science (JSPS) Post doc at IMR, Tohoku
University. 2008 Assistant professor at IMR, Tohoku University. 2011 associate professor at
International Research Center for Hydrogen Energy, Kyushu University.

Corresponding author: Hai-Wen Li, Email: li.haiwen.305@m.kyushu-u.ac.jp, Tel. (+81) (92) 802 3235

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STUDY OF THE DECOMPOSITION PATH OF Al-Li-BOROHYDRIDE
Inge Lindemann1, Elsa Callini2, Andreas Borgschulte2, Andreas Züttel2, Ludwig Schultz1,
Oliver Gutfleisch1
1

Leibniz Institute for Solid State and Materials Research Dresden (IFW), 01069 Dresden, Germany

2

Empa Materials Science & Technology , 8600 Dübendorf, Switzerland

The mixed metal borohydride Al3Li4(BH4)13 decomposes at moderate temperatures forming LiBH4 as a residual in thesolid phase. In particular the desorbed species in the gas phase were under investigation using combined
thermogravimetric and spectroscopic gas phase analysis. As a result the full decomposition pathway of Al3Li4(BH4)13 wasrevealed. It showed the formation of the single borohydrides LiBH4 and Al(BH4)3 upon decomposition.

Introduction

Results

The stability of borohydrides can be tuned by mixing
different cations. Most conventional borohydrides are too
stable as e.g. LiBH4 which decomposes above 350°C. [1]WhereasAl(BH4)3
decomposesatmoderate
temperatures but it is a volatile liquid at ambientconditions and therefore hard to handle. [2] The mixed
metal borohydride Al3Li4(BH4)13 shows decomposition atmoderate
temperatures~60°C.
In-situRaman
measurements showed the formation of LiBH4 upon
decomposition accompanied by a mass loss of ~25 %. [3]The decomposition products in the gas phase are hard to
identify and require a special experimental setup.

The TG measurement confirmed the mass loss of 25 %after decomposition of Al3Li4(BH4)13. Due to themetathesis process only 44 wt.% of the powder
correspond to the complex borohydride. LiCl is formed asa side product. The IR analysis of the desorbed gas
showed strong vibrations of Al(BH4)3 and a small amountof B2H6. Therefore Al3Li4(BH4)13 decomposes into its
component borohydrides LiBH4 and Al(BH4)3. Most of thevolatile Al(BH4)3 is evaporated. This can be reduced by
the addition of porous carbon. The vapour pressure ofAl(BH4)3 is smaller when adding carbon and therefore theoverall weight loss is reduced by 6 wt.%.
Al3Li4(BH4)13 → 4 LiBH4 + 3 Al(BH4)3

Experimental
Al3Li4(BH4)13 was prepared by metathesis reaction of
AlCl3 and LiBH4 (1:4.33) using high energy ball milling.
Another milling was carried out with 10 wt.% carbon
addition. The decomposition behaviour was followed witha TG measurement using a magnetic suspension
balance combined with FT-IR measurements of thedesorbed gas. [4]References[1] Züttel et al., J. Power Sources 118 (2003)[2] Schlesinger et al., J. Am. Chem. Soc. 62 (1940)[3] Lindemann et al., Chem. Eur. J. 16 (2010)[4] Borgschulte et al., J. Phys. Chem. C 115 (2011)

Born 8.4.1984 in Cottbus, Germany 2003-2009 Studies in Materials Science at the University ofTechnology in Dresden, Germany (Diploma 2009) 2006 Exchange student at Advanced
Nanotechnology Ltd. in Perth, Australia Since 2009 PhD student at IFW Dresden in the group of
Functional magnetic materials and hydrides, Germany

I. Lindemann
Corresponding author: Inge Lindemann, I.Lindemann@ifw-dresden.de, Tel. (+49) (351) 4659 337

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Stoos, Switzerland 2012

THEORETICAL AND EXPERIMENTAL INVESTIGATIONS OF KSIH3 AS A
REVERSIBLE HYDROGEN STORAGE MATERIAL
Wan Si Tang1, Jean-Noël Chotard1, Pascal Raybaud2 and Raphaël Janot1
1

Laboratoire de Réactivité et Chimie des Solides, UMR 6007 CNRS Université de Picardie Jules Verne 33 rue St Leu,
280039 Amiens (France) IFP Energies Nouvelles, Rond-point de l’échangeur de Solaize BP 3 - 69360 Solaize (France)
Abstract Potassium silicide (KSi) can absorb hydrogen to form the KSiH3 hydride. The full structure of KSiD3,
solved using neutron powder diffraction (NPD), shows a short Si-D bond length of 1.47 Å. Through a combination ofdensity functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of
the KSi/KSiH3 system are determined. This system can store 4.3 wt.% of H2 reversibly within a good P–T window; a0.1 MPa hydrogen equilibrium pressure is obtained at about 414 K. Owing to its relatively high hydrogen storage capacity
and its good thermodynamic values, the KSi/KSiH3 system is a promising candidate for reversible hydrogen storage.

Introduction
KSiH3 exists as 2 allotropes: the high temperature[1]phase with unknown hydrogen atomic positions andthe low temperature phase that has a fully resolved[2]
structure. Instead of using the wet chemistry synthesis[3]route for KSiH3 , it was interesting to first form KSi andthen perform a direct hydrogenation on this alloy. The
theoretically calculated capacity for this KSi/KSiH3
system is 4.3 wt.%. Because progress in density
functional theory (DFT) calculations has allowed forpredicting the thermodynamic properties of hydrides, the[2]completely solved KSiH3 structure was first used forpreliminary estimations for the KSi/KSiH3 system, giving-1[4]
an hydrogenation enthalpy value of -35 kJ.mol H2.
Prompted by such encouraging values of capacity andenthalpy, this system was looked into more closely as ahydrogen storage material, stated herein.

Results and Discussion
KSi was prepared by annealing its stoichiometricelements under Ar atmosphere at 500 °C. It was thensuccessfully hydrogenated by 2 methods to form therocksalt-type KSiH3 (Fm-3m): 1) volumetric absorption
at 100 °C for 20 hours, 2) ball-milling under H2 pressurefor 90 min. A huge cell expansion occurs uponabsorption: ΔV/V ca. 50 % - the largest known value, toour knowledge, indicating a complete atomic
redistribution within the unit cell. A deuterated sample ofKSiD3 was sent for neutron powder diffraction to solvefor its previously unknown hydrogen/deuterium atomic
position: D atoms sit in the 96k Wyckoff site with an

occupancy of 11.95% (refined composition KSiD2.87). The
Si-D bond distance is 1.47 Å, close to that of gaseoussilanes (dSi-H = 1.40 Å), a short distance very rarely seen
in solid state silicon hydrides. DFT calculations were thenre-made using the completely solved KSiH3 structure,
showing enthalpy and entropy values in very good
agreement with those found by experimental means-1-1-1(PCI/Van’t Hoff plot): 23 kJ.mol H2 and 54 J.K mol H2,
respectively. The low entropy value in this system iscaused by the huge disorder of the hydrogen atoms as
seen during NPD refinements (Biso = 5.19). Desorption of
KSiH3 at 200 °C allowed the release of 4.3 wt.% of H2
with the re-formation of KSi. Several cycling tests weremade showing good capacity retention.

Conclusion
A new synthetic route of preparing cubic KSiH3 by the
direct hydrogenation of KSi is performed and its complete
structure was solved using NPD. Both DFT calculations
and experimental methods show that the hydrogenation
process is fully reversible at 373-473 K with a hydrogen[5]
storage capacity of 4.3 wt.%. This is, to the best of ourknowledge, the first time that the hydrogen storage
properties of this K-Si-H system have been investigated.

References[1] M. A. Ring, D. M. Ritter, J. Phys. Chem. 1961, 65, 182 – 183.
[2] O. Mundt, G. Becker, H.-M. Hartmann, W. Schwarz, Z. Anorg.
Allg. Chem. 1989, 572, 75– 88.
[3] M. A. Ring, D. M. Ritter, J. Am. Chem. Soc. 1961, 83, 802 – 805.
[4] P. Raybaud, F. Ropital, US Patent No. US 2009/0302270, 2009.
[5] J-N. Chotard, W. S. Tang, P. Raybaud, R. Janot, Chem. Eur. J.,
2011, DOI: 10.1002/chem.201101865

2010 – present: Doctor of Philosophy; Laboratoire de Réactivité et Chimie des Solides, Université dePicardie Jules Verne, Amiens, France
2008 – 2010: Erasmus Mundus European Master, Materials for Energy Storage and Conversion;
Université de Picardie Jules Verne (Amiens), Politechnika Warszawska (Warszaw), Université Paul
Sabatier - Toulouse III, (Toulouse)
Wan Si TANG

2003 – 2007: Bachelor of Applied Science (Honours); National University of Singapore (Singapore)

Corresponding author:

Raphaël Janot, raphael.janot@u-picardie.fr, (+33) 322-82-79-01

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HYDROGEN STORAGE PROPERTIES OF LIBH4 DESTABILIZED BY INSITU FORMATION OF MGH2 AND LAH3
Yongfeng Liu, Yifan Zhou, Mingxia Gao, Hongge Pan
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China.

Abstract
The safe and efficient storage of hydrogen is recognized
as one of the key technological challenges for thewidespread use of hydrogen as an energy carrier in the
future. LiBH4 are attracting considerable attention as oneof the most promising hydrogen storage media becauseof its high gravimetric (18.5 wt%) and volumetrichydrogen density (121 kg m-3). However, highthermodynamic stability and large activation energy
barrier result in rather high operating temperatures, which
prevents it from practical applications for on-board hydrogenstorage. The present work demonstrates a significant
improvement on the hydrogen storage reversibility and a
distinct reduction on the operating temperatures of LiBH4
by introducing La2Mg17 reactive additive. The LiBH4xLa2Mg17 composite is prepared by means ofmechanochemical reaction under 40 bar H2. It is foundthat MgH2 and LaH3 are readily in situ formed duringhigh-pressure ball milling LiBH4 and La2Mg17. Hydrogen
desorption examinations show a strong dependency ofthe dehydrogenation performances on the content ofThe
as-prepared
LiBH4-0.083La2Mg17
La2Mg17.
composite under 40 bar H2 exhibits superior hydrogenstorage properties as ~ 6.8 wt% of hydrogen can bereversibly desorbed and absorbed below 400 ºC with a
two-step reaction. In dehydrogenation process, the self-

decomposition of MgH2 first occurs to convert into Mg
with hydrogen release, and subsequently catalyze thereaction of LiBH4 and LaH3 to liberate additionalhydrogen and form LaB6 and LiH. The in situ formed
MgH2 and LaH3 provide a synergetic thermodynamic andkinetic destabilization on the de-/hydrogenation of LiBH4,
which is responsible for the distinct reduction in theoperating temperatures of the as-prepared LiBH4xLa2Mg17 composites under 40 bar H2.

References[1] A. Züttel, S. Rentsch, P. Fischer, P. Wenger, P.
Sudan, Ph. Mauron, Ch. Emmenegger, J. Alloys
Compd. 2003, 356-357, 515-520.
[2] J. J. Vajo, S. L. Skeith, F. Mertens, J. Phys. Chem. B
2005, 109, 3719-3722.
[3] D. M. Liu, Q. Q. Liu, T. Z. Si, Q. A. Zhang, F. Fang, D.
L. Sun, L. Z. Ouyang, M. Zhu, Chem. Commun. 2011,
47, 5741-5743.
[4] T. Sun, H. Wang, Q. A. Zhang, D. L. Sun, X. D. Yao,
M. Zhu, J. Mater. Chem. 2011, 21, 9179-9184.

Yongfeng Liu received his PhD in Materials Science and Engineering from Zhejiang University in
2005. He then moved to National University of Singapore as a postdoctoral research fellow (working
with Dr. Ping Chen). In 2007, he joined Zhejiang University as an associate professor. His research
is focused on solid-state hydrogen storage materials and electrode materials of rechargeable
batteries.

Yongfeng Liu
Corresponding author: Hongge Pan, hgpan@zju.edu.cn, Tel: +86 571 87952615.

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THE DESTABILIZATION OF MG(BH4)2-2NAALH4 COMBINATION SYSTEMDOPED WITH TITANIUM FLUORIDES
Yanjing Yang, Mingxia Gao*, Jian Gu, Yongfeng Liu, Hongge Pan
Department of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, P.R. China
Abstract: A combination system of Mg(BH4)2-2NaAlH4 was ball-milled. The study of the structure, the hydrogen storage
property of the ball-milled system and the destabilization ability of the system by addition of titanium fluorides shows thata new system of Mg(AlH4)2 and NaBH4 was formed after the ball-milling. The ball-milled system starts to desorb hydrogenat ca. 120 °C, which is from the decomposition of Mg(AlH4)2, and the total hydrogen desorbed is 9.24 wt.% up to 500°C. The system is further destabilized by the addition of TiF3/TiF4 during the ball-milling process.

Introduction
Mg(BH4)2 is a promising candidate for hydrogen storage
1
materials . However, its relatively high decomposition
temperature, poor dehydrogenation kinetic properties andharsh hydrogenation conditions cannot fulfill therequirement for practical hydrogen storage systems.
Combining metal borohydride with metal alanate has
been proved to be an effective way to improve thehydrogenstorageproperties
ofalkalimetalborohydride2,3. In the present work, combination ofMg(BH4)2 and NaAlH4 was performed by ball-milling. The
structure and the hydrogen storage property of the ballmilled system were studied. Titanium fluorides of TiF3
and TiF4 were added in the combination system duringball-milling in order to further destabilize the hydrogenstorage system.

The structure and the hydrogen storage
property of the ball-milled system
A metathesis reaction occurred during the ball-milling
process with the transformation from Mg (BH4)2 to Mg(AlH4)2, forming Mg(AlH4)2 and NaBH4 as the final
products. The Mg(AlH4)2 in the combination product isunstable even stored in the glove box at room
temperature. It can decompose gradually into MgH2 andAl in several months. From the dehydrogenation curves
and the TPD (temperature-programmed desorption)
curves, it was found that three major dehydrogenation
steps occurred for the ball-milled combination systemupon heating up to 500 °C, corresponding to thedecomposition of Mg(AlH4)2, MgH2 and NaBH4,
respectively, where MgH2 was decomposed from
Mg(AlH4)2 in the first step. The hydrogen desorbed in theentire heating process is ca. 9.24 wt.%. The
dehydrogenation temperatures of the latter two are lower
than that of the corresponding hydride dehydrogenatedsolely, which is supposed to be attributed to the in-situ
formed medium product of Al decomposed from
Mg(AlH4)2. The effect of Al to the destabilization of NaBH4
and MgH2 was proved by the dehydrogenation process ofa ball-milled mixture of 2NaBH4+MgH2+2Al.

The destabilization to the system by doping
TiF3/TiF4
Both TiF3 and TiF4 show superior destabilization to theMg(AlH4)2, especially for TiF4. The in-situ formed
Mg(AlH4)2 decomposes almost completely during ballmilling with the extra addition of TiF3/TiF4 in a weightfraction of 5 wt.% at room temperature. The hydrogen
desorbed from the ball-milled combination system with
TiF3/TiF4 extra added during heating was mostly from thedecomposition of MgH2 and NaAlH4. The hydrogen
desorbed for MgH2 and NaAlH4 was comparable to thatwithout TiF3/TiF4 addition, being of 5.81 wt.% and 5.68
wt.% respectively. However, the decomposition
temperatures started for MgH2 and NaBH4 were further
reduced by the addition of TiF3/TiF4, showing close
reduced values of ca. 30 and 20 oC, respectively.

References
1. K. Chlopek, C. Frommen, A. Leon, O. Zabara, M.
Fichtner, J. Mater. Chem. 2007, 17, 3496.
2. J.F. Mao, X.B.Yu, Z.P. Guo, C.K.Poh, H.K.Liu, Z. Wu,
J. Ni, J. Phy. Chem. C 2009, 113, 10813.
3. D.B. Ravnsbaek, T.R. Jensen, J. Phy. Chem. Solids
2010, 71, 1144.

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Mingxia Gao received her PhD in Materials Science and Engineering from Zhejiang University in
2004. She is currently an associate professor of Zhejiang University. Her research interests include
advanced cathode and anode materials for lithium-ion batteries, hydrogen storage electrode alloys,
hydrogen storage compounds of light metal hydrides, ceramic matrix composites.

Mingxia Gao
Corresponding author: Mingxia Gao, email: gaomx@zju.edu.cn, Tel.:+86-571-87952615.

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GRAPHENE COMPOSITES FOR NEXT GENERATION LITHIUM ION
BATTERIES
Mohammad Choucaira*, John A. Stridea, Shi-Xue Doub, Shu-Lei Choub,c, Jia-Zhao Wangb,c,
Hua-Kun Liub,caSchool of Chemistry, University of New South Wales, Sydney 2052, Australia.

bInstitute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, NSW 2522, Australia.

c

ARC Centre of Excellence for Electromaterials Science, University of Wollongong, Wollongong, NSW 2522, Australia.

Abstract The facile synthesis of gram-scale quantities of graphene [1] has allowed us to develop composite anodic andcathodic materials that enhance the performance of lithium ion batteries. Such materials include nano-silicon/grapheneand sulfur/graphene composites. Assessments on the materials’ electrochemical nature, structural stability,
characteristics, and performance were conducted. The composites were shown to significantly improve the electricalconductivity, capacity, and cycle stability in a lithium cell compared with the bare electrodes.

Introduction
Rechargeable lithium-ion batteries are currently the
predominant power sources for portable electronic
devices. Over the past decade, substantial efforts havebeen devoted to developing energy storage systems thatcan be coupled to renewable sources as a solution toemission and pollution challenges. More advanced
lithium-ion batteries with high energy and high power
density still need to be achieved for the projected era of
hybrid electric vehicles [2].

were uniformly coated onto the surface of the graphenenanosheets. The S-GNS electrode contained 17.6 wt.%
sulfur. The materials utilization of sulfur is 96.35%. The
initial discharge capacity of S-GNS composite was
1611mAhg−1 at a current density of 50mAg−1. The initial
capacity of the S-GNS electrode is higher than that of thepure sulfur electrode. The cycling stability of the sulfur
graphene composite is also improved. The improvementin the capacity and cycling stability is due to graphene
improving the conductivity of the electrode.

Conclusion

Results
Si/graphene composite was prepared by simply mixing ofcommercially available nanosized Si and graphene.
Electrochemical tests showed that the Si/graphene
composite maintained a capacity of 1168 mAhg-1 and an
average coulombic efficiency of 93% up to 30 cycles. EIS
indicated that the Si/graphene composite electrode hasless than 50% of the charge-transfer resistancecompared with nanosize Si electrode, evidencing theenhanced ionic conductivity. The enhanced cyclingstability is attributed to the fact that the Si/graphene
composite can accommodate a large volume charge of Si
and maintain good electronic contact. Sulfur-graphene(S-GNS) composites were synthesized by heating a
mixture of graphene and elemental sulfur. Sulfur particles

Lithium ion batteries are amongst the longest lasting
batteries available. Our work has the potential tosignificantly improve the capabilities of emerging
consumer technologies and electronics, primarily thosewhich need to have a reliable source of energy.

References[1] M. Choucair, P. Thordarson, J.A. Stride. Nature
Nanotechnology 4 (2009) 30.
[2] J.M. Tarascon, M. Armand. Nature 414 (2001) 359.

Short CVPhD in Chemistry, University of New South Wales (2010).
Graduate Certificate in Research Management and Commercialisation, University of New South
Wales (2009).
Dr. Mohammad
Choucair

B Sc Nanotechnology (Honours Class 1), University of New South Wales (2007).

*Corresponding author: Mohammad Choucair, m.choucair@unsw.edu.au, +61293854672.

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CORROSION BEHAVIOUR OF STEEL INTERCONNECTS AND COATING
MATERIALS IN SOLID OXIDE ELECTROLYSIS CELL (SOEC)Ji Woo Kima, Cyril Radob, Aude Brevetb, Seul Cham Kimc, Yong Seok Choic, Karine
Couturierb, Florence Lefebvre-Joudb, Kyu Hwan Ohc, Ulrich F. Vogta, Andreas ZüttelaaDiv. Hydrogen & Energy, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerlandb

CEA-Grenoble, LITEN, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, FranceC

Dept. of Materials Science and Engineering, Seoul National University, Seoul 151-744, Republic of Korea

Introduction
High temperature steam electrolysis (HTSE), which is theelectrolysis of steam at high temperature, offers apromising way to produce hydrogen with high efficiency.
Compared with conventional water electrolysis, HTSE
reduces the electrical energy requirement for theelectrolysis and increases thermal efficiency of the power
generating cycle. Among the various methods, SOEC
(Solid Oxide Electrolysis Cell) has been considered oneof the efficient ways. One efficient way of reducing the
raw material and fabrication cost is to lower the operating
temperature of the SOEC (from 1000°C to 600~700°C)
thereby enabling the use of stainless steel interconnects.
Stainless steel interconnects in the SOEC stack connect
each cell in series by conducting electricity, distributeactive gas to the cells and separate the hydrogen andoxygen between the cells. Although stainless steel
interconnects can reduce the stack cost, they also
introduce
severalchallenges
thathindercommercialization of the technology. Chromium oxideforming alloys are preferred due to their high oxidation
resistance associated with low electrical resistance, thus
minimizing the ohmic loss within the stacks. However,chromium oxide scale can react with the anode materials
and form non-catalytic and/or resistive compounds.
These compounds finally lead to the degradation of the
SOEC performance. In order to reduce the reaction
between interconnect and anode electrode and to
improve electrical contact as well, LNF(La(NixFe1-x)O3),
LSMC((LaxSr1-x)(MnyCo1-y)O3) are proposed as a coating
material between anode and interconnect. In this study,
material compatibility between the proposed coating
materials and the commercialized interconnects isinvestigated at SOEC operating temperature (700°C) withsevere anode atmosphere (pure oxygen).

