Experimental aspects of R&D on hydrogen storage technologies .
Date: 2007-09-28
Institutions: Institute for Energy and Transport
Subjects: Joint Research Centre, energy policy, energy storage, energy technology, hydrogen, operation of the Institutions, research and development

 JRC-IE Enlargement & Integration Workshop  
 “Experimental Aspects of R&D on Hydrogen 

Storage Technologies” 

C. Filiou, P. Castello and P. Moretto (Eds.) 

DG JRC 

Institute for Energy 
Petten, The Netherlands 

March 2006 

EUR22177EN 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
  
 
 
 
 
 
 
Mission of the Institute for Energy 

The  Institute  provides  scientific  and  technical  support  for  the  conception,  development, 
implementation and monitoring of community policies related to energy.  

Special emphasis is given to the security of energy supply and sustainable and safe energy 
production. 

European Commission 

Directorate General Joint Research Centre (DG JRC) 

http://www.jrc.cec.eu.int/ 

Institute for Energy, Petten (the Netherlands) 
http://ie.jrc.cec.eu.int/ 

Contact details: 

C. Filiou 

+31.224-565171 

P. Castello 

+31-224-565041 

P. Moretto 

+31-224-565269 

http://www.jrc.cec.eu.int/ 

Legal Notice 

Neither the European Commission nor any person acting on behalf of the Commission is 
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The use of trademarks in this publication does not constitute an endorsement of the European 
Commission. 

The views expressed in this publication are the sole responsibility of the authors and do not 
necessarily reflect the views of the European Commission. 

A great deal of additional information of the European Union is available on the Internet. It can 
be accessed through the Europa server (www://europa.eu.int) 

©  European Communities, 2006 
Reproduction is authorised provided the source is acknowledged. 
Printed in the Netherlands 

COVER: Experimental activities at JRC-IE, Petten (NL) , JRC-IE, PR & Communication 

No commercial use. Credit “Audiovisual Library European Commission” 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
  
Systems for Alternative Fuels 
(SYSAF) 

This action supports the penetration of natural gas and hydrogen as 
alternative fuels in the energy sector, particularly in road transportation.  

In the particular field of hydrogen, the objective of SYSAF (Systems for 
Alternative Fuels) is to provide independent technical expertise and validation 
of storage performance, efficiency and safety of competing technologies. It 
aims at harmonising, validating and standardising test procedures for safety 
and operational performance of hydrogen systems. 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
  
Table of Contents 

Acknowledgements ..................................................................................................7 

1.  Introduction........................................................................................................9 

1.1. The energy issue, and the role of technological innovation .............................9 

1.2. The hydrogen option and the role of JRC........................................................9 

2.  JRC-IE E/I Workshop on Experimental Aspects of R&D on Hydrogen Storage 
Technologies – summary of the event..............................................................11 

3.  Highlights from the technical sessions presentations......................................12 

3.1. Technical Session I – Theoretical background ..............................................12 

3.2. Technical  Session  II  –  Technology  and  safety  aspects  of  hydrogen  storage 

systems......................................................................................................13 

3.3. Technical Session III – Practical aspects of testing and hands-on experience 14 

4.  References.........................................................................................................16 

Handouts of presentations 

The JRC at the Service of the European Citizen 

The JRC Enlargement and Integration Action 2005 

Overview of the Solid State Hydrogen Storage and related R&D Issues 

Micro- and Macro-scopic Characterisation Techniques and Modelling 

Hydrogen Storage Tank: Design and Heat Transfer Principles 

Testing of Hydrogen Safety Sensors at JRC  

Hydrogen Sorption Measurements 

Microscopical characterisation of H2 storage materials using SEM  

Appendices 

Workshop Agenda 

List of Participants 

Group photo 

5

 
 
 
 
6

 
 
Acknowledgements 

The  two-days  training  workshop  "  Experimental  aspects  of  R&D  on  Hydrogen  Storage 
Technologies"  was  organised  in  October  2005  by  the  Institute  for  Energy  (IE)  of  the  Joint 
Research Centre (JRC) of the European Commission, in the frame of the JRC Enlargement & 
Integration Action.  