Experimental
LNF and LSMC coated stainless steel interconnects(Crofer 22APU, K41X) are pre-heated at 750°C for 1.5h
and subsequently heat treated for 200h and 3000h at
700°C with pure oxygen flow. LNF and LSMC layers (~60
m) were deposited through screen-printing. In thisconfiguration, especially for LNF/Crofer 22APU sample,
Mn-Co oxide is additionally coated between LNF and
Crofer 22APU as a protective coating material. The heat
treated interconnect/coating samples are analysed using
scanning electron microscopy (SEM) with energy
dispersive spectroscopy (EDS) mapping and line
scanning. For selected samples, focused ion beam (FIB)
and transmission electron microscopy (TEM) are used toinvestigate the corrosion mechanism of the stainlesssteel interconnect and the perovskite coating material.

References[1] G.Y. Lau et al., J Power Sources 195 (2010) 7540
[2] R. Lacey et al., Solid State Ionics 181 (2910) 1294
[3] X. Montero et al., J Power Sources 188 (2009) 148

Born Jan. 1980 in Suwon, Korea. 2004 B.S. in Advanced Materials Science & Engineering from
Hong Ik University, Seoul, Korea. 2004-2011 M.S. and Ph.D. student at Dept. Materials Science &Engineering of Seoul National University, Korea. 2004-2011 Research student at Center for High
Temperature Energy Materials of Korea Institute of Science and Technology, Seoul, Korea. Feb.
2011 Ph.D. in Materials Science and Engineering from Seoul National University, Seoul, Korea.
Ph.D. Thesis; “A study on the correlation between hydrogen sorption behavior and microstructure ofmetal hydrides for hydrogen storage”. From April 2011 Post-Doc. working on solid oxide electrolysis
cell, Div. of Hydrogen & Energy, EMPA, Dübendorf, Switzerland.
Ji Woo Kim
Corresponding author: Ji Woo Kim, jiwoo.kim@empa.ch, +41 58 65 4153

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6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012SOLVENT-FREE SYNTHESIS AND DECOMPOSITION OF Y(BH4)3
Arndt Remhof, Andreas Borgschulte, Oliver Friedrichs, Philippe Mauron, Yigang Yan,
Andreas Züttel
Empa, Hydrogen and Energy, Dübendorf, Switzerland
The direct and solvent-free synthesis of yttrium borohydride was demonstrated by reactive ball milling of yttrium hydridein diborane/hydrogen atmosphere. The product contains only the solid elemental hydride as remaining contaminant.
Yields above 75% were obtained. The product crystallizes in the cubic α-phase and releases hydrogen above 460 K. The
decomposition was measured by in situ X-ray diffraction and the hydrogen release was monitored gravimetrically in
conjunction with infrared gas analysis. Only traces of diborane were detected during the thermal decomposition.

Introduction
The high hydrogen content of 9.1 wt%, the moderatehydrogen release temperature of about 460 K and thedemonstrated partial reversibility make Y(BH4)3 an
attractive candidate for hydrogen storage. In the present
study we demonstrate the direct, solvent-free synthesisof Y(BH4)3 at room temperature by a gas–solid reactionof YH3 with B2H6 and H2. The thermal decomposition ismeasured gravimetrically and by in situ X-ray diffraction(XRD). The evolved gas is investigated via infrared (IR)
spectroscopy.

Results
Figure 1 shows the XRD pattern of the product. All Bragg
peaks can either be attributed to Y(BH4)3, YH3 or YH2.
There are no unidentified reflections. The qualitative
phase analysis yields 77 wt.% Y(BH4)3, 17 wt.% YH3 and6 wt.% YH2. Given the hydrogen contents of 9.1 wt.% forY(BH4)3, 3.3 wt.% for YH3 and 2.2 wt.% for YH2,
respectively, the sample contains 7.7 wt.% hydrogen.
The onset of the hydrogen desorption lies at about 460 K,
in agreement with earlier reports. The maximum occurs
at 523 K, the integrated weight loss is 6.8%, which is well
below the theoretical value of 7.7 wt.%. Obviously, there
is still hydrogen contained in the residual phases. The
amount of released diborane is negligible.
In-situ X-ray diffraction reveal the disappearance of thestructural Bragg reflections of Y(BH4)3 prior to theevolution of the reflections from the solid decomposition
products, indicating that Y(BH4)3, like LiBH4, decomposes
from the melt. Above 600 K the decomposition iscompleted and we observe no further change in
diffracted intensity until the transformation from YH3 to
YH2 at 700 K.

Arndt Remhof

Figure 1: XRD pattern of the as-prepared Y(BH4)3.
The present study shows the applicability of reactive ball
milling for the direct and solvent-free synthesis ofborohydrides beyond alkaline and alkaline earthborohydrides. However, reactive ball milling is not
generally applicable, as there are thermodynamic
limitations. Obviously, the desired borohydride has to bestable under the milling conditions. Furthermore, thesynthesis reaction of the borohydride competes with theformation of the corresponding metal boride, as can beseen by the reaction of TiH2 with B2H6 to TiB2
Reference[1] A. Remhof, A. Borgschulte, O. Friedrichs, Ph.
Mauron, Y. Yan, A. Züttel, Scripta Mater, in press.
doi:10.1016/j.scriptamat.2011.11.010.

1994
University Diploma with distinction of the University of Kent at Canterbury, UK.
1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France.
1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany.
1999
Guest scientist at the Universidade Sao Francisco in Itatiba, Sao Paulo, Brazil.
2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands.
2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum.
From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.”
2010
Guest scientist at the Tohoku University in Sendai, Japan

Corresponding author: Arndt Remhof, arndt.remhof@empa.ch +41587654369

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HOW TO WATCH HYDROGEN DIFFUSE IN ANY ABSORBING MATERIAL
Andreas Bliersbach, Gunnar K. Pálsson, Atieh Zamani and Björgvin Hjörvarsson
Department of Physics and Astronomy, Materials Physics Division, Uppsala University, Box 516, SE-75120, Uppsala,Sweden.
The kinetics of interstitial hydrogen are of great interest and importance for many technologies. In particular nano-sizedmaterials motivate fascinating applications and scientific questions. Even though diffusion is one of the most studied
phenomena the complex combination of quantum effects and dynamic interplay with the displacement of host atoms [1,4]is still only partially understood. We present a method to quantify chemical diffusion of hydrogen in nano-sized materials.
The changes in the absorptance of a vanadium single crystal thin-film, induced by hydrogen, are observed visually and inreal-time as a function of position. Concentration profiles and their evolution in time, during chemical diffusion, can bemeasured down to a hydrogen content corresponding to just a few effective monolayers, randomly distributed within VHx.

Introduction
In the 1970s Fukai et al. used soft x-ray emission
spectroscopy, on hydrogenated vanadium, to observe a
substantial change in the density of states located 7 eV
below the Fermi energy [3]. They interpreted theobserved changes as the hybridization of the 1s-state ofhydrogen and one of the host lattices 3d-states.
Accompanied by this hybridization is a change in thedensity of states in the d-band, leading to an increased
Fermi level. The absorption of light by matter is strongly
correlated to the available states the electrons of theabsorbant can be excited to, the occupation and clearly
the photon energy. As hydrogen changes the density ofstates within vanadium under absorption, it will inducechanges in the absorptance correspondingly. Thesechanges in the absorptance can be used as a gaugeable
variable. From collected data and previous research [2]we can deduce continuous and linear dependence
between the hydrogen concentration
and
for a
certain wavelength. Where / stands for the transmitted
intensity with and without hydrogen. A scaling for∝ ln
can be estimated either by comparison withbulk data, if the assumption of comparable thicknesses
holds, or by measuring the concentration ex-situ.

Experiment
To quantify hydrogen diffusion in thin films changes in thetransmitted intensity are measured with a position
sensitive camera (CCD) as a function of position andtime. To ensure clearly defined and reproducible
conditions, i.e. temperature, hydrogen pressure andsurface cleanness, the sample is placed in a sample
chamber which is bakeable up to 523 K and connected toan ultra high vacuum (UHV) system with a base pressure
10 Pa. In addition to the mentioned features theof
UHV-system is used to minimize the amount of water
surrounding the sample. Water, present in form of
humidity, can condensate on the surface, at elevatedtemperatures deteriorate the sample through oxidation,
block dissociation of H2 and is therefore undesirable. The
sample chamber is connected to the vacuum system via
a bellow, to reduce transport of vibrations from the rest of
the system. A schematic of the experimental setup canbe seen in Figure 1.

Figure 1: Schematic illustration of the experimental approach.
Light at a specially chosen wavelength shines through thesample and is detected with a CCD camera. The sample iscovered with Al2O3 to prevent hydrogen from going in and out
except at a small opening at one end of the sample.

Conclusion
The experimental results are a spectacular realization of
Fick's second law of diffusion. No other experiment withsimultaneous measurement of concentration in space
and time is know to us at the moment. The method is in
general applicable to all materials that absorb hydrogenand its extraordinary sensitivity enables investigations ofhydrogen diffusion as a function of crystallographic
direction, strain, confinement, electronic proximity andfinite-size.

Figure 2: Comparison of three different times duringhydrogenation of a 50 nm vanadium sample. The initialconcentration, at 423 K, corresponds to the β-phase. The dottedline marks the end of the palladium window. The H migration,
visible as a darkening of the sample with increasing
cocentration, is easily followed.
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References[1] A. Blomqvist et. al. Phys. Rev. Lett., 105(18):185901,
Oct 2010.
[2] J. Prinz et. al. Applied Physics Letters,
97(25):251910, 2010.

Stoos, Switzerland 2012[3] Y. Fukai et. al. Solid State Communications,19(6):507 – 509, 1976.
[4] A. M. Stoneham. J Phys FMet Phys, 2(3):417–420,
1972.

Born 1986 in Cologne, Germany. 2011 Diploma in physics at the Rheinische Friedrich-Wilhelms
University Bonn, Germany. 2008 – 2009 studies and research, as exchange student, at Uppsala
University, Sweden. 2010 – 2011 research on hydrogen diffusion in nano sized materials by direct
imaging at Uppsala University, Sweden. Since December 2011 PhD student at EMPA, Dübendorf,
Switzerland and involved in smart carbon based hydrogen storage materials.

Bliersbach A,
Corresponding author: Bliersbach Andreas, andreas.bliersbach@empa.ch, 0041 / 58 / 765 48 62.

82

Preparation, testing and scale-up of nanoscale, doped amide systems for hydrogenstorageaabUlrich Ulmer , Jianjiang Hu , Matthias Franzreb and Maximilian Fichtneraa Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, D-76021 Karlsruhe, Germanyb Institute of Functional Interfaces, Karlsruhe Institute of Technology, P.O. Box 3640, D-76021 Karlsruhe, Germany

Abstract: The LiNH2 - MgH2 system has been intensively investigated as a hydrogen storage material due to its high hydrogen capacity1and favourable thermodynamics .
The reversible hydrogen storage reaction has been shown to occur via the following reaction mechanism:(MgH2 + 2 LiNH2 →) Mg(NH2)2 + 2 LiH ↔ Li2Mg(NH)2 + 2 H2
5.6 wt % H2
Hydrogen sorption of the pristine system shows poor kinetics and the formation of undesirable by-products (e.g. ammonia). Therefore
the effect of various additives has been studied in order to improve sorption kinetics and to minimize by-product formation.
LiBH4, ZrCoH3 and KH have been reported to be effective additives to enhance the hydrogen sorption kinetics via various
2-4
mechanisms . We have found that KH and ZrCoH3 significantly improve the de-/rehydrogenation kinetics, however, the addition of
LiBH4 does not improve absorption kinetics considerably. Furthermore, it was found that the addition of KH results in irreversible
reactions.
Testing of catalyst combinations revealed that a system composed of 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 shows excellent
absorption/desorption kinetics and a reversible capacity of 4.2 wt. %.
An optimal milling time of five hours was obtained by variation of ball-milling conditions, whereas too long milling durations resulted in alower capacity and reduced reversibility.
Based on optimized conditions, the system was scaled up on an industrial milling equipment in order to produce large quantity ofmaterial for testing in a tank coupled to a fuel cell.

Effect of single and combined catalysts on the de-/rehydrogenation properties
Two stoichiometric amide systems, the MgH2 + 2 LiNH2 and the 1.1 MgH2 + 2 LiNH2 systems, were prepared undoped and with theaddition of 0.1 LiBH4, 0.1 KH and 3 wt.% ZrCoH3 under constant ball-milling conditions (20 h, 300 rpm). Sorption properties of the asprepared materials were tested under constant de-/rehydrogenation conditions (desorption: 180 °C, 1 bar H2 – pressure; absorption:
150 °C, 100 bar H2 – pressure).
It was shown that an excess of MgH2 (1.1 MgH2) has a positive effect on the dehydrogenation kinetics. Therefore, this system waschosen for a more thorough investigation. The effect of varying the amount of dopant was investigated. Combinations of catalysts wereprepared and tested. A composition of 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 was found to exhibit the best kinetics and agood reversible capacity. The temperature effect on the rehydrogenation kinetics was investigated. A decrease of rehydrogenation time
was observed, explicable by the temperature dependence of reaction kinetics (Arrhenius’s law).
Effect of ball-milling conditions on the de-/rehydrogenation properties
Ball-milling time of the 2 LiNH2 - 1.1 MgH2 - 0.1 LiBH4 - 3 wt. % ZrCoH3 system was varied between 5 and 60 h. By FTIR it wasobserved that the conversion reaction MgH2 + 2 LiNH2 → Mg(NH2)2 + 2 LiH takes place within the first 10 milling hours.
Sorption properties of the samples were investigated. Variation of milling time between 5 and 30 h does not have a significant effect on
the sorption properties in terms of kinetics and capacity. However, ball-milling for 60 h leads to a decrease of capacity after cycling thematerial.
Scale-up of the milling process
Based on optimized stoichiometry and milling conditions, the system was scaled up in order to produce 200 g of material on anindustrial vibrational ball mill.
Total ball-milling time was 300 min; small samples were removed and tested after 90 and 180 min. De- and Absorption kinetics were
found to have decreased as compared to the material prepared in the lab-scale. A decrease in capacity was measured during the firsttwo cycles; the material received after 90 min was shown to have a constant capacity of 3.5 wt. %. No hydrogen was desorbed afterball-milling for 300 min. This indicates milling in a vibrational ball mill is a very high-energetic process.
References
12
3
4

Jianjiang Hu, Maximilian Fichtner, Chem. Mater., 2009, 21, 3485-3490
Jianjiang Hu, Maximilian Fichtner, Ping Chen, Chem. Mater., 2008, 20(22), 7089-7094
Xugang Zhang, Zhinian Li, Fang Lu, Hualing Li, Jing Mi, Shumao Wang, Xiaopeng Liu, Lijun Jiang, Int. J. of Hydrogen Energy 35,
2010, 7809-7814
G. Wu, Z. Xiong, P. Chen, Angew. Chem. Int. Ed. 2009, 48, 5828-5832

83

Short CV
Name: Ulrich Martin Ulmerth
Date of birth: May 29 , 1985
Nationality: German

Education:
Since 11/2011

Karlsruhe Institute of Technology, Institute of Nanotechnology, Karlsruhe, Germany:
Research Associate in the “Energy Storage” groupResearch interest: Hydrogen storage, heat storage

04/2008 – 07/2011

Karlsruhe Institute of Technology, Karlsruhe, Germany:
Studies of Chemical and Process Engineering (Final Grade: 2.0 good)
Academic title: Diplom-Ingenieur (equivalent to Master of Science)

07/2009 – 11/2009

Indian Institute of Technology Madras, Chennai, India:
Semester abroad at an Indian University

09/2004 – 02/2008

University of Applied Sciences Frankfurt, Frankfurt/Main, Germany:
Studies of Biological Process Engineering (Final Grade: 1.4 very good)
Academic title: Bachelor of Engineering

Work Experience:
03/2010 – 04/2010

E.ON Ruhrgas AG, Essen, Germany:
Division of Natural Gas Dispatching
Modelling of business contracts using various modelling tools

03/2009 – 04/2009

E.ON Ruhrgas AG, Essen, Germany:
Division of Research and Development
Comparing study of innovative processes to separate CO2 from raw biogas

09/2008 – 10/2008

E.ON Ruhrgas AG, Essen, Germany:
Division of Energy Measurement Technology
Development of a tool for the calculation of thermodynamic properties of natural gas

02/2007 – 03/2007

Dechema e.V., Frankfurt/Main, Germany:
Division of Biological Process Engineering
Build-up and evaluation of experiments for the biotechnological production of preservatives

08/2006 – 10/2006

The Scripps Research Institute, La Jolla, Ca, USA:
Division of Arthritis ResearchExperiments for studying the influence of gene deletions on the bone formation in strains of mice

Scholarships:
07/2011

Ford Motor Company:
Fee waiver for the participation at the Gordon Research Conference on Hydrogen-metal systems,thndStonehill college, Easton, USA, July 17 – 22 201102/2008 – 02/2011

E.ON Ruhrgas AG, Essen, Germany:
Participation at the program „E.ON Supports Engineering Students“(E.SIS)

Publications:U. Ulmer, M. Franzreb, J. Hu, M. Fichtner:
Preparation, testing and scale-up of doped, nanoscale amide systems for hydrogen storage
The Gordon Research Conference on hydrogen-metal systems, July 17th - 22nd 2011, Easton MA,
USA (Poster)N. Taniguchi, B. Caramés, L. Ronfani, U. Ulmer, S. Komiya, M.E. Bianchi, and M. Lotz:
Aging-related loss of the chromatin protein HMGB2 in articular cartilage is linked to reduced
cellularity and osteoarthritis
Proceedings of the National Academy of Sciences, 2009, vol. 106 (4), 1181 - 1186

84

6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012

MELTING TEMPERATURE OF COMPLEX HYDRIDES
Marius van den Berg, Andreas Züttel
Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
Abstract:
To help narrowing down the selection of promising complex metal hydrides two models have been investigated. Thesemodels have been expanded in an attempt to predict key abilities of the complex metal hydrides. Especially the proposed
relation between electronegativity and the melting seems promising. These results will be presented on the poster.

Hydrogen storage in Complex hydrides
Hydrogen is the ideal means of storage, transport andconversion of energy for a comprehensive clean-energy
concept. The availability of a safe and effective way tostore hydrogen reversibly is one of the major issues for
its large scale use as an energy carrier. Hydrogenstorage in solids offers a safe alternative to storage incompressed or liquid form. However, at present, nosingle material fulfilling all requirements is in sight. Metal
borohydrides seem to be ideal candidates for thispurpose. Some preliminary studies have already shownin the past few years that this can be a promising way.
Appealing is the high gravimetric capacity that thesecompounds can provide, storing up to 17 wt% ofhydrogen, and the low temperature of hydrogen release,close to the room temperature, a target for technologicalapplications.

Need for empirical modelling
The configuration and setup of complex hydrides allows
for an almost infinite amount of atomic combinations.
While the complex hydride should still match thepreviously mentioned requirements of at least functioning
around room temperature and a good gravimetric- andvolumetric density. Looking for the desired atomic
configuration basically equals looking for a needle in ahaystack. There are a few boundary conditions which doallow for a narrowing of the search. As a rule of thumb it
can be said that any metallic element beyond the 5th
period of the periodic table is too heavy to of interest.
Even the second half of the 5th period is actually alreadyfalling short of the required gravimetric density ofhydrogen. With a few standard “complexes” used (BH4,

AlH4, NH2) the selection field narrows down to about 2025 possible cations. Lacking a complete, theoretical,
understanding of all the phenomena responsible for thephysical abilities of these compounds only empiricalmodels and theoretical approximations are available forsome physical abilities. Not being able to predict optimal,
or near optimal, atomic combinations based on thosetheoretical predictions slows down the development ofcomplex hydrides. Using available data and expanding
existing models could lead to an enhanced model which
could predict essential abilities like melting temperature,enthalpy of fusion etc. If such a model could be found anext step towards finding a functional, reliable andportable energy carrier would be completed. On thisposter I compare various models to predict the melting ofcomplex hydrides.

References

Buchter, F. Investigation of the existence andthe properties of liquid complex hydrides. 2006.

Über ein periodensystem der metallboranate.
Schrauzer, G.N. s.l. : Die Naturwissenschaften,
1955, Vol. 42, p. 438.

F.R. de Boer, A.R. Miedema, R.Boom,
W.C.M.Mattens and A.K. Niessen. Cohesion inmetals; transition metal alloys. s.l. : North
Holland
Physics
Publishing,
1988.
ISBN:0444870989.

Marius van den Berg, Born: 25.06.1986, Veenendaal, Netherlands, Bachelor: Applied Physics at
Fontys Universities, Eindhoven, Netherlands, 09.2005 – 03.2010, Internship : Lithography dep. at
CNSE, Albany, NY, USA, 08.2007 – 01.2008, Bachelor thesis: In-situ neutron radiography ofhydrogen absorption in zirconium alloys, KIT, Germany, 10.2009 – 03.2010, European Master instMaterial Science exploiting Large Scale facilities 09.2010 – 08.2012, 1 year: Université Rennes 1,
Rennes, France, Internship: Melting Temperature of Complex hydrides, EMPA, Switzerland 04.2011
nd– 08.2011, 2 year: LMU and TUM, München, Germany 09.2011 – Current
M. v.d.Berg
Corresponding author: Marius van den Berg, E-mail:mariusvdberg@gmail.com Tel. +31 6 4375 199085

6th Int. Symposium Hydrogen & Energy

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6th Int. Symposium Hydrogen & Energy

MARKET POTENTIALSYSTEMS

Stoos, Switzerland 2012FOR

HYDROGENIN

OFF-GRID

ENERGY

Michael Bielmann
Empa Materials Science and Technology, Hydrogen and Energy, Überlandstrasse 129, CH-8600 Dübendorf
Off-Grid energy systems relying on renewable sources have to solve demand – supply – mismatch. Batteries with low
energy storage density do not qualify to store bulk energy over long periods of time. Hydrogen is an ideal energy carrier
for long term storage. We present the cost metrics for battery storage as a function of initial cost and usage frequency.
We present a model to assess the cost of energy for the hydrogen cycle. Cost of electrolysis is the mayor cost driver
dominating cost of storage and fuel cell by a large margin. The solution has the potential for cheaper storage thanbatteries over periods of months even today.

The Off-Grid Energy Market
Off-Grid energy solutions are dominated today by Diesel
generator solutions usually combined with batteries andsome degree of renewable energy sources. The main
advantage of generators is the dispatchability of energy
on demand. Fuel cost and especially transport of fuel canincrease the cost of energy well above 1$/kWh with
unsecure future trends. PV/Wind-Battery systems on theother hand suffer from low production capacity usage due
to limited battery capacity and capability of loaddeference. Unused, excess production is the norm, withsometimes as little as 20% of the total production used.

defined by electrolyzer and fuel cell, while energy isfreely scalable by the storage size. Assessing costcompetitively to other forms of system implementation
therefore has to be abstracted from the individual size ofthe implementation to get a generalized estimate of thecost of energy through this pathway.

Technology Limitations and Opportunities
PEM electrolysis is available in the low to medium power
regime and allows for fast power modulation and partload, a necessity for excess energy usage in renewablesystems. High pressure electrolysis is a key technology
to leverage on cheap storage. Currently, this technology
is very expensive and with limited availability, but ascaught strong attention in R&D [2]. Currently, it is the key
cost driver in hydrogen hybrid systems and therefore
offers opportunity for improvement. Fuel Cells today do
not contribute substantially to the cost of energy in such asystem, if stack life around 5000h are achieved. Current
technology satisfies this criterion [3].

References[1] Bielmann, M., et al.,. Journal of Power Sources, 2011.
196(8): p. 4054-4060.
[2] Clarke, R.E., S. Giddey, and S.P.S. Badwal,
International Journal of Hydrogen Energy, 2010.
35(3): p. 928-935.

Integrated Hydrogen Cycle for Energy
By integrating the hydrogen cycle, excess energy can be
harvested, stored and made dispatchable over long
periods of time[1]. The main difference to battery storageis the total decoupling of power and energy. Power is[3] Kammerer, M., in Proceedings of the WHEC, D.G.
Stolten, Thomas;, Editor 2010, Schriften des
Forschungszentrums Jülich: Jülich.

1999 University Diploma in Solid State Physics, Fribourg, Switzerland
1999-2005 PhD student at nanotech@surfaces Labs, EMPA Thun and University of Fribourg,
Switzerland
From 2006 PostDoc and Project Leader, Hydrogen and Energy Labs, EMPA Dübendorf

Michael Bielmann
Corresponding author: Michael Bielmann, michael.bielmann@empa.ch, Tel. +41(0)587654342

876th Int. Symposium Hydrogen & Energy

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6th Int. Symposium Hydrogen & Energy

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HYDROGEN SORPTION PROPERTIES OF THE MgB2 BASED CaH2 AND
CaH2-CaF2 REACTIVE HYDRIDE COMPOSITES
C. Pistidda1, K. Suarez Alcantára2, F. Karimi1, C. Bonatto Minella1, L. Rude3, J. Bellosta
von Colbe1, K. Taube1, T. R. Jensen3, T. Klassen1, M. Dornheim113Helmholtz Zentrum Geesthacht, Max-Planck-Strasse 1, D-21502 Geesthacht, Germany, 2 MAX-Lab, Lund, Sweden.
University of Aarhus, Denmark

The hydrogen sorption properties of MgB2 based Reactive Hydride composites (RHC), prepared from mixtures of CaH
and MgB2 and CaH, MgB2 and CaF2, were studied in detail. In order to understand the phase developments and reaction
pathways, the two MgB2 based mixtures, were investigated by Powder X-ray diffraction (PXD), in situ Synchrotron
Radiation Powder X-ray diffraction (SR-PXD), High Pressure titration (volumetric measurement), High Pressure
Differential Scanning Calorimetric techniques (HP-DSC) and solid state magic angle spinning nuclear magnetic
resonance spectroscopy (MAS NMR). It was found, that the enhancement of the formation of the borides CaB6 and MgB2
will be the key to develop a fully reversible hydrogen storage material with good kinetics and working temperatures.

Motivation
Compared to the pure borohydrides, the so called
Reactive Hydride Composites exhibit full (mixtures of
LiBH4 + MgB2 [1.]) or partial reversibility (Ca(BH4)2 +MgB2 [2.]) at much more moderate conditions. The
reactive hydride composite Ca(BH4)2 + MgH2 is of highinterest, as it combines a rather low hydrogenation
enthalpy (expected to be below 50 kJ/(mol H2) [3.] with atheoretical gravimetric hydrogen capacity of 8.3 wt.%.
Addition of fluorine is expected to further reduce thereaction enthalpy, in case it substitutes for hydrogen in
the (BH4)- groups. In addition, an enhancement of thereaction kinetics is also expected [2.]. In order to fully
exploit the potential of F substitution, the reaction
pathways of CaH2 and CaH2-CaF2, respectively, + MgB2
based RHC were studied.

Experimental Results) [a.u.]Heat flow (exo.

3CaH2+4MgB2+CaF2
300

Addition of fluorine significantly enhances the formationof Ca(BH4)2 in a CaH2 and MgB2 containing RHC.
Furthermore, it lowers the hydrogen desorption
temperature. So far the effect of F was found to be notstable upon cycling. In this study, full reversibility was notachieved for any of the investigated systems.

References

First hydrogen desorption
200

Discussion

Further studies of the effects of reaction pressure andtemperature have to take place, in order to findconditions to hinder the formation of the unwanted side
and end products like MgF2, amorphous boron and othertoo stable boron compounds. New additives have to befound, in order to enhance the formation of the wantedboron compounds (CaB6 and MgB2).

2 K min-1
5 K min-1
10K min-1

100

that of the not fluorinated material (roughly 50 °C less).
Upon cycling, the starting hydrogen desorption
temperature decreases further. Ex situ and in situ XRD
show the partially reversible formation of Ca(BH4)2 and
MgH2, plus MgF2 and rests of CaF2, the latter being
stable during further cycling of the material. Results from
the MAS NMR analysis indicate, that the formation of
CaB6 upon cycling is a key factor for the reversible
formation of the Ca(BH4)2.

400

Temperature [°C]Fig. 1: DSC measurements of hydrogenated mixtures of(i) CaH2+MgB2 and (ii) 3CaH2+4MgB2+CaF2.
CaH2 and MgB2 were milled in a Spex 8000 ball mill, witha ball to powder ratio of 10:1. A fluorine containing
compound was produced under the same conditions
starting from CaH2, MgB2 and CaF2 [3.]. Zirconia balls
were used in order to reduce the contamination by Fe,
which is detrimental for MAS NMR measurements.

[1.] U. Bösenberg et al., Acta Materialia 55 (2007) 39513958[2.] C. Bonatto et al., Journal of Physical Chemistry
C 115 (2011) 18010-18014[3.] D. J. Siegel, C. Wolverton, V. Ozolins, Phys. Rev. B
76 (2007) 134102-1 – 134102-6[4.] K. Suarez Alcantára et al., J. Solid State Chem., inpress, DOI: 10.1016/j.jssc.2011.09.019

Fig. 1 shows the DSC traces of the two hydrogenatedcompounds. As can be seen, the hydrogen release fromfluorinated compound starts at a temperature lower than

89

6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012

1979-1986: Study of physics at the University of Hamburg, 1987-1991: PhD Thesis at the Philips
Research Laboratory Hamburg, Dept. Thin Films, 1991-2000: Scientist at the Fraunhofer Institute for
Surface Technology and Thin Films, Braunschweig, 2000-2001: Head of Dept. Forming Technology
at IFU Institute for Forming Technology, Lüdenscheid, since 2002:Scientist at the Institute ofMaterial Science at Helmholtz-Zentrum Geesthacht Research Centre

Klaus Taube

Coordinator of the EU Collaborative Project "FLYHY" (2009 - 2011), Coordinator of the Marie Curie
RTN COSY (2006 - 2010)

Corresponding author: Dr. Klaus Taube, klaus.taube@hzg.de, Tel. +49 4152 87 25 4190

6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012

SELF IGNITING CATALYTIC HYDROGEN BURNER WITH ZERO IMMISSON
Ulrich F. Vogt1,2, Benjamin Fumey1, Noris Gallandat1 and Andreas Züttel1
1

EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland

2

Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

For the development of a catalytic hydrogen diffusion burner, a highly porous silicon carbide foam ceramics (SiC) with aplatinum based catalytic coating has been utilized. Passive safety measures are achieved through the strict separation ofhydrogen and air, feed to the reaction zone and the catalytic response of platinum for the hydrogen oxidation.

Set up of the catalytical H2 burner
If hydrogen is available, the direct combustion ofhydrogen for cooking and heating purposes is favorable
before converting hydrogen to electricity and then toheat due to the higher efficiency and lower systemcomplexity. For this purpose a novel catalytic hydrogen
diffusion burner based on highly porous silicon carbide
ceramic foams with platinum (Pt) coating has beendeveloped. The catalytic properties and the separated
supply of hydrogen and oxygen as air to the catalytic
active area assures a high passive safety standard.
Owing to the absence of hydrocarbon fuel and due to
combustion temperatures just below 1000°C, no harmful
exhaust gases such as CO, CO2 and NOx are emitted,
achieving yet another decisive system safety benefit.
The burner development has undergone two mayor
steps. Initially one Pt coated porous SiC foam was used,
whereby hydrogen is fed from below the SiC plate andair is supplied to the surface. A forced air stream is
supplied through a web of perforated steel tubes
overlaying the SiC plate as shown in figure 1. For anadvancement development, a second Pt coated SiC
foam was introduced above the air supply, as
demonstrated in figure 2. Reaching the lower
flammability limit outside of the reaction zone is so
definitely prevented, the hydrogen slip above thereaction zone was measured to be below 100 ppm. For
indoor applications and zero hazard emission
combustion this is a decisive issue.

Fig. 1: Principle of the burner setup with one catalytic coated SiC
foam and overlying air supply system.

Fig. 2: Principle the advanced burner setup with primary andsecondary catalytic SiC foam and intermediate air supply
system.

Dr. Ulrich Vogt is Senior Scientist at EMPA, Laboratory “Hydrogen & Energy” and leader of thegroup electrolysis & membranes. He received his PhD and his P.D at the Albert-Ludwig-University
Freiburg, Germany. Topics of his research work are hydrogen production via “high temperature
steam electrolysis”, “new membrane materials for low temperature alkaline water electrolysis” and“applying hydrogen for cooking and heating” by a novel developed catalytic hydrogen burner system.
U. Vogt authored over 50 publications and he is lecturer at the University of Freiburg, with the topic“Materials for Energy Research”.
Dr. Ulrich Vogt
Corresponding author: ulrich.vogt@empa.ch, Tel. (+41) 58 765 4160

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DYNAMICS IN SOLID AND LIQUID LIBH4
Pascal Martelli1,2, Arndt Remhof1, Andreas Borgschulte1, Philippe Mauron1, Dirk
Wallacher3, Margarita Russina3, Andreas Züttel1,2
1

Empa Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf,
Switzerland, 2 Physics Department, University of Fribourg, 1700 Fribourg, Switzerland, 3 Department Methods andInstruments, Helmholtz-Zentrum Berlin, Hahn-Meitner Platz 1, 14109 Berlin, Germany
The hydrogen dynamics of LiBH4 were studied by means of incoherent quasielastic neutron scattering (QENS). In thesolid phase, we observe rotational jump diffusion of the BH4 subunits. And we measured the diffusion coefficient in theliquid phase. This one shows an Arrhenius behavior.

Introduction
The use of complex hydrides as hydrogen storage
materials is hindered by the slow sorption kinetic;
therefore it is more than welcome to study carefully the
dynamical processes. The two phases of LiBH4 were
investigated by means of incoherent quasielastic neutron
scattering. In the solid phase, experimental results
reported in [1] were reproduced. The liquid phase wasstabilized by applying a hydrogen overpressure of 50 bar.
While there are rapid localized molecular motions of the
BH4- anion, the lateral mobility of individual H atoms is+orders of magnitude slower than that of Li cations.
Thereby, the main mechanism of hydrogen transport isdiffusion of the BH4- units is found. The measured-52
diffusion coefficients are in the 10 cm /s range attemperatures around 700 K, which is in the same order ofmagnitude as the self-diffusion of liquid lithium or the
diffusion of ions in molten alkali halides. The temperaturedependence of the diffusion coefficient shows an
Arrhenius behaviour, with an activation energy of Ea=88
meV and a prefactor of D0=3.1×10-4cm2/s [2].

Take-home message
The use of complex hydrides as hydrogen storage
materials is hindered by the slow sorption kinetics. One
possible barrier is a slow diffusion of species. However,-5
the measured diffusion coefficient in the order of 10
2
cm /s is relatively fast when compared to hydrogen
diffusion in conventional metal hydrides with fasthydrogen sorption. Therefore the diffusion can be
excluded as the rate limiting step for hydrogen sorption in
molten LiBH4. The rate limiting step is thus yet due toother mechanisms, such as the formation or the breakingof the B-H bonds [3].

References[1] Remhof, A.; Łodziana, Z.; Martelli, P.; Friedrichs, O.;
Züttel, A.; Skripov, A. V.; Embs, J. P.; Strässle, T.,
Phys. ReV. B, 2010, 81, 214304.
[2] Martelli, P.; Remhof, A.; Borgschulte, A.; Mauron, Ph.;
Wallacher, D.; Russina, M.; Züttel, A.; et Al., J. Phys.
Chem. A, 2010, 114, 10117
related to the diffusion of complete BH4- units.
Left: Arrhenius plot of self-diffusivities of BH4 in liquid
LiBH4, Right: The right panel compares the Li diffusivities
in elemental, liquid Li, and molten salts.

[3] Friedrichs, O.; Remhof, A.; Borgschulte, A.; Buchter,
F.; Orimo, S. I.; Züttel, A., Phys. Chem. Chem. Phys.
2010, 12, 10919.

Results
Rotational jump diffusion of the BH4- subunits on thepicosecond scale were observed in solid LiBH4. In themolten phase of LiBH4 above 553 K, translational
Born 12.05.1981 in Fribourg, Switzerland. 1998 language course in Germany. 2002 College in Math,
Fribourg, Switzerland. 2007 Master in physics and math of University of Fribourg. 2011 PhD in
Condensed Matter Physics from University of Fribourg, at A. Züttel lab "Hydrogen & Energy", EMPA
Dübendorf, Switzerland.
Corresponding author: Pascal Martelli, email: pascal.martelli@hotmail.com, Tel. (+41) (79) 354 60 44

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SOLID STATE ELECTROCHEMICALELECTRONS TO FUELSCONVERSION

OF

CLEAN

John TS Irvine
School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, Scotland, United Kingdom
Abstract
High temperature steam electrolysis (HTSE) is a highly efficient process for the production of pure hydrogen using a
combination of electrical and thermal energy and is environmentally clean provided that the electricity used comes from arenewable source (e.g. solar, wind, wave, tidal).

SummaryHigh temperature steam electrolysis (HTSE) is a highly
efficient process for the production of pure hydrogenusing a combination of electrical and thermal energy andis environmentally clean provided that the electricity usedcomes from a renewable source (e.g. solar, wind, wave,
tidal). HTSE is carried out using a solid oxide electrolysis
cell (SOEC), which is essentially a solid oxide fuel cell
(SOFC) operated in reverse. That is, steam iselectrochemically reduced to hydrogen gas and oxideions at the hydrogen electrode (cathode), followed byoxide ion migration across the solid electrolyte to the air
electrode (anode) where oxygen is evolved. This study
considers (La,Sr)TiO3 perovskites as alternativeelectrolysis cell cathode materials to Ni/YSZ due to theirchemical, dimensional, redox, thermal and mechanicalstability. The influence of defect chemistry on steam
electrolysis properties in particular is investigated bycomparing oxygen-excess (La0.3Sr0.7TiO3+) and A-site
deficient (La0.2Sr0.7TiO3) compositions. La0.3Sr0.7TiO3+ ispart of the LaxSr1-xTiO3+ series (x = 0.3) and the parent
perovskite SrTiO3.
In a different approach, synthetic hydrocarbon
fuels prepared from water and carbon dioxide areproposed as alternatives to hydrogen as an energy
carrier to enable a carbon neutral energy cycle, given
their inherent advantages of high H/C ratio andconvenience of storage and transportation. Here wedemonstrate the successful synthesis of methane via
direct electrochemical reduction of carbon dioxide in a
proton conducting solid oxide electrolyzer based on
BaCe0.5Zr0.3Y0.16Zn0.04O3-δ and composite Iron/Iron oxide
cathode.

John Irvine is Professor of Chemistry at the University of St Andrews. His research interests are insolid state ionics, new materials, ceramic processing, electrochemistry, fuel cell technology,hydrogen, photoelectrochemistry, electrochemical conversion and heterogeneous catalysis.

John TS Irvine
Corresponding author: John TS Irvine, Tel: +44 1334 463817, Email: jtsi@st-andrews.ac.uk

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SORPTION ENHANCED REACTIONS FOR RENEWABLE SYNFUELS
Andreas Borgschulte, Shunsuke Kato, Benjamin Probst, Riccardo Suter, Andreas Züttel,
Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
Starting from findings by Sabatier in 1902, it is known that CO2 can be reduced by H2 over a catalyst producing
eventually methane and water. If the hydrogen is produced from renewable energy sources by electrolysis and thecarbon dioxide is extracted from the atmosphere, the methane from such a process represents a CO2 neutral synthetic
fuel. Apart from being a model system for the investigation of synfuels, a ready-to-go application is the upgrade of biogas
using this process. Biogas produced by fermentation of biological materials contains approximately 60% CH4 and 40%
CO2. Instead of separating the CO2 and releasing it into the atmosphere, it is converted into CH4 using the Sabatierprocess. In this talk I demonstrate the concept of the sorption enhanced reaction to improve the efficiency of process.

Sorption enhanced reaction
The reduction of CO2 by hydrogen eventually forminghydrocarbons depends on the interaction of CO2 and H2
with a catalyst surface, i.e. ad- and desorption ofhydrogen, CO2 and products [1]. A significant increase of
the process efficiency requires a novel concept tocatalyze the complex chemical reactions. In this talk, wewill utilize the link between surface and bulk to control
the surface reaction. This will be done either bycontrolling the educts’ side, or by controlling the products’side, both by using bulk sorption reactions (Sorption
enhanced reaction) [2].