This  initiative  was  one  from  a  catalogue  of  technical  workshops,  training  courses  and 
temporary  job-opportunities  sponsored  and  coordinated  by  the  Enlargement  and  Integration 
(E/I) Unit of the JRC. Further information on the opportunities available in 2006 can be found 
on the JRC E/I website, at http://www.jrc.cec.eu.int/enlargement/. 

The  organizers  are  grateful  to  the  invited  speakers  for  their  willingness  to  participate  and 
share  their  knowledge  and  experience,  and  to  all  participants  for  contributing  in  setting  up 
lively, instructive and productive discussion on the workshop topics.  

7

 
 
  
8

 
 
1.  Introduction 

1.1. The energy issue, and the role of technological innovation 

Designing a liveable context for future generations while preserving the environment requires 
a  long-term  balancing  of  many  elements,  one  of  which  is  driving  the  energy  sector  to  a 
sustainable path.  
Neither  for  the  preservation  of  industrialized  countries  quality  of  life,  nor  for  fuelling  the 
expansion of emerging economies, the world can rely indefinitely on the present base of fossil 
fuels.  Since  the  first  oil  crisis  in  1973,  the  present  system  has  revealed  multiple  Achille's 
heels: fossil fuels, notably oil, are not unlimited in quantity, they are unevenly spread on the 
globe and therefore their availability is subjected to political factors, their consumption causes 
the emission of CO2, a greenhouse gas (GHG) responsible for global climate change.  

Alongside  its  commitment  to  the  Kyoto  protocol  and  the  reduction  of  GHG  emissions,  the 
European  Union  looks  at  the  energy  issue  with  the  concern  of  a  growing  dependency  from 
outside  its  borders.    Recent  analyses  clearly  showed  that  the  energy  dependence  of  the 
European  Union  from  imports,  which  is  at  present  around  50%,  will  reach  70  %  in  2030. 
Furthermore,  the  Union  has  very  limited  possibility  to  influence  energy  supply  conditions, 
and  it  is  only  on  the  demand  side  that  the  EU  can  intervene,  mainly  by  promoting  energy 
saving in buildings and the transport sector. 

Thus, reality is demanding a transition towards some new architecture of the energy sector, 
with time running short for implementing new technology options before the changes occur 
disruptively for society and the world economy. Whilst political and socio-economic drive in 
this  direction  are  indispensable,  making  new  options  available  at  economically  affordable 
conditions is a task for science and research.  

Technology innovation can help solving questions of fundamental importance: 
·   diversify from oil use and limit imports without excessive economic costs 
·   use the vast coal resources without intolerable environmental impacts 
·   expand  the  use  of  nuclear  energy  while  reducing  risks  related  to  safety,  waste  & 

proliferation 

·   capitalise on the intermittency of renewable energy technologies 
·   use  in  a  cost  effective  and  clean  manner  energy  resources  to  meet  local  needs,  thus 

promoting competitiveness, employment and rural development 

·  

·  

improve air quality while sustaining growth in road transport 

increase efficiency in energy use, i.e. conserve energy whilst energy demand is growing 

and, last but not least, introduce carbon-neutral/carbon-free fuels, such as hydrogen, and 
electricity. 

1.2. The hydrogen option and the role of JRC 

The  perspective  of  a  so-called  “hydrogen  economy”  has  received  particular  attention  in  the 
recent  past.    As  an  energy  carrier,  hydrogen  is  free  from  emissions  in  the  final  use,  with 
pollutant  emissions  that  can  be  controlled  and  heavily  reduced  during  the  production 
processes.  In  combination  with  internal  combustion  engines,  fuel  cells  and  gas  turbines, 

9

 
 
 
hydrogen can provide an effective replacement of petroleum products, in the transport sector 
as well as in portable and small stationary power generation applications.  

Available  on  earth  only  in  combination  with  other  elements  (typically  oxygen  in  water  and 
carbon  in  fossil  fuels),  it  can  be  obtained  pure  from  a  variety  of  different  primary  sources 
(fossil, renewable, nuclear). In this respect, it can be considered an excellent complement to 
electricity, which can also be produced in many different ways, is much easier to transmit and 
distribute, but cannot be stored in significant amounts. 