Educts’ side
The golden rule of catalysis (Sabatier principle) is
usually depicted by the volcano curve: an optimal catalyst
has intermediate binding energy to the adsorbent,
because an enhanced bonding strength increases theadsorption, but decreases the desorption reaction. Due tothe high mobility of hydrogen, it is most simple to control
the driving force of the Sabatier reaction by enhancing
the amount of chemisorbed hydrogen on the catalyst’s
surface. I will discuss the surface reactions of CO2 onvarious metal hydrides.

CO2 + 4H2

CH4Products’ side
The desorption reaction is strongly enhanced by theremoval of water by its absorption in the inner bulk of asorption catalyst (see picture). As a proof-of-concept, an
improvement of the reaction yield of more than 100% of
the Sabatier was realized using Ni-zeolite sorption
catalysts.

References[1] J. K. Nørskov, et al., Nature Chemistry 1, 37 (2009).
[2] B. T. Carvill, et al. , AIChE J. 1996, 42, 2765.

A. Borgschulte

Born 1973 in Lippstadt, Germany. 1998/2002 diploma and PhD in physics from Technical University
Braunschweig, Germany. 2002-2005: PostDoc at the VU Amsterdam, The Netherlands, head Prof.
R. Griessen, “Combinatorial Research for New Light Weight Complex Hydrides by Optical
Spectroscopy.” 2005–2006: Project co-ordinator of the hydrogen storage project FuncHy, GKSS
Research Centre Geesthacht, Germany, head Prof. R. Bormann, “Kinetics and Stability ofmagnesium hydride.” Since 2006 Group leader in the Laboratory Hydrogen & Energy at Empa,
Dübendorf, Switzerland.

Corresponding author: Andreas Borgschulte: andreas.borgschulte@empa.ch, Tel. +41 58 765 4639

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HYDROGEN STORAGE AND DELIVERY
Gábor Laurenczy
EPFL, École Polytechnique Fédérale de Lausanne, ISIC, LCOM, Groupe de catalyse pour l’énergie et l’environnement –GCEE, CH-1015 Lausanne, Switzerland
Carbon dioxide and carbonates have been proven to be viable H2 vectors, as these widely available natural C1 sources
can be easily hydrogenated to formic acid and formates in water. Although ruthenium(II) and other platinum group metalcompounds are the predominant catalysts in these reactions, iron(II) can be also active, giving a new perspective to use
abundant and inexpensive Fe based compounds in CO2 reduction. On the other hand, formic acid can be selectively
decomposed into CO free (< 10 ppm) carbon dioxide and hydrogen. We have shown, that beside the ruthenium(II)mTPPTS system, the iron(II) – hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex also catalyses with an-1-1
exceptionally high rate and efficiency (turnover frequency, TOF= 9425 h mol ; turnover number, TON= 92400) theformic acid cleavage, opening the way to use cheap, non-noble metal based catalysts for this reaction.

Introduction
Hydrogen is one of the potential candidates to replacefossil fuels both for environmental and economic
reasons. H2 has the advantage to form only water when it
is burned; and combined with fuel cell technology a very
efficient conversion of the chemical energy into electricity
can be achieved. However, the delivery of H2 remains achallenge: conventional hydrogen storages like highpressure gas containers and cryogenic liquid containers
have weight and safety issues. Therefore a variety of
new materials and methods are under development; theH2 storage and generation currently are active areas ofresearch.

Results and discussion
For the first time, the reduction of CO2 and bicarbonates
to formate/formic acid in the presence of an iron catalyst(Fe(II)hydrido-tris[(2-diphenylphosphino)ethyl]phosphine)
have been demonstrated.

The same complex, formed by mixing Fe(BF4)2·6H2O andthe ligand tris[(2-diphenylphosphino)ethyl]phosphine(P(CH2CH2PPh2)3, PP3) has been proven very active informic acid decomposition: Applying 50 ppm of thiscatalyst precursor, H2 generation is carried out withoutstanding turnover frequencies up to 9425 h-1; andturnover numbers as high as 92.000 were achieved.
Acknowledgment. Swiss National Science Foundationand EPFL are thanked for financial support.

References[1] C. Fellay, P. J. Dyson, G. Laurenczy*, A Viable
Hydrogen-Storage System Based On Selective
Formic Acid Decomposition with a Ruthenium
Catalyst, Angew. Chem. Int. Ed., 2008, 47, 3966.
[2] C. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn,
P. J. Dyson, R. Scopelliti, G. Laurenczy*, M. Beller*;
A Well-Defined Iron Catalyst for the Reduction of
Bicarbonates and Carbon Dioxide to Formates, Alkyl
Formates, and Formamides, Angew. Chem. Int. Ed.,2010, 49, 9777.
[3] G. Papp, J. Csorba, G. Laurenczy, F. Joó, A
Charge/Discharge Device for Chemical Hydrogen
Storage and Generation, Angew. Chem. Int. Ed.,
2011, in press, DOI: 10.1002/anie.201104951[4] A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H.
Junge, P. J. Dyson, G. Laurenczy*, R. Ludwig*, M.
Beller*, Efficient Dehydrogenation of Formic Acid
Using an Iron Catalyst, Science, 2011, 333, 1733.

Figure 1. View of the molecular structure of the catalyst[FeH(PP3)]BF4.

Gábor LaurenczyBorn in Békéscsaba, Hungary, 1954. Chemistry M.Sc. at the Univ. Debrecen, Hungary, 1978. PhD.
in Physical Chemistry, Univ. Debrecen, Hungary, 1982. Habilitation in Inorganic Chemistry,
Hungarian Academy of Sciences, 1991. Assistant professor, Dept. of Inorganic Chemistry, Univ.
Debrecen, Hungary, 1984. Maître assistant, Université de Lausanne, 1991. Maître d’enseignement
et de recherche, Univ. Lausanne, 1997. M.E.R., EPFL, École Polytechnique Fédérale de Lausanne,
2002. Chairman of the Management Committee of the European COST D10 Chemistry Action:
Innovative Methods and Techniques for Chemical Transformation, 2001-2002. Chairman of the M.
C. European COST D30: High Pressure Tuning of Chemical and Biochemical Processes, 20022007. Visiting professor, Dept. of Chemistry, University of Bourgogne, France, 2007. Prof. EPFL,
2010. Head of Group of Catalysis for Energy and Environment – GCEE, 2010.

Corresponding author: Prof. Gábor Laurenczy, email: Gabor.Laurenczy@epfl.ch, Tel. (+41) (21) 693 9858

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REVERSIBILITY OF
ALANATE

H2

Stoos, Switzerland 2012

SORPTIONIN

NANOCONFINEDSODIUM

Jinbao Gao, Krijn P. de Jong, Petra E. de Jongh
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Sorbonnelaan 16,3584 CA Utrecht, the Netherlands
Abstract: Nanoconfining NaAlH4 in porous materials improve the reversibility of desorption, but still capacity decay isobserved during cycling. Present study showed that the large Al grains (>100 nm) formed after desorption could reactwith Na and H2 forming nanoconfined NaAlH4. With additional Na, almost full reversibility was obtained under mild
conditions. These findings indicate that the solid state diffusion of large Al grains was not the limiting factor for hydrogen
absorption; instead, it was the availability of Na that limits the reversibility of this nanoconfined NaAlH4 desorption.

Introduction
Sodium alanate (NaAlH4) releases H2 in three steps witha total H2 content of 7.4 wt%. However, it shows slow
kinetics for H2 sorption, and only limited reversibility ofdesorption can be achieved. In addition to the catalyst
doping, improved kinetics and reversibility were obtainedby confining NaAlH4 in nano-porous materials [1, 2].
However, only partial reversibility was achieved. In ourcontribution, we discuss the factors that govern the H2absorption of fully desorbed nanoconfined NaAlH4, andhow full reversibility can be achieved.

nanoconfined NaAlH4/C system, large Al grains were also
formed after full desorption, it is found that the solid Al
has a remarkable mobility and can be reconverted into
nanoconfined NaAlH4 under mild conditions. Further
study shows that it is the availability of Na after firstdesorption hinder the rehydrogenation. With addition of
extra Na, almost full reversibility of desorption wasachieved (Figure 1, red curve). The unavailability of Na ismainly caused by the side reactions between Nacontaining species and impurity (especially O-groups) on
the surface of carbon support.

Materials and Methods
st

1

nd

2

0.9

Al : Na = 0.8
0.6

1

st

2

nd

0.3

0.0
60

Results and Discussion
Nanoconfined NaAlH4 shows improved reversibility
without a metal-based catalyst. However, only partial
reversibility of desorption was observed (Figure 1, black
curve). For bulk NaAlH4, high pressures and extended
charging times are needed to achieve partial reversibility,
which has commonly be ascribed to the hypothesis that
H2 absorption is limited by solid state diffusion of
decomposition products, especially Al. Although indesorption nanocomposited with
Al : Na = 1.3

1.2

wt% H2 / g Sample

Nanoconfined 20 wt% NaAlH4 in porous carbon was
synthesized by melt infiltration as described earlier [2].
Extra Na was introduced to the dehydrogenated sample
by desorbing physical mixture of melt infiltrated 20 wt%
NaAlH4/C and NaH. Dehydrogenation was conducted in aotubular oven at 325 C under Ar flow. Rehydrogenation
was conducted in an autoclave under 55 bar H2 and 150oC. H2 sorption properties were studied by temperature
programmed desorption (TPD) and Sieverts apparatus.

120

180

240

300

360

420

o

Temperature Cstnd

Figure 1. 1 and 2 H2 release of nanocomposites
with Al / Na molar ratios of 1.0 and 0.8

References[1] B. Bogdanovic, M. Schwickardi, J. Alloys
Compd., 1-9, 253 (1997)[2] J. Gao, P. Adelhelm, M. H.W. Verkuijlen et al.,J. Phys. Chem. C, 114, 4675 (2010)

Born 08. 02. 1982 in Inner Mongolia, China. 2004 Science Degree in Chemistry, Shanghai, China.
2007 Master Degree in Physical Chemistry from the East China Normal University, China. 2008now PhD student in the group of Inorganic Chemistry and Catalysis at Utrecht University, theNetherlands.
Jinbao Gao
Corresponding author: Jinbao Gao, email: mail to: J.Gao@uu.nl, Tel. (+31) (30) 253 676

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Development Of Alkylation Toluene With
Methanol for fuel On Modified ZSM-5 Zeolites
By Amphoteric surfactant
A.K.El Morsi* , A.M.A.Omar1
Nora Y Almehbad2
1 Egyptian Petroleum Research Institute.
2 University of Gizan, Kingdom Of Saudi Arabia.

* abdelazimomar@yahoo.co.uk

ABSTRACT:
Methylation of toluene over ZSM-5 zeolites modified by the
introduction of Sr of 2.5 % , 5 % , 10 % by weight was studied.
Experiments were performed in a fixed bed,reaction temperatures
between 300-500o C and liquid hour space velocity of 4 g toluene / h.g
catalyst and methanol to toluene ratio 4:1 and 0.01% of N-Octyl-Nbenzyl- N-methylglycine as emulsifier .
Microemulsion are stable emulsions of surfactants and co-surfactants.
The wide spread interest in microemulsion and use in industrial
applications are based mainly on their high solublization capacity for bothhydrophilic and lipophilic compounds , large interfacial areas and on theultra- low interfacial tensions achieved when they coexist with exessaqueous and oil phases
Data for conversion of toluene and selectivity towards xylene isomers
showed that 2.5 % Sr/ZSM-5 catalyst has the highest conversion of
toluene at 500 o C , and the lowest p-xylene selectivity , while 10 %Sr/ZSM-5 catalyst has the highest selectivity for p-xylene production.
Nevertheless , the catalyst 2.5 % Sr/ZSM-5 has the highest selectivity for
m-xylene. The two catalysts 2.5% and 5% Sr/ZSM-5 give nearly thesame selectivity for the three xylene isomers at all conversions obtainedat the reaction conditions under study.

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OPTICAL NANOANTENNAS SHINE LIGHT ON SINGLE NANOPARTICLES
Christoph Langhammer
Department of Applied Physics, Chalmers University of Technology and Insplorion AB, Göteborg, Sweden
Studying nanomaterials in situ in real time and relating details in structure and local chemistry to functionality is a key
challenge in modern (nano)materials science. The exploitation of plasmonic optical nanoantennas as single particle
sensing units opens up a completely unique avenue towards real time single particle in situ spectroscopy of functional
nanomaterials operating in harsh environments typical for (photo-) catalysis as well as hydrogen storage.
New and more efficient implementation of nanomaterials
requires the correlation of details in nanoparticle size,
structure and local chemistry with the targeted
functionality. Scrutinizing such systems and relating
details in their chemistry and geometry to functionality
remains, however, a significant experimental challengewith two main aspects.
The first one relates to the fact that the only fully
satisfactory way to acquire such information is by the useof real time in situ spectroscopy. The latter is, however,experimentally very tough, in particular in harshenvironments (high temperatures, reactivegas
atmospheres) such as those typical for heterogeneous
catalysis or hydrogen storage applications and relates tothe well-known material (structure) and pressure gaps.
The second one relates to unwanted “artifacts” andaveraged response as always present in ensembles ofsample material and mainly caused by inhomogeneous
size-distributions, and differences in the local chemistry
and the local structure of (quasi-identical) nano-entities inthe ensemble.
Experiments aiming at the characterization of single
functional nano-entities in situ have the potential tocompletely eliminate or significantly alleviate suchproblems by facilitating highly relevant systematic studies
of correlations between details in nano-entity
geometrical, physical and chemical properties, andfunctionality.
1,2
exploits
Indirect Nanoplasmonic Sensing (INPS)
plasmon excitations in gold nanoparticles (so-called
optical nanoantennas) to scrutinize processes in adjacentcomplex nanomaterials in situ and in real time. Studies ingas and liquid environments are possible at hightemperatures and pressures, which qualifies INPS as avaluable addition to the existing methodologies used to

study nanomaterials’ structure-functionality relations inharsh environments.
Here particular focus will be put on the unique possibility
to use the INPS concept to study single functional
nanoparticles for hydrogen storage and hydrogensensing applications3,4. The latter will be illustrated on a
study of the hydride formation thermodynamics of single
Pd and Mg nanoparticles. Aspects relating to the longstanding question of the origin of slope on the equilibrium
plateau will also be addressed together with a discussionof the general potential of single particle optical antennabased spectroscopy for materials science applications.

Figure 1: (a) Environmental SEM picture of truncated Au
nanocone antennas functionalized with Ti/Mg/Ti/Pd “tips” forsingle particle hydrogen storage experiments. (b) Dark-field
scattering microscope image of a single nanocone antenna.

References[1] E.M. Larsson et al., Science 326, 1091-1094 (2009)[2] C. Langhammer et al., Nano Lett. 10, 3529–3538(2010)[3] T. Shegai and C. Langhammer Adv. Mater. 23, 44094414 (2011)[4] N. Liu et al. Nat. Mater. 10, 631–63 (2011)

M.Sc. in Materials Science 2004, Swiss Federal Institute of Technology (ETH), Department ofMaterials, Zürich, Switzerland.
Ph.D. in Materials Science 2009, Chalmers University of Technology, Applied Physics, Göteborg,
Sweden.
Current: Assistant professor, Department of Applied Physics, Chalmers University of Technology,
Göteborg, Sweden
C. Langhammer

CTO at Insplorion AB, Göteborg, Sweden (www.insplorion.com).

Corresponding author: Christoph Langhammer, clangham@chalmers.se, Tel. +46 (0)31 772 3331

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LONG-TERM STABILITY OF SOFC CATHODES
Werner Sitte, Edith Bucher and Andreas Egger
Chair of Physical Chemistry, Montanuniversität Leoben, 8700 Leoben, Austria
Abstract: Within this work the long-term stability of promising SOFC cathode materials with respect to the oxygen surface
exchange kinetics in dry as well as in H2O- and CO2-containing atmospheres is reported: the chemical surface exchange
coefficients kchem of oxygen of the perovskite oxide La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF) is compared to that of the K2NiF4-typeoxide Nd2NiO4+δ (NNO) in long-term tests (t>1000 h) between 600 and 700°C in dry and humid atmospheres. Post-test
XPS-depth profiles of LSCF and NNO samples, especially those which were kept in humid atmospheres show significant
changes of the surface and near-surface cation compositions correlated with a strong decrease of kchem.

Overview
With the efforts to reduce the operating temperature of
SOFCs to 600-750°C, the development of a number ofnovel mixed conducting cathode materials has beenstimulated. A main issue of these cathodes is the longterm-stability in ambient atmospheres. Within this work
the long-term behaviour of the oxygen exchange kineticsof the two cathode materials La0.58Sr0.4Co0.2Fe0.8O3-δ
(LSCF, perovskite structure) and Nd2NiO4+δ (NNO,
K2NiF4-structure) in H2O- and CO2-containing atmospheres is described.

Experimental
Chemical surface exchange coefficients kchem of oxygen
are obtained from dc-conductivity relaxation experiments
in long-term tests (t>1000h) in dry (Ar-O2) and humid
atmospheres (Ar-O2-H2O; 30% relative humidity) at 600700°C. Pre- and post-test analyses of the samples werecarried out by X-ray photoelectron spectroscopy (XPS,
Thermo MultiLab 2000, alpha 110 hemisphericalanalyzer, Thermo Electron). Elemental depth profiles
were obtained by Ar ion etching. The sputter rate wascalibrated by use of a Ti layer.

Results and discussion
The chemical surface exchange coefficient kchem ofoxygen of LSCF and NNO was monitored for t>1000h in
dry and humid atmospheres at 600-700°C. XPS-depth
profiles of LSCF and NNO - especially those samples
which were kept in humid atmospheres - show significant
changes of the surface and near-surface cation
compositions which are correlated with a decrease ofkchem [1, 2].
At 600°C, kchem of LSCF decreases at least by a factor of
two within a time scale of 1000 h in a dry O2–Ar reference

atmosphere. XPS-depth profiles show that the decreaseof kchem can be attributed to a change of the cation
composition at and near the surface (La- and Srenrichment within about 30 nm depth) together with anincreased oxygen content. Under comparable conditions
at 700°C, the chemical surface exchange coefficient of
NNO remains perfectly stable.
In a humidified atmosphere at 600°C an additional strong
decrease of kchem by a factor of 10 is observed with
LSCF. XPS post-test analysis identifies severe Sipoisoning within a 10 nm thick Sr- and O-enrichedsurface zone as the origin of the degradation. It is
assumed, in agreement with thermodynamic data, thatsilicon is transported in humid atmospheres as Si(OH)4(g)via the gas phase towards the surface of the sample.
Also for NNO a decrease in kchem by a factor of 10 isobserved in humid atmospheres at 700°C. According to
XPS, the degradation of NNO can be interpreted by theformation of a 100 nm thick zone with significant changes
in the Nd:Ni cation ratio. No indication of Si-poisoning
was found for NNO.
In this respect the use of dry air as an oxidant for ITSOFCs operating at 600-700°C is recommended. Since
Sr-containing cathodes such as LSCF seem to degrade
to some extent even in a dry atmosphere, the use ofalternative Sr-free materials may be one way to increase
the long-term stability of SOFCs.

References[1] A. Egger, W. Sitte, F. Klauser, E. Bertel,
J. Electrochem. Soc., 157 (2010) B1537-B1541.
[2] E. Bucher, W. Sitte, F. Klauser, E. Bertel,
Solid State Ionics 191 (2011) 61-67.

Short CV
Born in Salzburg (Austria); Studies of Technical Chemistry at Graz University of Technology
1990: Habilitation in the field of Physical Chemistry
Since 2000: Full Professor of Physical Chemistry, Chair of Physical Chemistry, Montanuniversität
LeobenSince 2004: Head of Department of General, Analytical and Physical Chemistry, Montanuniversität
LeobenWerner Sitte
Corresponding author: Prof. Werner Sitte, sitte@unileoben.ac.at, Tel.: +43 3842 402 4800

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ELECTROCHEMICAL CHARACTERISATION OF A
ALKALINE ELECTROLYZER AND NOVEL MEMBRANESSMALL-SCALE

Ivo Trajkovic1, Michal Gorbar1,2, Ulrich F. Vogt1,3, Andreas Züttel1,2
1

EMPA, Materials Science & Technology, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy,
Dübendorf, Switzerland

2

University of Fribourg, Dept. of Physics, Fribourg, Switzerland

3

Albert Ludwigs University, Freiburg i. Br. Faculty of Crystallography, Germany

Abstract In the industry, hydrogen is used for producing ammonia and fertilizers, refining metals, and as energy carrier.
Electrolysis with alkaline electrolytes is established and proven to extract hydrogen from water. If the driving electricity is
produced based on renewable resources, electrolysis can be clean and environment-friendly.
Traditionally, asbestos membranes separate the oxygen and hydrogen inside the electrolyser. The geometrical pore
constitution in these membranes ensures high ion conductivity when the pores are filled with an electrolyte solution. In
most industrialized countries, asbestos is declared to be dangerous to health, and hence its usage is prohibited. Thus,
the overall aim is to replace asbestos by alternative materials which, in addition, work at higher temperatures and higher
KOH concentrations and are not dangerous to health. Novel membranes made of these new materials shall be cheap,
broadly available and be advantageous concerning ion conductivity and gas separability as well.
We present (i) a simple experimental setup with a previously built small-scale alkaline electrolyser for estimating the ion
conductivity through the novel membranes, (ii) the estimated conductivity values for each novel membrane compared toasbestos, (iii) the measuring and data evaluation procedures and (iv) the measured potential drop values along theelectrolyser.
Conclusively, our experimental setup has been successfully built up and used to electrochemically characterise novel
membranes which will replace asbestos membranes in industrial electrolysers.



Born on March 3, 1980 in Belgrade, Serbia

2007, Dipl. El. Ing. / Master of Science ETH in the field of digital communications, ETH
Zürich.



2010, Dr. sc. ETH in the field of signal processing and biomedical engineering, ETH Zürich.



2011, postdoctoral research fellow in the field of alkaline electrolysis, EMPA.

Ivo Trajkovic
Corresponding author: Ivo Trajkovic, ivot@alumni.ethz.ch, Tel. +41 44 823 4746

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FAST IONIC CONDUCTION IN COMPLEX HYDRIDES
Motoaki Matsuo1, Arndt Remhof2, Andreas Züttel2, Shin-ichi Orimo1
1

Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan2

Empa, Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

Complex hydrides exhibit various energy-related functions such as hydrogen storage, microwave absorption, andneutron shielding. Furthermore, we recently discovered another novel energy-related function, that is, lithium fast-ionic
conduction, suggesting that complex hydrides can be a potential candidate for solid electrolytes for lithium ion batteries.
A review of our recent progress in the development of lithium fast-ionic conductors of complex hydrides is presented.

Lithium Fast-Ion Conduction in LiBH4
The ion conductivity of LiBH4 increases by threeorders of magnitude at 390 K due to its structuraltransition from the orthorhombic low-temperature(LT-)phase to the hexagonal high-temperature (HT)phase1. From the application point of view, it ishighly desirable to enhance the conductivity of
LiBH4 at RT.

Enhanced Conductivities in LiBH4–LiI and
LiBH4–LiNH2 systems
The enhanced conductivities in LiBH4–LiX (X = Cl,
Br, and I)2 and LiBH4–LiNH23 have been
demonstrated. In LiBH4–LiI, the HT-phase of LiBH4
can be stabilized below 390 K by forming solid
solution phase with a wide range of compositions;as a result, the conductivity (4 × 10−5 S/cm)
becomes three orders of magnitude higher thanthat of pure LiBH4 (2 × 10−8 S/cm) at RT. In theLi2(BH4)(NH2)
and
case
of
LiBH4–LiNH2,
Li4(BH4)(NH2)3 both with combinations of [BH4]– and[NH2]– complex anions, show fast-ion conductivitiesof 1 × 10−4 S/cm at RT because of new occupationsites available to Li+ ions. Furthermore, the total ion
conductivities of Li2(BH4)(NH2) and Li4(BH4)(NH2)3
reach 6×10–2 S/cm (378 K) and 2×10–1 S/cm (513K) after melting, respectively, suggesting thepossible ionic liquids.4

New Complex Hydride in LiNH2–LiI system
The new complex hydride, Li3(NH2)2I, with anunique double-layered structure was synthesized.5
Because of the characteristic structure, Li3(NH2)2I
exhibits fast-ion conductivity of 1 × 10–5 S/cm at
296 K with lithium ion transport number of almost
unity although the conductivities of the hostmaterials LiNH2 (3 × 10–9 S/cm) and LiI (3 × 10–8S/cm) are very low.
This research was funded by KAKENHI (22760529)
and the Integrated Project of ICC-IMR.

References[1] M. Matsuo et al., Appl. Phys. Lett. 91, 224103 (2007).
[2] M. Matsuo et al., Appl. Phys. Lett. 94, 084103 (2009).
[3] M. Matsuo et al., J. Am. Chem. Soc. 131, 16389(2009).
[4] M. Matsuo and S. Orimo, Adv. Energy Mater. 1, 161(2011).
[5] M. Matsuo et al., Chem. Mater. 22, 2702 (2010).

Born 1977 in Kanazawa, Japan. 2008 Ph.D. degree in materials science Tohoku University. 2008
Postdoctoral Fellow, Institute for Materials Research, Tohoku University. 2010 Assistant Professor in
Orimo group. Research interests: fundamental, physical, and chemical properties of lightweight
hydrides; especially solid-state ionics and hydrogen storage.
http://www.hydrogen.imr.tohoku.ac.jp/

Motoaki Matsuo
Corresponding author: Motoaki Matsuo, Email: mmatsuo@imr.tohoku.ac.jp, Tel.: +81-22-215-2094

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CONTROLING THE HYDROGEN DESORPTION OF LIBH4
1

Yigang Yan, 1Arndt Remhof, 2Sonjong Hwang,
5
Shin-ich Orimo, 1Andreas Züttel

3, 4

Hai-wen Li,

1

Philippe Mauron,

1

EMPA, Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA
3International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395, Japan
4
International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka 819-0395, Japan
5
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan2

The dehydrogenation pathway is crucial for the applicability of LiBH4 as a hydrogen storage material. We discuss andcompare the different dehydrogenation pathways of LiBH4 according to the thermodynamic parameters and show theexperimental ways to realize them. Two dehydrogenation pathways of LiBH4, i.e. the direct decomposition into boron andthe decomposition via Li2B12H12, were realized by choosing appropriate conditions, respectively.

Lithium borohydride
The results of PCT measurement by Ph. Mauron suggest
a one-step direct decomposition of LiBH4 into boron [1],according to reaction (1). Based on the observation of
Li2B12H12 by Raman spectroscopy and 11B NMR
measurements [2, 3], LiBH4 is considered to decompose
according to reaction (2).
LiBH4 → LiH + B + 3/2H2
LiBH4 → 5/6LiH + 1/12Li2B12H12 + 13/12H2(eq.1)(2)

Thermodynamic consideration
The enthalpy change of the decomposition reaction into
Li2B12H12 (reaction (2)) is predicted to be 56 kJ/mol H2 [4],which is approximately 18 kJ/mol H2 lower than that ofthe direct decomposition (reaction (1)). This suggeststhat by applying appropriate external pressures, thereaction (1) can be supressed and the decomposition of
LiBH4 will be forced via Li2B12H12 according reaction (2).
The decomposition reactions of LiBH4 at 873 K in
different hydrogen external pressure of 50, 10, 2 and 0.1
bar were carried out. On the other hand, the temperaturedependence of the decomposition was investigated by
fixing the H2 pressure as 10 bar and adjusting
temperature from 873 to 700 K.

Dehydrogenation pathway
The two reaction pathways were realized at approximate
conditions, respectively. By applying a H2 pressure of 50

bar at 873 K and 10 bar at 700 K, LiBH4 is forced todecompose into Li2B12H12. In a lower pressure range of
0.1 to 10 bar at 873 K and 800 K, both two
dehydrogenation pathways are observed. Raman
spectroscopy and 11B NMR MAS measurement confirm
the formation of intermediate phase Li2B12H12 andamorphous boron.
The knowledge of the thermodynamic properties of thehydride and its possible decomposition products andintermediates allows choosing the decomposition
pathway by tuning the external parameters such aspressure and temperature. Therefore, unwanted byproducts or boron sinks that prevent reversibility can be
circumvented.

References[1] Ph. Mauron, F. Buchter, O. Friedrichs, A. Remhof,
M.Bielmann, C. N. Zwicky, A. Züttel, J. Phys. Chem.
C 112, 906 (2008).
[2] S. Orimo, Y. Nakamori, N. Ohba, K. Miwa, M. Aoki, S.
Towata, A. Züttel, Appl. Phys. Lett. 89, 021920(2006).
[3] S. J. Hwang, R. C. Bowman, J. W. Reiter, J.
Rijssenbeek, G. L. Soloveichik, J.-C. Zhao,
H.Kabbour, C. C. Ahn, J. Phys. Chem. C 112, 3164
(2008).
[4] N. Ohba, K. Miwa, M. Aoki, T. Noritake, S. Towata,
Y.Nakamori, S. Orimo, Phys. Rev. B 74, 075110(2006).

Born 14. 2. 1980 in Hubei Province, China. 2001 Bachelor in Chemical Engineering, Chengdu,
China. 2004 Master in Chemical Process Equipment from Sichuan University, China. 2007 Ph.D in
Material Science from Sichuan University. 2008 Post doc Orimo Lab in Institute for Materials
Research (IMR), Tohoku University in Sendai, Japan. 2009 Japanese Society for the Promotion of
Science (JSPS) Post doc at IMR, Tohoku University. Research field: Fundamental properties andhydrogen storage functions of metal borohydrides. 2011 Post doc Züttel Lab in EMPA Swiss Federal
Laboratories for Materials Science and Technology, Switzerland.
YIGANG YAN
Corresponding author: Yigang Yan, email: yigang.yan@empa.ch, Tel. (+41) 58 765 4082

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VERIFICATION OF THE ENTHALPY-ENTROPY COMPENSATION EFFECT IN
METAL HYDRIDES
C. Boelsma1, L.P.A. Mooij1, R. Griessen2, and B. Dam1
1

DelftChemTech, Delft University of Technology, Julianalaan 136, 2600 GA Delft, The Netherlands
Department of Physics and Astronomy, VU University Amsterdam, De Boelelaan 1801, 1081 HV Amsterdam, The
Netherlands
2

The enthalpy-entropy compensation effect is extensively discussed in literature. Although it is observed in many
experiments (e.g. in the analysis of reactions considering proteins or metal hydrides), it is not clear whether this effecthas a physical or a statistical origin. For situations with a compensation temperature close to the harmonic mean
measurement temperature, it is often impossible to distinguish a possible physical origin from a statistical one. We
present and demonstrate a method to verify this kind of compensation in metal hydrides. We show, without using any
statistical analysis, that it is possible to determine the compensation temperature with a much higher accuracy than the
involved temperature range. This indicates a non-statistical origin of the effect.

Introduction
The enthalpy-entropy compensation effect, characterized
by the compensation temperature Tcomp, is known for
more than a century. It is observed in the analysis of thethermodynamics of many reactions, for example in the(de)formation of metal hydrides [1]. Since in many of theobserved compensations the obtained Tcomp is close to
the harmonic mean temperature of the performed
measurements,astatisticalorigincannotbedistinguished from a physical one. Therefore the true
nature of the compensations is questioned [1,2].
Nevertheless, for compensations in metal hydride
systems we present a method to verify whether thecompensation has a statistical origin or not. We
demonstrate this method with use of MgyTi1-yHx, thatshows a compensation for 0.6 < y < 0.8 with Tcomp close
the harmonic mean temperature of the performed
measurements.

The Method
To determine the thermodynamics of each fraction y in
MgyTi1-yHx, we need two ingredients: 1) pressure-opticaltransmission-isotherms (PTIs) and 2) the Van ‘t Hoff
relation given by:
!!"
∆! ∆!
!"
=
−
!"
!
!!
The PTIs, identical to pressure-composition-isotherms(PCIs), are obtained with hydrogenography, an opticaltechnique that can produce PTIs of thousands different

sample compositions from one measurement [3]. This
technique allows us to obtain PTIs at one temperature T
for many MgyTi1-yHx compositions, all measured at thesame conditions. From these PTIs, the pressure plateauswith Peq can be obtained at different T. With use of theVan ‘t Hoff relation, we are able to obtain the (change of)enthalpy ΔH and entropy ΔS for each composition. These
parameters show a correlation, known as enthalpyentropy compensation, which can be expressed as∆! = !!"#$ ∆! + !
where φ is constant. Inserting this expression in the Van ‘t
Hoff equation results in two situations. At T=Tcomp, Peq isthe same for all y. At T≠Tcomp, Peq is different for each y;
there is a spread in Peq and this spread increases whenincreasing the difference between T and Tcomp.
We investigate this temperature dependence of thepressure plateau spread in the PTIs of MgyTi1-yHx, which
are obtained without applying any statistics on them. This
allows us to determine Tcomp with a precision much higher
than our measurement temperature range. From ouranalysis we conclude that there exist a non-statisticalorigin of the compensation effect.

References[1] Andreassen et al., J. Phys. Chem. B, 2005, 109,
3340-3344[2] Cornish-Bowden, J. Biosci., 2002, 27, 121-126[3] Gremaud et al., Adv. Mat. 2007, 19, 2813

2004 – 2008:

Bachelor Physics and Astronomy, VU University Amsterdam;

2008 – 2011:

Master Physics, Spec. Advanced Matter and Energy Physics;

2011 – Present: Ph.D. in Chemical Engineering, Materials for Energy Conversion and Storage, Delft
University of Technology

C. Boelsma
Corresponding author: Christiaan Boelsma, c.boelsma@tudelft.nl, 0031-152782676

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FUNCTIONALIZED METAL-ORGANICCHEMICAL HYDROGEN STORAGE

FRAMEWORKSFOR

Samir Barman,a Arndt Remhof,b Oliver Friedrichs,b Thomas Fox,a Philippe
Mauron,b Olivier Blacque,a Andreas Züttel,b Heinz BerkeaaUniversity of Zurich, Institute of Inorganic Chemistry, CH-8057 Zurich, Switzerland.

b

Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div.Hydrogen & Energy,
CH-8600 Dübendorf, Switzerland.

A strategy for incorporating the ammonia borane (AB) derivatives as functional spacers of the frameworkmaterials namely DMOF-1-NH2 and IRMOF-3 following gas solid phase reactions were investigated.[1]From the hydrogen desorption experiments of the AB functionalized MOFs, it was evidenced that in somespecial circumstances room temperature hydrogen release from AB derivatives could be achieved.

Introduction
The extraordinary high gravimetric H2 content(19.6 wt %) and moderate operating temperatureof ammonia borane (NH3BH3) stimulated research
efforts to change it into a practical H2 storage
material.[2] Among the several strategies known
to improve hydrogen desorption kinetics,
nanoconfinement is of special interest. Hydrogen
release is supported by decreasing the pore sizein combination with a metal catalyst or ligand
deficient metal sites. The increased confinement
effect of the reduced pore size is exploited.

Incorporation of ammonia borane
derivatives in MOFs
Room temperature in situ PXRD measurements
were carried out to investigate the structural
responses of the dry MOFs under diborane (B2H6)
atmosphere. Which further allowed us tostandardize a precise reaction condition where AB
functionalized materials could be prepared.
Further evidence of the incorporation of covalently
bound AB derivatives in MOFs were corroboratedusing FTIR spectroscopy, ICP-AES analysis and11
B, 15N, 2H NMR spectroscopic
solid state
analysis.

Hydrogen desorption
As expected both the AB functionalized MOFs
showed onset of hydrogen release at below 50 °C.
Our investigation supports the fact that strong
confinement effect should permit to achieve
lowered onset temperature even with relativelarge pore size materials. More interestingly, oneof these AB functionalizes MOFs show room
temperature hydrogen release. It is hypothesizedthat in addition to the confinement, a special
structural effect are thought to play an importantrole for such an abnormal behaviour.

References[1] Z. Wang, K. K. Tanabe, S. M. Cohen, Inorg.
Chem. 2009, 48, 296; J. L. C. Rowsell, O. M.
Yaghi, J. Am. Chem. Soc. 2006, 128, 1304.
[2] F. H. Stephens, V. Pon, R. T. Baker, Dalton
Trans. 2007, 25, 2613.

Born 24. 02. 1983 in Dubrajpore, India. 2001-2005 B.Sc. (Hons.) in Chemistry,
Vidyasagar University, India. 2005-2007 M.Sc in Chemistry, Indian Institute ofTechnology, Bombay, India. Since 2008 PhD student in the group of Prof. Dr. Heinz
Berke, at the University of Zurich, Switzerland.

Samir Barman
Corresponding author: Samir Barman, email: samir.barman@aci.uzh.ch, Tel. (+41) (44) 635 4696

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NEW MATERIALS FOR HYDROGEN STORAGE
Torben R. Jensen
Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO) and Department ofChemistry, Aarhus University, Denmark.
Hydrogen is recognized as a potential and extremely interesting energy carrier system, which can facilitate efficientutilization of unevenly distributed renewable energy. A major challenge in a future ‘hydrogen economy’ is thedevelopment of a safe and efficient means of hydrogen storage, in particular for mobile applications. Here we report an
overview of our recent results within different experimental approaches for (i) synthesis of novel metal borohydrides andstudies of their properties, (ii) tailoring materials properties by anion substitution or nano-confinement, and (iii) in situ
powder X-ray diffraction for studies of hydrogen release and uptake reactions.

Metal borohydrides

Nanoconfinement

We have recently explored mechano-chemical andsolvent based methods for synthesis of new hydrides andhave discovered new series of metal borohydridesMM’BH4, typically containing an alkali metal, M, and adi- or tri-positive cation, M’. Apparently, the structuralcomplexity increase with the increasing size of the alkali
metal and also the tendency to form mixed chlorideborohydride compounds and ternary chlorides. The latter
illustrate a fundamental drawback for mechano-chemical
synthesis method [1,2], which, on the other hand, haslead to the discovery of a new type of combined fast Liion conductors and H2-storage materials based on heavy
metals. Systematic ball-milling synthesis experiments will
also be presented, which reveal new information on thewide parameter space for this synthesis technique. Both
synthesis and hydrogen release and uptake reactions
often occur via several coupled chemical reactions, which
can be utilized to stabilize boron in the solid state.

Nanoconfined chemical reactions has a high degree ofreversibility and stability and possibly also improved
thermodynamic properties as compared to bulk
conditions. This new scheme of nanoconfined chemistry
may have a wide range of interesting applications in the
future, e.g. within the merging area of chemical storageof renewable energy. Reversible chemical reactions cantake place at the nano-scale, e.g. LiBH4-MgH2 system or
NaAlH4 in Ti-nano-particle functionalised nano-porous
carbon aerogels. Systematic studies where pore size andscaffold surface area are varied will be presented.

A fascinating structural chemistry is discovered within
metal borohydrides, e.g. interpenetrated ‘MOF-like’
networks or zeolite-type structures with up to 30% ‘empty’
space in the porous structures with chemical bonding
ranging from ionic to more covalent and containing
composite polynuclear complex anions in the solid state[2]. Magnesium borohydrides form the most open3
structured material ( = 0.55 g/cm ), which is the first
hydride storing both chemically bonded hydrogen (14.9
wt% H2) and additionally physisorped molecularhydrogen, i.e. Mg(BH4)20.80H2, m = 17.4 wt% H2 [3].

References

In this talk, we will also illustrate that in situ powder X-ray
diffraction is a unique, sensitive and informativetechnique for probing gas-solid reactions. We conclude,that the chemistry of hydrogen is divers and a lot still
remain to be discovered with a hope to discover the‘magic’ hydride that may become the successor ofgasoline.
[1] Rude, et al, Physica Status Solidi 2011, 208(8) 1754.
[2] Ravnsbæk, et al, Z. Kristallogr. 2010, 225, 557–569.
[3] Filinchuk, et al, Angew. Chem. Int. Ed. 2011, DOI:
10.1002/anie.201100675.
[4] Nielsen, et al, Nanoscale, 2011, 3, 2086 (review).
[5] Nielsen, et al, ACS Nano, 2011, 5, 4056–4064.

Torben received his Ph.D. degree in materials chemistry and did postdoctoral research at Risø
National Laboratory and DESY, Hasylab, Hamburg. He became Assistant Professor (2000) andResearch Associate Professor (2002) at the Interdisciplinary Nanoscience Center (iNANO) and
Department of Chemistry, Aarhus University. He was awarded a Steno research stipend (2002) by
the Danish research council and a Carlsberg research stipend (2005) form the Carlsberg
Foundation. His research interests are focused on synthesis, structural, physical and chemical
properties of inorganic materials and utilisation of synchrotron X-ray radiation for materials
characterization.
Corresponding author: Torben R. Jensen, trj@chem.au.dk, +45 8942 3894

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MECHANOCHEMICAL REACTION OF SODIUM BOROHYDRIDE WITH
TRANSITION METAL FLUORIDES
Georgios N. Kalantzopoulos, Stefano Deledda, Bjørn C. Hauback
Department of Physics, Institute for Energy Technology, Instituttveien 18, NO-2007, Kjeller, Norway
Abstract
In this study we are exploring the effect of the mechano-chemical reaction between NaBH4 and transition metal fluorides.
Pressure and temperature evolution have been monitored during the mixing of the materials. The compounds have been
examined by TPD and DSC studying the gas release temperature and melting temperature respectively. The structure of
the ball milled compounds in elevated temperatures was investigated by In-situ PXD.

Introduction
Ball milling techniques are widely used as a synthesis
technique of potential hydrogen storage materials. The
grain-size reduction process that takes place duringcontinuous and vigorous fracturing occurs from mixing of
powder particles enhancing the possibility of interaction
between them [1]. The produced compounds can exhibit
altered thermodynamic properties. The energy offered
due to the mechanochemical reaction can favour theformation of new phases [2]. Borohydrides are materials
that recently have attracted lot of attention as potential
hydrogen storage materials. The mixture of borohydrides
with other compounds can lead to the formation ofphases with attractive thermodynamic properties [3].

Experimental
Powder mixtures of NaBH4 and transition metal fluorides
with 4:1 ratio were ball-milled in Ar using a Fritsch P6
planetary ball mill. The ball-to-powder ratio was 100:1.
Differential Scanning Calorimetry (DSC) measurements
were performed with a SensysDSC from Setaram.
Samples were placed in high-pressure capable stainlessosteel crucible (pmax = 500 bar; Tmax = 600 C) and data
were collected upon heating and cooling in Ar flow (15ml/min) using a constant rate of 2 oC/min. Gas release
was examined using a home-made apparatus for
Thermal Programmed Desorption (TPD) coupled with a
MULTIVISION IP detector system for residual gas

detection analysis. Measurements were carried out in-5ovacuum (10 mbar) between RT and 600 C. Hightemperature powder x-ray patterns were collected using
an imaging plate system (MAR345) with an exposure
time of 30 s.

Results
Results for 4 NaBH4 + TMF3 (TM = Fe, Mn, Ti) will bepresented. Data from diffraction analysis will be
discussed with respect to phase selection processes that
occur during ball-milling and during in-situ heating of the
as-milled powders. DSC and TPD show changes in thethermal stability of the milling products, depending on the
TMF3 used as a starting material. The effect of thedifferent TMF3 on the selective release of H2 instead of
B2H6 which is investigated by residual gas analysis willbe also discussed.

References[1] Zaluska, et al., J. Alloys Compounds, 288, (1999),
217.
[2] Zhang, et al., J. Alloys Compounds, 393, (2005), 147.
[3] Hai-Wen Li, et al., Energies, 4, (2011), 185-214.

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Graduation from Materials Science & Engineering, University of
Ioannina, Greece

20.02.2009 – 15.05.2009

Visiting Researcher, Max Planck Institute for Metals Research,
Stuttgart, Germany, Dr. Michael Hirscher group

09.12.2009

Ph.D in Physics, University of Calabria, Italy, ph.D Dissertation in“Hydrogen Physisorption Processes on Porous Solids”.

Georgios
Kalantzopoulos

Supervisor: Prof. Raffaele G. Agostino
10.12.2009 – 01.10.2010

Post-Doctoral fellow, University of Calabria, Italy

02.10.2010 till present

Post-Doctoral fellow, Institute for Energy Technology (IFE),
Department of Physics, Kjeller, Norway under the supervision ofProf. Bjørn C. Hauback.
Member of the EU project: SSH2S.

Corresponding author: Georgios Kalantzopoulos, georgiosk@ife.no, Tel.: +47 6380-6181

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METAL HYDRIDE BASED PREHEATER FOR HT-PEM FUEL CELLSMarc Linder, Inga Utz, Niko Schmidt, Christian Brack, Antje Wörner
German Aerospace Center – DLR e.V., Institute of Technical Thermodynamics, Stuttgart Pfaffenwaldring 38-40,
70569 Stuttgart, Germany
This work focuses on the application of thermochemical energy storage for the start-up process of high temperature PEM
fuel cells in order to avoid additional external measures such as electrical heater or catalytic burners.

Thermochemical Heat Storage
The dissociation of a compound (AB) into two phases (Aand B) by means of thermal energy can be used as heatstorage if the products of the reaction are stored
separately. The heat is released again if the two reaction
partners are brought together:AB

endothermic⇌

A+B

exothermicThis general principle is investigated at DLR with various
gas-solid reactions operating at different temperaturelevels ranging from 100 °C to around 1000 °C forindustrial waste heat utilization as well as solar
applications. In case of oxygen or water vapour asreaction partner an open process can be realized,
whereas for hydrogen a closed system is necessary.

additional benefit of this technology is its lossless storageof heat as long as the reactants are separated.

Operation Principle
In Figure 1 the operation principle of the thermochemical
preheater is shown. During start-up (left) hydrogen is
supplied by the available supply connection of the fuelcell with its nominal operation pressure (pFC). According
to the chemical equilibrium, the metal hydride heats up
and releases heat at the respective start-up temperature(Tmin).
ln p

pFC

ln p

MeH
H2

QPreheating

pFC

QWaste Heat (FC)
H2

MeH

Application for HT-PEM Fuel Cells
High Temperature PEM fuel cells operating attemperatures between 120-180°C offer several
advantages such as improved CO tolerance, reduced
system complexity (no humidification) and simplified
waste heat removal due to higher operation temperaturesin comparison to PEM fuel cells. However, in order toavoid liquid water in the fuel cell preheating is required
which is in most cases based on electrical heaters andconsequently demands additional battery packs,
compare [1]. Therefore, this work focuses on theapplication of a thermal energy storage that is charged
during fuel cell operation and discharged during thepreheating process. Due to the available hydrogen
supply for the fuel cell, a thermochemical heat storage(TC) based on metal hydrides seems promising. An

Marc Linder

Tmin

Figure 1:RT

1/T

Tnom Tmin

1/T

Operation Principle of TC preheater

Since the nominal operation temperature (Tnom) of the
HT-PEM fuel cell is higher than the necessary start-up
temperature, waste heat can be used to charge thethermochemical heat storage. Thereby the desorbedhydrogen can be released to the hydrogen supply
connection of the FC (pFC, Figure 1, right). A proof ofprinciple of this preheating concept will be shown
including thermodynamic and kinetic analysis of suitable
metal hydrides.

References[1] S. J. Andreasen, S. K. Kaer, Int. J. Hydrogen Energy
33, 4644-4664 (2008)

Dr.-Ing. Marc Linder graduated in Energy Engineering at the University of Stuttgart in 2006. During
his PhD work at the Institute of Nuclear Technology and Energy Systems (IKE, University of
Stuttgart) he was working with closed and open sorption systems based on metal hydrides. As
postdoctoral research fellow at IKE he was responsible for the metal hydride laboratory and thelaboratory for thermophysical properties of solids at high temperatures. In 2010, he joined theInstitute of Technical Thermodynamics at the German Aerospace Center (DLR e.V.) where he ismanaging the research area Chemical Energy Storage with core activities on chemical hydrogenstorage and the thermochemical storage of heat at different temperature ranges for solar
applications as well as industrial waste heat utilization.

Corresponding author: Marc Linder, marc.linder@dlr.de, + 49 (0) 711 6862 8034

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TOWARDS UNDERSTANDING THE MOLECULAR REARRANGEMENTS
IN COMPLEX HYDRIDES
Dr. Michael Felderhoff
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany
Abstract After more than a decade of intense research on NaAlH4 doped with transition metals as hydrogen storage
material, the actual mechanism of the decomposition and rehydrogenation reaction is still unclear. Early on, monomeric
AlH3 was named as a possible transport shuttle for aluminium, but never observed experimentally. Trapping of volatile
AlH3 produced during the decomposition of undoped NaAlH4 by an adduct of sodium alanate and crown ether is27
reported. The resulting Al2H7 anion was identified by solid-state Al NMR spectroscopy. Based on this indirect evidenceof volatile alane, a simple description of the processes occurring during the reversible dehydrogenation of NaAlH4 andrelated compounds is presented.

Crown ether adducts of complex hydrides
The crown ether adduct Na(18C6)AlH4 can be producedby ball milling of a mixture of both educts. This complex iscompletely transformed into Na(18C6)Al2H7 by trapping
AlH3 which can be observed with 27Al NMR-spectroscopy
not exceeding 343K.
This trapping is regarded as strong evidence of volatile
alane on pristine NaAlH4.
Based on this experimental evidence a simple descriptionof the catalysed dehydrogenation and hydrogenation of
sodium alanate is proposed. In this mechanism volatile
AlH3 plays the central role as transport species foraluminium.

Simplified mechanism of the decomposition of NaAlH4
based on volatile AlH3 as transport species.

The role of the catalyst in doped NaAlH4 is limited tofacilitating the decomposition and formation of alane
during the dehydrogenation and rehydrogenation.

References[1] Michael Felderhoff, Bodo Zibrowius, Formation of
Al2H7 anions - indirect evidence of volatile AlH3 on
sodium alanate using solid-state NMR spectroscopy;
Phys.Chem.Chem.Phys. 2011, 13, 17234.

born 1960
PhD 1993 University Essen
1993-96 scientific co-worker, University Essen
1996-97 scientific co-worker, Eberhard Karls University, Tübingen
1997-98 scientific co-worker, University Osnabrück
since1999 scientific co-worker, Max-Planck-Institut für Kohlenforschung, Department of
Heterogeneous CatalysisAbteilung

Michael Felderhoff
felderhoff@mpi-muelheim.mpg.de, +(49 (0)208 306 2448

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FIRST AND SECOND UNIVERSALITIES – PHENOMENA AND MODELLING
Klaus Funke
University of Muenster, Institute of Physical Chemistry
Abstract
Ion-conducting materials with quite different kinds of disordered structures have been found to show an unexpected degree of similarity in their broadband conductivity spectra. In particular, two surprising “universalities” have been detected.
One of them, the “first universality”, is a fingerprint of activated hopping along interconnected sites, while the other, the“second universality”, reflects non-activated, strictly localised movements of the ions. The former is observed at sufficiently high temperatures, while the other is found at sufficiently low ones, e.g., in the cryogenic temperature regime. In
either case, rate equations have been found that reproduce the relevant time dependence of the ion dynamics as well as
the spectra themselves. Therefore, these equations may be regarded as manifestations of the underlying common laws.
At the same time, they also form a sound basis for understanding and visualising the phenomena in terms of simple
physical pictures.
Reference:
See, e.g., K. Funke, R.D. Banhatti, D.M. Laughman, L.G. Badr, M. Mutke, A. Šantić, W. Wrobel, E.M. Fellberg, C. Biermann, “First and Second Universalities: Expeditions Towards and Beyond”, p. 459 – 518 in: Progress in Physical Chemistry Vol. 4, “Ionic Motion in Materials with Disordered Structures – From Elementary Steps to Macroscopic Transport”,
Klaus Funke, Ed., Oldenbourg, München, 2011

Klaus Funke, short CV:
Ph.D. with Wilhelm Jost, University of Göttingen (1970); Professor, Institute of Physical Chemistry and Electrochemistry,
University of Hannover (1979 - 1985); Founding Editor of SOLID STATE IONICS (since 1979); Walter Schottky Award of
Deutsche Physikalische Gesellschaft (1980); Successor to Ewald Wicke, Institute of Physical Chemistry, University of
Münster (1985, retired 2010); Wilhelm Jost Memorial Lecture (1996); Chairman of SFB 458 (Collaborative ResearchCenter), “Ionic motion in materials with disordered structures”, (Jan. 2000 - Dec. 2009); Chairman, Association of German Chemistry Professors (2001 - 2003); President, Deutsche Bunsen-Gesellschaft für Physikalische Chemie (2003 and2004); President, International Society of Solid State Ionics (2007 – 2009)

Corresponding author: Prof. Dr. Klaus Funke, k.funke@uni-muenster.de, phone ++ 49 – 251 - 8323418

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VIBRATIONALAND
BOROHYDRIDES

Stoos, Switzerland 2012

STRUCTURAL

CHARACATERIZATIONOF

Hans Hagemann, Vincenza D’Anna, Juan Carlos Fallas, Latevi Max Lawson Daku
Département de Chimie Physique, Université de Genève, 30, quai E. Ansermet, CH 1211 Geneva 4 Switzerland
Abstract The bending modes of borohydrides are compared in several crystalline surroundings. Experimental andytheoretical spectra of complex M(BH4)x ions allow clearly to distinguish between tridentate and bidentate binding. The
new compound K2Mg(BH4)2 was studied by powder x-ray diffraction, periodic DFT calculations and vibrational
spectroscopy. Isotope exchange reactions of Ca(BH4)2 were monitored using IR spectroscopy.

Bending modes of BH4In alkali and alkaline earth borohydrides the individualborohydride groups can be considered as isolated ions,i.e. they do not form a complex with the metal ion. Thus,
the vibrational infrared spectrum can be analyzed interms of its symmetry: for the tetrahedron (as in MBH4
with M = Na, K, Rb,Cs), only one deformation mode
(triply degenerate) is IR-active. Upon lowering thesymmetry (as in LiBH4), this band is split and thepreviously inactive mode becomes also active. Sometrends are shown for different compounds.
y-powder X-ray diffraction. K2Mg(BH4)4 crystallizes in space3
group P21/n with a unit cell volume around 1000 Å .
Periodic DFT calculations for this compound converged
only very slowly, as a combined result of many degrees
of freedom and possibly a relatively flat potential energy
surface. The calculations showed that locally the BH4ions show bidentate bonding towards the central Mg ion,in agreement with the X-ray refinement and the IR
spectra. An analogous Mn compound presents similar
structural and vibrational properties.

Isotope exchange reactions

Complex ions M(BH4)x can present either tridendate orbidentate binding towards the central metal atom. Bothsituations show characteristic patterns of the bending
mode region. Bidentate binding is reflected by a relatively
strong IR band around 1400 -1450 cm-1, which is shifted-1
to even higher values (1530 cm ) for neutral molecules
such as Al(BH4)3 [1].

We have performed a series of deuterium exchange
reactions (at 40 and 80 bars) and achieved an almost
complete replacement of hydrogen by deuterium at 170°C in Mg(BH4)2 [2]. The isotope exchange takes place ateven lower temperatures in Ca(BH4)2: after 6h at ca
130°C, about 75% of hydrogen was replaced bydeuterium (deuterium pressure 40 bar).

However, DFT calculations show that partial substitutionof borohydride by chloride (as observed for samples
prepared by ball milling reactions) does not lead tosignificant spectral changes in the BH4 bending mode
region.

This work is supported by the Swiss National Science
Foundation.

K2Mg(BH4)2[1] J.O. Jensen, Spectrochim Acta A59 (2003) 15651578.

We have prepared the two new compounds K2Mg(BH4)4and K3Mg(BH4)5 by ball milling of mixtures of KBH4 andMg(BH4)2 in different ratios. In parallel, similar mixtures
based on KBH4 and MgCl2 or MnCl2 were prepared. Allcompounds were studied using FTIR spectroscopy andReferences[2] H. Hagemann, V. D'Anna, J.-P. Rapin and K. Yvon,
Journal of Physical Chemistry C, 114 (21) (2010),
p10045-10047.

Hans Hagemann is born in Wuppertal, Germany. 1979 Diploma thesis, Univ. of Geneva, 1984 PhD
thesis Univ. of Geneva, 1985-1986 postdoctoral stay at UC Berkeley with H.L. Strauss and R.G.
Snyder, since 1987 at University of Geneva. The research interests cover solid state chemistry,
vibrational spectroscopy (IR and Raman), luminescence of rare earth ions in solids, and more
recently high pressure techniques and DFT calculations, both on isolated ions as well as on periodic
structures. Hans Hagemann teaches thermodynamics, statistical thermodynamics, vibrational
spectroscopy and a seminar on spectroscopy of rare earth ions.
Hans
HagemannCorresponding author: Hans Hagemann, hans-rudolf.hagemann@unige.ch, +41 22 3796539

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Stoos, Switzerland 2012"NEW CATALYTIC APPROACH FOR THE DEHYDROGENATION OF
AMINE BORANES AND RELATED COMPOUNDS”
Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich Switzerland.
Nowadays hydrogen generation from renewable sources and storage in a safe and reversible manner remainchallenging. Amine boranes and related compounds have become promising storage materials in this regard. Here, we
present a highly active nickel catalyst system for the liberation of H2 from organoamine, ammonia and amido boranes.
Specifically, catalyst loading as low as 0.3 mol% of a diolefine nickel (I) complex is enough for the efficient dihydrogen
releasing in few minutes and at room temperature. The isolation and characterization of diverse nickel hydride species
has allow us to explain possible reaction mechanisms involved in the process.

Introduction
Amino olefin ligands, specifically the bis(5 Hdibenzo[a,d]cyclohepten-5-yl)amine = bistropylidenylamine = trop2NH, give rise to rhodium amido complexes(B), which serve as superb transfer hydrogenation
catalysts.[1] Complex B, which is simply derived throughdeprotonation of the very stable amine complex[Rh(trop2NH)(PPh3)]OTf A is a highly active catalyst in
the dehydrogenative coupling (DHC) of primary alcohols
to carboxylic derivatives.[2]While the Rh based complex A shows only limited activity
in the DHC reaction of dimethyl amine borane (Me2HN–
I
BH3), the Ni complex 2 is highly active promoting thecatalytic DHC of (Me2HN-BH3) to the cyclic dimer (Me2N–
BH2)2. Ammonia borane (H3N-BH3) and related metal
amido boranes have been also tested.

H

H
H
H

Scheme 1. Synthesis of rhodium(I), nickel(I) and nickel(0)complexes B, 2 and 3.

We were able to isolate and fully characterize two rareexamples of amino-olefin complexes of Ni in theoxidation state +I and 0: [NiI(trop2NH)(OOCCF3)] 2 and[Ni0(trop2NH)(PPh3)] 3, respectively.

N

H

[Ni]

B
H
> 2 H2

HB N
N
BH
HB N
B NH
HN
B
B N
B
HN
HB

HB NH
N
B
B NH
N
B
NH

x

Scheme 3. Dehydrogenative coupling of (Me2NH–BH3) and H3NBH3 mediated by complex 2 / [KMe2N–BH3].

References[1] Trincado, M.; Gruetzmacher, H.; Vizza, F.; Bianchini,
C. Chem. Eur. J. 2010, 16, 2751
[2] Trincado, M.; Kuehlein, K.; Gruetzmacher, H. Chem.
Eur. J. 2011, 17, 11905[3] Vogt, M.; de Bruin, B.; Berke, H.; Trincado, M.;
Gruetzmacher, H. Chem. Sci. 2011, 2, 723

Scheme 2. Molecular structure of complex 2.

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M. Trincado received her PhD degree from the University of Oviedo, working with Prof. J. Barluenga
and with Prof. B. M. Trost at Stanford University. This was followed by a Fulbright postdoctoral
fellowship with Prof. J. A. Ellman at UC Berkeley. In 2008, she joined the research group of Prof. H.
Gützmacher at ETH Zürich and currently is pursuing her Habilitation. Research interests span fromthe study of a variety of metal complexes in catalyzed processes, especially those involved in thetransformation of biomass for the simultaneous production of energy and useful organic compounds
and development of new strategies for the efficient and reversible hydrogen storage in main groupbased compounds.
Corresponding author: Dr. Monica Trincado, trincado@inorg.chem.ethz.ch, 044 633 48 15132

6th Int. Symposium Hydrogen & Energy

Stoos, Switzerland 2012

REVERSIBLE HYDROGEN RELEASE AND UPTAKE IN NABH4 CONFINEDIN NANOPOROUS CARBON MATERIALPeter Ngene, Roy van den Berg, Krijn P. de Jong, Petra E. de Jongh
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University,
Universiteitweg 99, P.O. Box 80083, 3508 TB Utrecht, The Netherlands
NaBH4 is a promising material for on-board hydrogen storage in cars due to its high gravimetric hydrogen content(
10.8wt %). However the elevated temperatures (above 530 °C) [1] required to release the hydrogen and non reversibilityof the hydrogen release render it unfit for practical application. Nanoconfinement in porous materials has been shown tobe an effective strategy to improve the H2 sorption kinetics of light metal hydrides [2]. In this study, we investigate thethermal hydrogen release from NaBH4, and the effect of nanoconfinement in porous carbon material on the kinetics,
reversibility and thermodynamics of hydrogen release and uptake from NaBH4.

Preparation
NaBH4/C nanocomposites were successfully prepared
via pore volume impregnation of nanoporous carbon
material with an aqueous alkaline NaBH4 solution, andalso by melt infiltration under hydrogen pressure.

The equilibrium decomposition temperature of NaBH4 is~540 °C in 1 bar H2 [1], however for the nanoconfined
NaBH4 hydrogen release started around 280 °C under
1.1 bar H2.

Hydrogen sorption properties
XRD, solid-state NMR and hydrogen releasemeasurements revealed that NaBH4 decomposes intoelemental Na and Na2B12H12 when heated to 600 °C
under Ar, with a release of 8.1 wt % H2. Nanosizing andconfinement of NaBH4 in a nanoporous carbon material
resulted in much faster hydrogen desorption kinetics asshown in figure 1(A). The onset of hydrogen release was
reduced from 470 °C for the bulk to below 250 °C for thenanoconfined NaBH4. Remarkably, reversible formationof NaBH4 from its dehydrogenation products wasdemonstrated for the first time; the dehydrogenated
NaBH4/C nanocomposites released about 3.4 wt% H2
after rehydrogenation at relatively mild condition ( 325 °C
and 60 bar H2), while a negligible amount of hydrogen
was released from the dehydrogenated bulk after
rehydrogenation under similar conditions. Reversibility ofthe system is limited by loss of Na at high temperaturesduring hydrogen release. Compensation of Na loss by
extra Na resulted in almost full rehydrogenation of thedehydrogenated products to NaBH4.[3]Figure.1 H2 release from (A): bulk NaBH4, solution impregnated(SI) and melt infiltrated (MI) NaBH4/C nanocomposites. (B):
Dehydrogenated samples of A after rehydrogenation at 325 C,
50 and bar H2 for 5h.

References[1] Martelli, et al. J. Phys. Chem. C (2010), 114, 7173
[2] Gross et al. J.Phys. Chem. C. (2008), 112, 5651
[3] Ngene, de Jongh et al., Energy Environ. Sci, (2011),
4, 4108

Petra de Jongh received her PhD in photoelectrochemistry in 1999, and worked 5 years as a seniorscientist at Philips Research. She is now associate professor at Utrecht University, where she (co)supervises researchers working on supported nanoparticles, especially for applications in catalysis
and energy storage and conversion.
Petra de Jongh

Corresponding author: Petra E. de Jongh, email: mail to: p.e dejongh@uu.nl, Tel +31 6 22736345

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PERSPECTIVES OF H STORAGE AND ELECTROCHEMICAL STORAGE
METHODS
M. Fichtnera, S. Büschel, R. Prakash, M. Anji ReddyaInstitute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany

The perspectives are outlined and discussed of materials for energy storage based on solid storage materials forhydrogen, and for batteries. Whereas there are already established systems on the market which are based onintercalation type materials, conversion type systems seem to be the only option at the moment for reaching high storage
capacities for hydrogen or electrons. Perspectives, principle disadvantages, and scientific and technical challenges areassociated with each of these principles. Selected examples will be discussed in the contribution.

The contribution will start with an introduction to the
problem of energy storage. Chemical methods offer thehighest energy density for storing energy; they are themost interesting option for high energy and high power
applications such as automobiles and for seasonal
storage of electric energy from renewables. Each storage
method has its own perspectives, limits of its physicalpotential, technical limitations, associated with cost andsafety issues.
For storage of hydrogen or lithium, today´s systems are
based on intercalation materials which have theadvantage of being well reversible and available on themarket. However, as the energy density shall be
improved by a factor of two (H storage materials) or five(battery materials), a paradigm change is necessary inthe materials development in order to be able to reachthese goals. From the current knowledge, only systems
based on the conversion principle offer such high energy
densities [1].
Conversion materials are based on solid state chemical
reactions where several reaction partners may be
involved depending on whether the material is charged ordischarged. The systems undergo a massive
reconstruction of their structures, which is different inintercalation based systems. Examples from H storage
materials and battery research will be presented anddiscussed, and current directions of research in thesefields will be outlined.
There is a growing interest for electrochemical storage
systems with higher storage densities and better safety.
Novel sustainable battery systems have to be developedwith storage densities which exceed those of current Liion systems considerably. This can only be achieved if
new principles are applied where the chemical
conversion of nanocomposites is utilized.

A new type of secondary battery which might fit in thiscategory is based on fluoride ion shuttle and has thepotential to meeting these demands. The reaction ofhighly electronegative fluorine with metal leads to theformation of metal fluorides which are accompanied bylarge change in free energy and thus high electromotoric
force [2]. By choosing appropriate metal/metal fluoride
combinations, electrochemical cells can be built withtheoretical gravimetric and volumetric energy densities
which exceed the theoretical potential of current Li ion
batteries by an order of magnitude.

References[1] M. Fichtner, Conversion materials for hydrogenstorage and electrochemical applications - concepts andsimilarities, J. ALLOYS COMPD. 509S, S529-S534(2011)[2] M. Anji Reddy and M. Fichtner, Novel batteries basedon fluoride shuttle, J. MATER. CHEM. 21, 17059 (2011)

Maximilian Fichtner is Group Leader for “Energy Storage Systems” at KIT, Institute of
Nanotechnology. His research interests include solid state chemistry on nanoscale systems forhydrogen storage and for batteries.

Corresponding author: M. Fichtner, m.fichtner@kit.edu, +49 721 6082 5340

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF
HYDROGEN &ENERGY AWARD
The “Science of Hydrogen & Energy” award is a price, just similar to the Nobel
price, for an extraordinary contribution to the sciences of hydrogen. The aim is
to award a prize to a distinct scientist for his scientific work of a life time.

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Prof. Dr. Ronald Griessen

Ronald Pierre Griessen, was born March 7, 1945 in Switzerland.
He received 1964 his Baccalauréat, from Gymnase français in
Bienne, Switzerland. From 1964 – 1969 he studied Physics andMathematics at the Swiss Federal Institute of Technology (ETH)in Zürich and finished with a Diploma-thesis on: "Magnetostrictionof type-II superconductors". From 1969 – 1973 he was PhD
student in the Low Temperature Physics Group of Prof.dr J.L.
Olsen at the ETH. PhD-thesis on: "Oscillatory Magnetostriction
and the stress dependence of the Fermi Surface of Al, In, Zn andMg". From 1974 – 1976 he was Research Associate at the
McLennan Physical Laboratory of the University of Toronto,
Canada where he worked on the electronic structure of spindensity-wave systems and quantum oscillations.In 1976 he wasvisiting scientist at the ETH, Zürich and from 1976 – 1980 seniorlecturer at the Vrije Universiteit in Amsterdam. Since 1980 he is
Full Professor in charge of the Department of Condensed Matter
Physics.

Ronald Griessen has investigated the thermodynamics of palladium films and the isotope effecton the electronic structure of hydrides. Furthermore, the effect of anharmonicity and DebyeWaller factor on superconductivity of PdHx and PdDx have been studied by Ronald before hedeveloped a semi-empirical model for the heat of solution of hydrogen in transition metals. He
also studied the trapping energy for hydrogen on lattice defects as well as the heat of solution ofdisordered transition metals. The volume expansion upon hydrogen absorption, the Gorskyeffect, the diffusion, electromigration and the hydrogen diffusion in magnetig fields are just a few
other subjects treated and described by Ronald Griessen. Then Ronald decided to test theworld of high pressure hydrogen and described the properties of hydrides formed at very highpressure as well as the properties of hydrogen gas in a wide temperature and pressure range.
During the intense investigation of superconductors and metal hydrides under high hydrogenpressure in a diamond anvil cell, Ronald has discovered the switchable optical properties ofyttrium and lanthanum hydride films. This has then stimulated Ronald to investigate thin films
with optical methods and to develop new methods for the combinatorial search of new hydride
phases as well as for the determination of the thermodynamic parameters e.g. stability andkinetics of the hydrides. Furthermore, new applications for hydrides as hydrogen detectors andoptical filters have been developed in his group.

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Louis Schlapbach, born March 4, 1944 in Belp Switzerland. He
graduated from the Swiss Federal Institute of Technology Zurich(ETHZ) in Experimental Physics and got his PhD in Solid State
Physics – Magnetism also at ETHZ. As a postdoc at a CNRS
laboratory in Paris, he studied hydrogen storage in intermetallic
compounds. Back at ETHZ, he developed the surface science
aspects of the hydrogen interaction with metals and alloys. From1988 till 2001, Louis Schlapbach was Full Professor for Physics
at the University of Fribourg. As such he built up a research teamof 20-25 people working on the topic „New Materials and theirSurfaces“ resulting in about 40 PhD, 200 scientific papers andsome patents. A strong collaboration with industry wasestablished. In spring 2001, he has been appointed CEO of
Empa, the materials science and technology institution of theProf. Dr. Louis Schlapbach ETH domain with 750 coworkers in Dübendorf, St. Gallen and
Thun.
Louis Schlapbach started his scientific work in 1970, 38 years ago, with the investigation of theHall effect, electrical transport and magnetic susceptibility of liquid rear earth elements like
Cerium. 30 years ago in 1970 he was coauthor with Busch and Waldirich on a paper about thehydrides of La-Ni compounds. LaNi5 was subsequently investigated in view of the structure,surface segregations, hydrogen occupation of interstitial sites and as electrode material.LaNi5 isstill the base material for most of the electrochemical applications of metal hydrides today. The
work on LaNi5 was complemented by the research on FeTi. Louis Schlapbach realized theimportance of the surface composition for the hydrogen sorption process and he was able todescribe the role of the surface-active species. Furthermore, he investigated the changes of thesurface composition of LaNi5 and FeTi in oxidizing atmospheres and he found the formation of
metallic clusters as superparamagnetic particles acting as the active sites in hydrogendissociation and recombination. The investigation of the surface of metal hydrides was further
intensified by means of X-ray photoelectron spectroscopy. Louis Schlapbach was the firstscientist correctly describing the activation process of a metal hydride and, furthermore, tomodel the chemical composition and states of the elements in a surface profile. He also
succeeded to analyze the electronic structure of raere earth elements and their hydrides bymeans of photoemission spectroscopy. In 1990 Louis Schlapbach edited the two books"Hydrogen in Intermetallic Compounds I & II" of the Springer Sereies. The books became a very
important reference for all the researchers active in the field of hydrides.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Dr. Gary Sandrock

Gary Sandrock received his master from the Institute ofTechnology, Cleveland in 1965 and his Ph.D. from the Western
Reserve University, Cleveland in 1971. He worked from 19621969 as a research metallurgist in the NASA Lewis ResearchCenter, Cleveland, Ohio. From 1971-1983 he was Section
Manager of Energy Systems at Inco Research and Development
Center, Suffern, NY. From 1983-1991 he was Vice President andDirector of Technology at Ergenics, Inc., Ringwood, NJ. From
1992-1993 Gary Sandrock was visiting professor at the Kogakuin
University, Hachioji, Tokyo, Japan where he developed a newchemical surface treatment and investigated the activation
characteristics of chemical treated AB5 alloys. Gary then became
the president of SunaTech, Inc., Ringwood, NJ, where hedeveloped reversible hydrogen storage systems. At the sametime Gary Operating Agent, International Energy Agency
Hydrogen Implementing agreement Tasks 12 & 17 (Hydrogen
Storage Materials) and worked as a consultant for the US DOE
via Sandia National Laboratories, Livermore, CA.

In 1995 Gary Sandrock started to creat and mainten Hydride Databases of IEA(HIA)/DOE/SNL(http://hydpark.ca.sandia.gov) and he is author of several book chapters and review papers e.g.
“A panoramic overview of hydrogen storage alloys from a gas reaction point of view”. His recent
research concentrates on the catalysis of the hydrogen desorption from alanates and mostrecently Gary investigated the hydrogen desorption behavior of AlH3 and explaned themechanism of the kinetic stabilisation of aluminumhydrid. Furthermore, he published a paper
entitled “Accelerated thermal decomposition of AlH3 for hydrogen-fueled vehicles” where heshows the possible ways to change the activation barrier for the hydrogen desorption in acontrolled way.
Gary Sandrock not only made significant achevements in understanding metal hydrides he also
built the bridge from sciences to application. Furthermore, his scientific review papers and thehydride database are inestimably value for the hydride society.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Prof. Dr. Jens Norskov

Jens Norskov was born on September 21 in 1952. He received
his Master dgree in physics and chemistry from the University of
Aarhus, Denmark in 1976 and his PhD in theoretical physics in
1979. During his PhD he published papers about the electronic
structure of H and He in metal vacancies and the contraction of
diatomic molecules upon chemisorption. Jens Norskov was a
Post Doc at IBM in Yorktown Heights, New York in 1979 and wasaffiliated with Nordita, (Nordic Institute for Theoretical Physics) in
Copenhagen before he became a member of the scientific staff ofHaldor Topsøe A/S, Lyngby in 1981. He continued theinvestigation of gas molecules at the surface of metals anddeveloped a picture of adsorption and desorption of hydrogenemerging from self-consistent model calculations. In 1992 he wasappointed as a professor of theoretical physics in the departmentof physics at the Technical University of Denmark, Lyngby andbecame the director of the Center for Atomic-scale Materials
Physics (CAMP), Department of Physics, Technical University ofDenmark, Lyngby.

Recent research of the group of Jens Norskov covers several of the most relevant topics: 1) The
development of theoretical methods e.g. “Scaling Properties of Adsorption Energies for
Hydrogen-Containing Molecules on Transition-Metal Surfaces”; 2) Theoretical surface sciencee.g. “Role of strain and ligand effects in the modification of the electronic and chemical
properties of bimetallic surfaces”; 3) Nanostructures and materials properties e.g. Atomic-scale
imaging of carbon nanofiber growth”; 4) Heterogeneous catalysis e.g. “Ammonia synthesis fromfirst principles calculations”; 5) Biomolecules e.g. “Biomimetic hydrogen evolution”; 6)Electrochemistry and fuel cells e.g. “The origin of the overpotential for oxygen reduction at a fuelcell cathode”; 7) Hydrogen storage e.g. “Metal ammine complexes for hydrogen storage”
Jens Norskov is not only a creative and brilliant scientist, he also belongs to the few scientist
able to successfully combine theoretical approches with experimental observations for theunderstanding of the basic phenomena. It is always a great pleasure to listen to Jens Norskovs
talks, which are exciting eye opening stories combined with some great new stimulating ideas.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rüdiger Bormann was born September, 14 1952 in Germany.,
He received 1977 his diploma in physics (Metalphysics), from the
University Göttingen and 1979 his Dr. rer. nat. from the University
Göttingen. From 1981 to 1982 he was visiting scientist in theDept. of Applied Physics at Stanford University, U.S.A. From1982 to 1988 he was Assistant Professor (Hochschulassistent) at
the University Göttingen where he received the Habilitation
University Göttingen, venia legendi in 1988. From 1989 to 1997
he was Professor of Metalphysics (GKSS Research Centre,
Geesthacht and Hamburg University of Technology) and from1996 to 2009 he was director of the Institute for Materials
Research, GKSS Research Centre, Geesthacht and since 2009
he is Professor of Applied Materials Physics and President of theProf. Dr. Rüdiger Bormann University of Bayreuth
Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses,
metastable crystalline and amorphous alloys as well as the thermodynamics and kinetics of theamorphous phase formation by mechanical alloying. This was the basis for the investigation of
Mg and Mg-Ni hydrides and the thermodynamics of nanoscale magnesim hydride. The
discovery catalytic effect of metal oxides on the hydrogen sorption kinetics of magnesium was agreat step forward in the development of hydrogen storage materials. Furthermore, very
important was also the interpretation of the role of the grain boundaries for the diffusion ofhydrogen in the passivating hydride phase formation. Recently the discovery of the so called
reactive hydride composites by the combination of two hydrides has opened a new field ofmaterials design for hydrogen storage. Therefore, we aword Prof. Rüdiger Bormann with the
Science of Hydrogen & Energy prize 2010.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Ivor Rex Harris was born August 31, 1939 in United Kingdom. In
1960 he rewceived his B.Sc. in Physical Metallurgy from the
University of Birmingham), 1964 his Ph.D and became a ICI
Research Fellow. From 1966 he was lecturer in the Departmentof Physical Metallurgy and1988he became a full Professor ofMaterials Science. From 1989 to 2002 he was Head of School,
Metallurgy and Materials and from 2004 to 2005 acting director of
the Institute for Energy Research and Policy. Since 2008
he is Honorary Professor of Materials Science of the School ofMetallurgy and Materials at the University of Birmingham.

Prof. Dr. Ivor Rex Harris
For around 40 years, Rex Harris was leader of the Applied Alloy Chemistry Group (AACG) in
Metallurgy and Materials. During this time he maintained a long-standing research interest in thefields of rare earth alloys, permanent magnets and hydrogen purification and storage materials.
He developed a close synergy between these fields with the development and application of theHydrogen Decrepitation (HD) process to the manufacture of NdFeB magnets. The HD process
resulted in up to a 25% saving in production cost and is now used world-wide in the fabricationof NdFeB sintered magnets. These materials are playing a vital role in the production of energy
efficient electric drives, actuators and generators. The latest development within the group is theuse of the HD process in the recycling of 2/17 and NdFeB magnets. His research also made avery significant contribution to the development and understanding of the Hydrogenation,
Disproportionation, Desorption and Recombination (HDDR) process which enabled coercive
powder and hence bonded magnets to be formed from bulk NdFeB alloys. He has publishedover 500 scientific papers and edited and co-edited a number of books. During these years hehas successfully supervised around 120 postgraduate students, many of whom are still working
in applied materials science and occupy senior positions in industry, government and academia
throughout the world. Since stepping down as group leader and head of school he has focusedhis activities on the application of NdFeB magnets and hydrogen storage materials to practicaldemonstrators such as the Ross Barlow hybrid canal boat. This zero- carbon emission craft isserving to highlight the huge potential of magnets and hydrogen in the drive towards asustainable transport system and he has given a large number of public lectures on this subject
with the aim of raising public awareness of the dual threats of climate change and resource
depletion. He continues to be very active in this campaign which he considers to be ofparamount importance. Therefore, we aword Prof. Rex Harris with the Science of Hydrogen &Energy prize 2010.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rainer Kirchheim was born May 24, 1943 in Halle/Saale,
Germany. He studied Physics at the University of Stuttgart from
1966-1971 and received the diploma for the work
“Electrochemical studies of oxygen solid solutions in high melting
metals” at the Max-Planck-Institut für Metallforschung/Universityof Stuttgart. He received his Ph.D. for the thesis entitled “Thermoand electrotransport of oxygen and nitrogen in Va metals “ fromthe
UniversityofStuttgart,
Max-Planck-Institut
fürMetallforschung in 1973. In 1988 he received the Habilitation“Measurements and modelling of hydrogen solubility anddiffusivity in disordered metal lattices“ from the University of
Stuttgart, Faculty of Chemistry Metallurgy.
Since 1993 he is Full Professor (Gustav Tamman Chair)Prof. Dr. Rainer Kirchheim University of Göttingen Göttingen Germany and Director GeorgAugust-Universitaet Goettingen, Institut für Materialphysik
Göttingen Germany .
Prof. Rainer Kirchheim has investigated 30 years ago oxygen in metals, especially diffusion,
thermo-transport and thermo-power of oxygen in transition metals and alloys. In 1980 he started
to study diffusion of hydrogen in dillute alloys of copper and niobium in palladium. He developed
an electrochemical method for the measurement of the hydrogen diffusion in palladium andpalladium alloys and performed fundamental studies on the diffusion mechanism of interstitial
species. The interaction of hydrogen with dislocations in palladium and the interpretation with amodel based on the Fermi-Dirac distribution are of great importance for the understanding of theinterstitial site occupation of hydrogen in alloys and amorphous metals.
For the enormous contributions on the hydrogen dynamics and thermodynamics in metals aswell as the hydrogen interaction with dislocations, grain bounderies and interfaces we award
Prof. Rainer Kirchheim with the Science of Hydrogen & Energy prize 2010.

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Koji Hashimoto was born October 23, 1935 in Japan. He received
the M. Sc. In Chemistry from the Faculty of Science of the Tohoku
University, Sendai, Japan. In 1966 he received the Doctor degreein sciences from the Tohoku University and in the same year hebecame an associate professor in the Institute for Materials
Research (IMR) of the Tohoku University. From 1967 to 1969 he
was a Post Doctorate Fellow in the Division of Applied Chemistryof the National Research Council in Canada.
From 1987 to 1999 he was a Professor in the Institute forMaterials Research (IMR) of the Tohoku University and from 1999
to 2006 he was Professor at the Tohoku Institute of Technology.
Prof. Dr. Koji Hashimoto
Prof. emeritus Koji Hashimoto has published over 520 papers in scientific journals in addition toreview articles and book chapters. He has worked on corrosion-resistant alloys, electrolysis,
especially he pioneered the electrolysis of seawater. He tailored the catalysts for carbon dioxidemethanation, in particular, he has built a prototype plant for global CO2 recycling in 1995 on theroof top of the Institute for Materials Research, Tohoku University. The plant consists of power
generation by photovoltaic cells, hydrogen production by seawater electrolysis and methane
formation by the reaction of carbon dioxide with hydrogen, carbon dioxide recovery at an energy
consuming district, and transportation of carbon dioxide. The plant uses tailored key materials
with high performance and durability, that is, cathodes for hydrogen production, anodes for only
oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for rapid andselective production of methane by the reaction of carbon dioxide with hydrogen. The
performance of the plant has substantiated that global CO2 recycling can supply abundant
energy generated from solar energy on deserts in the form of methane and can really prevent
global warming induced by carbon dioxide emissions. In 2003, he has built a pilot plant of global
CO2 recycling at Tohoku Institute of Technology which is the minimum unit of industrial scale forseawater electrolysis and carbon dioxide methanation.
He is in the Editorial Board of "Corrosion Science", a Member of NACE International, theElectrochemical Society and the International Society of Electrochemistry. Member of Japan
Society of Corrosion Engineering, the Japan Institute of Metals, the Surface Finishing Society ofJapan, the Iron and Steel Institute of Japan, the Electrochemical Society of Japan, the Societyof Chemical Engineers, Japan, the Chemical Society of Japan, and other scientific societies inJapan.
He received many awards among those also The Electrochemical Society Fellow Award in 1997
in recognition of contribution to the advancement of science and technology, for leadership inelectrochemical and solid state science and technology and for active participation in the affairsof the Electrochemical Society, Inc.
We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogen and theuse of hydrogen for the reduction of CO2 with the Science of Hydrogen & Energy prize 2011.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012SCIENCE OF HYDROGEN & ENERGY AWARD 2012
Mogens Mogensen is research professor in the fuel cells andsolid state chemistry division, Risø National Laboratory for
Sustainable Energy, Technical University of Denmark (DTU).
He has spent 39 years in electrochemistry. He received his
MSc in 1973 and PhD in 1976 from the Department ofMetallurgy, DTU. After a postdoctoral period at the
Department of Chemistry A, DTU, and a short period in thebattery industry (Hellesens A/S), he was employed at Risø
National Laboratory in 1980. He was manager for numerous
projects and programs (mainly within R&D of practicalelectrochemical cells such as solid oxide fuel cells) and now
the Strategic Electrochemistry Research Center (SERC). He
has coauthored more than 250 scientific papers and reports,and has 16 patents/patent applications.
Prof. Dr. Mogens MOGENSEN
Mogens Mogensen from the Department of Energy Conversion and Storage, Technical
University of Denmark (which contains what previously was Fuel Cells and Solid State
Chemistry, Risø National Laboratory for Sustainable Energy) was involved in the development
for electrochemical systems like SOFCs (High Temperature Solid Oxide Fuel cells), SOEC
(Solid Oxide Electrolyser Cells) as well as oxygen separation membranes over the latest 25
years (and in electrochemistry for 39 years). His topics include the material development forelectrodes, electrolytes as well as interconnects, coatings and sealings. Mogens is known forhis broad knowledge and understanding of the total systems and especially the deep knowledgeof the cells thermodynamics and electrochemical behavior.
His research activities are the principle understanding of the mechanisms including the aging in
SOEC and SOFC systems, the electrochemical behavior, and the development of newmaterials for better performance and competitive prices. In the field of advanced materials he
was very active and successful in the further development of catalytic metal oxides with fluorite
and perovskite related structures. These compounds are extremely flexible with respect tosubstitution of host cations and non-stoichiometry. With this purpose he has done “material
engineering” by tailoring the basic materials properties for aspects like high electronic and ionic
conductivity, matching thermal expansion coefficient, stability in hydrogen and/or oxygen
atmosphere, etc. The development of novel materials was leading to the “world record” in power
density for electrochemical cells, accompanied by a low aging- and degradation rate (<1%/1000 h) and an outstanding mechanical strength and flexibility. Mogens was also involved incells and stack development with high electrical efficiency and fuel flexibility including naturalgas, biogas, diesel, LPG, methanol, DME and ethanol.
Recently his topic and interest are the synthetic fuels derived from water and CO2. This isinteresting as the produced syngas (H2 + CO) can react to form methane, methanol, DME or
many other hydrocarbons, which are a more suitable energy carrier. These catalytic processes
may take place inside the cell if the temperature is lowered compared to normal SOEC, orinside the electrolyser system, so the reaction heat can be utilized.
We award Prof. Mogens Mogensen for his outstanding work on the electrochemistry ofelectrolysers and fuel cells with the Science of Hydrogen & Energy prize 2011.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012BEST POSTER AWARD 2011
Ms. Alondra TORRES TRUEBA“Hydrogen Storage in Structure II
Clathrate Hydrates with Various
Promoters”
Department of Process & Energy,
Delft University of Technology,
Delft, Netherlands
M.Sc. Alondra Torres earned herbachelor degree from Universidad
Autonoma del Estado de Mexicoand her master degree (cum laude)from Universidad Iberoamericana in
Mexico City. Currently Alondra
Torres is appointed as a Ph.D.
student at Delft University ofTechnology in the Netherlands.
During her studies Alondra Torres
has been involved in several
projects including; heavy metals
removal from waste water withorganic material and the formationof polymeric membranes withforgassupercritical
CO2
separation. Her current Ph.D.
project involves the study of thepotential of clathrate hydrates forhydrogen storage.

Hydrogen Storage in Structure II Clathrate Hydrates with Various Promoters
Hydrogen (H2) is a promising alternative to fossil fuels, because it offers a solution for threemain global challenges: (i) reduction of greenhouse gas emissions, (ii) fulfilment of energy
requirements and (iii) reduction of local air pollution. However, due to the difficulty in finding aneffective storage medium, the application of H2, for instance in the automotive sector, iscurrently limited. Clathrate hydrates, have been regarded as a favorable alternative for H2
storage. Their profitability, safety, fast and high reversibility and efficient production make themmore suitable for this application than other H2 storage materials.

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012PARTICIPANTS

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012

ARAMINI Matteo, Mr

University of Parma
Department of Physics
Via G. Usberti 7/A
IT-43100 Parma

Tel: +39 0521 906067
email: matteo.aramini@fis.unipr.it

AU Yuen, Mr

Utrecht University
Inorganic Chemistry &Catalysis
Universiteitsweg 99
NL-3584 CG Utrecht

Tel: +31 622 736385
email: y.s.au@uu.nl

BARMAN Samir, Mr

University of Zurich

Tel: +41 44 635 4696
email: samir.barman@aci.uzh.ch

Winterthurerstrasse 190
CH-8057 Zurich

BERKE Heinz, Prof.

University of ZurichAnorganisch-Chemisches
Institut
Winterthurerstrasse 190
CH-8057 Zurich

Tel: +41 44 635 4680
Fax: +41 44 635 6802
email: hberke@aci.uzh.ch

BIELMANN Michael, Dr.

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4342
Fax: +41 58 765 4022
email: michael.bielmann@empa.ch

BLIERSBACH Andreas, Mr

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4862
Fax: +41 58 765 4022
email: andreas.bliersbach@empa.ch

email: c.boelsma@tudelft.nl

BOELSMA Christiaan, Mr
Granaat 8
NL-1703 BC
Heerhugowaard

BORGSCHULTE Andreas, Mr

PROCEEDINGSEMPA Materials Science &Technology
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4639
Fax: +41 58 765 4022
email: andreas.borgschulte@empa.ch149

6th Hydrogen & Energy Symposium
CALLINI Elsa, Dr.

Stoos, Switzerland 2012

EMPA Materials Science &Technology
Hydrogen and EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4933
Fax: +41 58 765 4022
email: elsa.callini@empa.ch

Dalian Institute of Chemical
Physics

Tel: +86 411 84379905
email: pchen@dicp.ac.cn

CAMPESI Renato, Mr

CHEN Ping, Prof. Dr.

457 Zhongshan Road
CN-116023 Dalian
CHOUCAIR MOHAMMAD, Dr.

UNIVERSITY OF PARMA
PHYSICSVIA G.P. USBERTI NO.
7/A
IT-43124 PARMA

email: mohammad.choucair@fis.unipr.it

DE JONGH Petra, Prof.

Utrecht University
Inorganic Chemistry and
Catalysis
Universiteitsweg 99
NL-3584 CG Utrecht

email: P.E.deJongh@uu.nl

FELDERHOFF Michael, Dr.

MPI für KohlenforschungHeterogeneous Catalysis
Kaiser-Wilhelm-Platz 1
DE-45470 Mülheim/Ruhr

Tel: +49 208 306 2248
email: felderhoff@mpimuelheim.mpg.de

FICHTNER Maximilian, Dr.

KIT
INT
P.O. Box 3640
DE-76021 Karlsruhe

email: m.fichtner@kit.edu

FRISCHKNECHT Urs, Mr

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: urs.frischknecht@empa.ch

FUNKE Klaus, Prof.

University of Muenster
Physical Chemistry
Corrensstrasse 30
DE-48149 Muenster

Tel: +49 251 8323418
Fax: +49 251 8329138
email: k.funke@uni-muenster.de

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6th Hydrogen & Energy Symposium

Stoos, Switzerland 2012GABOARDI Mattia, Mr

Università degli Studi diParma
Physics
Viale G.P. Usberti n.7/A(Parco Area delle Scienze
IT-43124 Parma

Tel: +39 052 1906067
email:
mattiagianandrea.gaboardi@fis.unipr.it

GAO Jinbao, Ms

utrecht university

email: J.GAO@uu.nl

Universiteitweg 99
NL-3584 CG UTRECHT

GAO Mingxia, Dr.

Zhejiang University
Department of Materials
Science and Engineering
Zheda Road, No.38
CN-310027 Hangzhou

Tel: +86 571 87952615
Fax: +86 571 87952615
email: gaomx@zju.edu.cn

GIANOLA Corinne, Ms

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4692
Fax: +41 58 765 4022
email: corinne.gianola@empa.ch

GORBAR Michal, Mr

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4301
Fax: +41 58 765 4022
email: michal.gorbar@empa.ch

GRINBERGA Liga, Dr.

Institute of Solid State
Physics
Hydrogen storage
materials
8 Kengaraga Street
LV-LV-1063 Riga

email: Liga.Grinberga@cfi.lu.lv

HAGEMANN Hans, Dr.

Univ. of Geneva
Dept. Physical Chemistry30, quai E. Ansermet
CH-1211 Geneva

email: hansrudolf.hagemann@unige.ch

HAZRATI Ebrahim, Mr
Electronic Structure ofMaterials
Heyendaalseweg 135
NL-6525 AJ Nijmegen

PROCEEDINGS

Tel: +31 243 652810
email: ehazrati@science.ru.nl

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6th Hydrogen & Energy Symposium

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IRVINE John, Prof.

University of St Andrews
School of ChemistryNorth Haugh
GB-KY16 9ST St Andrews

email: jtsi@st-andrews.ac.uk

JENSEN Torben R., Prof. Dr.

Aarhus University
iNANO, Department ofChemistry
Langelandsgade 140
DK-8000 Aarhus

Tel: +45 2272 1486
email: trj@chem.au.dk

KALANTZOPOULOS
Georgios, Dr.

Institute for Energy
Technology (IFE)
Physics Department
P.O. Box 40
NO-NO-2027 Kjeller

Tel: +47 6380 6181
Fax: +47 6381 0920
email: georgiosk@ife.no

KATO Shunsuke, Mr

EMPA Materials Science &Technology Materials
Science and Technology
Dept. Environment, Energy
and MobilityÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4327
Fax: +41 58 765 4022
email: shunsuke.kato@empa.ch

KIM Ji Woo, Dr.

EMPA
Hydrogen & EnergyÜBERLANDSTRASEE 129
CH-8600 Dübendorf

Tel: +41 58 765 4153
Fax: +41 58 765 4022
email: jiwoo.kim@empa.ch

LANGHAMMER Christoph,
Prof.

Chalmers University ofTechnology
Applied Physics
Fysikgränd 3
SE-41296 Göteborg

email: clangham@chalmers.se

LAURENCZY Gabor, Prof.

EPFL
ISIC LCOM GCEEBCH 2405
CH-1015 LausanneTel: +41 21 693 9858
Fax: +41 21 693 9780
email: Gabor.Laurenczy@epfl.ch

LI Haiwen, Dr.

Kyushu University
International ResearchCenter for Hydrogen
Energy744 Motooka, Nishi-ku
JP-819-0395 Fukuoka

email: li.haiwen.305@m.kyushu-u.ac.jp

LINDEMANN Inge, Ms

email: I.Lindemann@ifw-dresden.deHelmholtzstr. 20
DE-01069 Dresden

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LINDER Marc, Dr.

German Aerospace Center- DLR
Institute of Technical
Thermodynamics
Pfaffenwaldring 38-40
DE-70569 Stuttgart

email: marc.linder@dlr.de

LIU Yongfeng, Prof. Dr.

Zhejiang University
Department of Materials
Science and Engineering
38# Zheda Road
CN-310027 Hangzhou

Tel: +86 571 87952615
Fax: +86 571 87952615
email: mselyf@zju.edu.cn

LOHSTROH Wiebke, Dr.

Technische Universität
München
FRM 2
Lichtenbergstr. 1
DE-85747 Garching

Tel: +49 89 289 14735
Fax: +49 89 289 14989
email: wiebke.lohstroh@frm2.tum.de

MARTELLI Pascal, Mr

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: pascal.martelli@empa.ch

MATSUO Motoaki, Dr.

Tohoku UniverstiyInstitute for Materials
Research
2-1-1 Katahira, Aoba-ku
JP-980-8577 Sendai

Tel: +81 22 215 2094
Fax: +81 22 215 2091
email: mmatsuo@imr.tohoku.ac.jp

MAURON Philippe, Dr.

EMPA Materials Science &Technology
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4099
Fax: +41 58 765 4022
email: philippe.mauron@empa.ch

MOGENSEN Mogens Bjerg,
Prof. Dr.

Technical University ofDenmark DTU
Fuel Cells and Solid State
Chemistry
Frederiksborgvej 399
DK-4000 Roskilde

Tel: +45 2132 6622
email: momo@risoe.dtu.dk

MULLER Jiri, Dr.

IFE

email: jiri@ife.no

Kjeller
NO-2027 Kjeller

OMAR Abdelazim, Prof.

PROCEEDINGSEGYPTIAN PETROLEUMRESEARCH INSTITUTE
Processes desigin anddevelopment depart.
cairo nasr city
EG-11727 nasr city

email: abdelazimomar@yahoo.co.uk

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ORIMO Shin-ichi, Prof. Dr.

Tohoku University
Institute for Materials
Research
2-1-1, Katahira
JP-980-8577 Sendai

Tel: +81 22 215 2093
Fax: +81 22 215 2091
email: orimo@imr.tohoku.ac.jp

PAN Hongge, Prof. Dr.

Zhejiang University
Department of Materials
Science and Engineering

Tel: +86-571-87952615
email: hgpan@zju.edu.cn

CN-310027 Hangzhou
PONTIROLI Daniele, Dr.

Università di Parma
Dipartimento di Fisica
Via G. Usberti 7/a
IT-43124 Parma

Tel: +39 0521 90 5231
Fax: +39 0521 90 5223
email: Daniele.Pontiroli@fis.unipr.it

RAMIREZ-CUESTA Timmy,
Dr.

STFC
ISIS Facility
Room 1-51
GB-OX11 0QX Chilton

Tel: +44 7787 105335
email: timmy.ramirezcuesta@stfc.ac.uk

RATISHVILI Ioseb, Prof. Dr.

Javakhishvili St. Univ.,
Andronikashvili Ins.Phys.
Dep. Cond. Matter Physics
6 Tamarashvili str.
GE-GE_0177 Tbilisi

Tel: +99 532 2290798
email: ratisoso@gmail.com

REMHOF Arndt, Dr.

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrASSE 129
CH-8600 Dübendorf

Tel: +41 58 765 4369
Fax: +41 58 765 4022
email: arndt.remhof@empa.chRICCÒ Mauro, Prof. Dr.

Parma University
Physics Department
Via G. Usberti 7/a
IT-43124 Parma

Tel: +39 349 96609300
Fax: +39 052 1905223
email: Mauro.Ricco@fis.unipr.it

SHEPTYAKOV Denis, Mr

Laboratory for Neutron
Scattering

email: denis.cheptiakov@psi.ch

Paul Scherrer institut
CH-5232 Villigen

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SITTE Werner, Prof.

Montanuniversitaet Leoben
Physical ChemistryFranz-Josef-Strasse 18
AT-A 8700 Leoben

Tel: +43 384 24024800
Fax: +43 384 24024802
email: sitte@unileoben.ac.at

SIVARS Andris, Mr

Institute of Solid State
Physics

Tel: +371 67262145
email: a.sivars@gmail.com

Kengaraga iela 8
LV-LV-1063 Riga
STADIE Nicholas, Mr

California Institute ofTechnology
Materials Science
1200 E California Blvd, MC
138-78
US-91125 Pasadena

Tel: +1 602 363 8883
Fax: +1 626 795 6132
email: nstadie@caltech.edu

SUTER Riccardo, Mr

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4729
Fax: +41 58 765 4022
email: riccardo.suter@empa.ch

TANG Wan Si, Ms

LRCS UMR 6007 UPJV
Material Chemistry
33 Rue St Leu
FR-80000 Amiens

Tel: +33 3 22 82 75 92
Fax: +33 3 22 82 75 90
email: wan-si.tang@u-picardie.fr

TAUBE Klaus, Dr.

Helmholtz-Zentrum
Geesthacht
Nanotechnology
Max-Planck-Strasse 1
DE-21502 Geesthacht

Tel: +49 4152 87 25 41
Fax: +49 4152 87 4 25 41
email: klaus.taube@hzg.de

TORRES Alondra, Ms

TU Delft
Department of Process &EnergyLeeghwaterstraat 44
NL-2628 CA Delftemail: alondra_t@hotmail.com

TRAJKOVIC Ivo, Dr.

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4746
Fax: +41 58 765 4022
email: Ivo.Trajkovic@empa.ch

TRINCADO Monica, Dr.

ETH Zurich
LAC, Chemistry
Wolfgang-Pauli-Str. 10
CH-8093 Zurich

Tel: +41 76 238 8779
email: trincado@inorg.chem.ethz.ch

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6th Hydrogen & Energy Symposium
ULMER Ulrich, Mr

KIT

Stoos, Switzerland 2012
email: ulrich.ulmer@kit.edu

Hermann-von-HelmholtzPlatz 1
DE-76344 EggensteinLeopoldshafen
VAN DEN BERG Marius, Mr

Tel: +31 643751990
email: mariusvdberg@gmail.com
Friedenheimer strasse 139
DE-80686 Muenich

VOGT Ulrich, Dr.

EMPA Materials Science &Technology
Hydrogen & Energy
Ueberlandstr. 129
CH-8600 Dübndorf

Tel: +41 58 765 4160
Fax: +41 58 765 4022
email: ulrich.vogt@empa.ch

WU Chaoling, Prof. Dr.

Sichuan UniverstiyMaterials Science andEngineering
Wangjiang Road 29#
CN-610064 Chengdu

Tel: +86 28 85466916
Fax: +86 28 85466916
email: wuchaoling@scu.edu.cn

YAN Yigang, Dr.

EMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4082
Fax: +41 58 765 4022
email: yigang.yan@empa.ch

YUAN Peipei, Ms

Zhejiang University(Yuquan Campus)
CN-310027 Hongzhou

Tel: +86 13567138396
email: yuanpeipei8023@yahoo.cn

ZHAO-KARGER Zhirong, Dr.

Karlsruhe Institute ofTechnology
Institute of Nanotechnology
Hermann-von-HelmholtzPlatz 1
DE-76344 EggensteinLeopoldshafen

Tel: +49 72160828908
email: zhirong.zhao-karger@kit.edu

ZHU Min , Prof. Dr.

South China University ofTechnology
School of Materials
Science and Engineering

Tel: +86-20-87113924
email: memzhu@scut.edu.cn

CN-510640 Guangzhou

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6th Hydrogen & Energy SymposiumZÜTTEL Andreas, Prof. Dr.

PROCEEDINGSEMPA Materials Science &Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Stoos, Switzerland 2012
Tel: +41 58 765 4038
Fax: +41 58 765 4022
email: andreas.zuettel@empa.ch157

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6th Hydrogen & Energy Symposium

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Information

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Map from Zürich (upper left corner) to Stoos (center bottom)

Map of the region Schwyz-Stoos

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Travel to Stoos from Zürich airport:
Please go to the ticket counter in the airport and ask for a ticket to Stoos (roundtrip). Pleasealso ask the person at the counter to print you the timetable for your connection e.g.:
So, 23.01.11
Zürich Flughafen
ab 14:13
3
IC 726, InterCity BZ RZ
Zürich HB
an 14:23 17
walk from track 17 to track 4
Zürich HB
ab 14:35
4
IR 2345, InterRegio
Zugan 15:01
4
change to train on opposite side of platformZug
ab 15:05
3
S2 21247, S-Bahn Linie 2
Schwyzan 15:33
2
the bus is parked in front of the station
Schwyz, Bahnhof
ab 15:36
Bus 1, Richtung: Muotathal, Hölloch
Schwyz, Schlattli
an 15:54
the bus stops in front of the cable car station, show your ticket at the counter
Schlattli SSSF
ab 16:10
FUN 19, Standseilbahn
Stoos
an 16:18
Time for trip: 2:05
http://www.sbb.ch

EMERGENCY TELEPHONE NUMBERS
country code for Switzerland +41...
POLICE

117

FIRE FIGHTERS

118

AMBULANCE144

RESCUE HELICOPTER

1414

Corinne Gianola
Andreas Züttel
Hotel Stoos, Reception

076 398 9985
079 484 2553
041 817 4444

Seminar- und Wellnesshotel Stoos (AG Sporthotel Stoos)Ringstrasse 10
CH-6433 Stoos
info@hotel-stoos.ch
http://www.hotel-stoos.ch

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STOOS Region

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