The European vision of a hydrogen future is embodied by the activities of the Hydrogen and 
Fuel Cells Platform, and it has been laid down in a number of policy and strategy documents 
concerning  both  the  necessary  European  R&D  agenda  and  the  related  envisaged  hydrogen 
deployment strategy [1].   
At  international  level,  the  International  Partnership  for  the  Hydrogen  Economy  (IPHE)  was 
established  in  2003  as  an  international  mechanism  to  organise  and  implement  effective, 
efficient  and  focused  international  research,  development,  demonstration  and  commercial 
utilisation activities related to hydrogen and fuel cells [2]. The partnership provides a forum 
to  accelerate  the  cost-effective  transition  to  a  global  hydrogen  economy,  to  enhance  energy 
security and environmental protection.  

In  summary,  introducing  hydrogen  as  an  energy  vector  raises  questions  concerning  the 
development  of  adequate  technologies  and  infrastructure  for  large-scale  production, 
transmission and distribution, storage and efficient utilization. Furthermore, at least the same 
levels of safety for the industry, the environment and the public as that associated with today's 
fuels and energy carriers must be provided [3-4, 5, 6, 7,8]. 

In  this  context,  the  mission  of  the  Institute  of  Energy  of  the  European  Commission 
Directorate  General  Joint  Research  Centre  is  to  provide  customer-driven  scientific  and 
technical  support  for  the  conception,  development,  implementation  and  monitoring  of 
community policies related to energy, with special emphasis given to the security of energy 
supply and sustainable and safe energy production. For this purpose, the Institute carries out 
several  activities  related  to  the  performance  assessment  of  energy  systems  (e.g.  efficiency, 
safety,  environmental  compliance)  and  with  the  development  of  new  energy  carriers  and 
hydrogen  in  particular  [9].  Like  the  rest  of  JRC,  and  as  a  service  of  the  European 
Commission,  the  Institute  functions  as  a  reference  centre  of  science  and  technology  for  the 
Union.  Close  to  the  policy-making  process,  it  serves  the  common  interest  of  the  Member 
States, while being independent of special interests, whether private or national. 

By organizing workshops and seminars at its premises as well as at those of other Research 
Institutions all over the enlarged EU, the JRC aims at promoting exchange and dissemination 
of  information,  supporting  training  of  young  researchers  and  promoting  collaboration 
between  EU  member  states,  EU  candidate  and  associated  Countries,  thereby  fostering 
integration and contributing to the development of a true European Research Area. 

10

 
 
2.  JRC-IE E/I Workshop on Experimental Aspects of R&D on Hydrogen 

Storage Technologies – summary of the event 

The Enlargement and Integration Workshop presented here was organised under the  Systems 
for Alternative Fuels (SYSAF) institutional research action of the Clean Energies  Unit of the 
JRC-IE.  It  was  a  training  event  attended  by  twenty-two  participants  coming  from  six  New 
Member  States  (Hungary,  Latvia,  Lithuania,  Poland,  Slovakia  and  Slovenia),  three  EU 
Candidate Countries (Bulgaria, Romania and Turkey), three Countries in the Western Balkan 
region  (Croatia,  F.Y.R.O.M.,  Serbia  and  Montenegro)  and  invited  lecturers  from  Greece, 
Switzerland  &  the  United  Kingdom.  This  event  was  mainly  targeted  to  young  researchers 
with  direct  laboratory  experience  in  hydrogen  storage  technologies  and  on  the  performance 
characterisation  of  solid-state  materials  and  the  development  of  safety  procedures  and 
devices.  

The main objectives of this Workshop were:  

·  

·  

·  

to facilitate the exchange of information on hydrogen storage technologies with respect to 
experimental methodologies, processes and facilities 

to generate open discussion among participants on scientific issues and on the definition 
of best practices 

to spread information concerning safety and standardisation work in the field 

testing 

In line with these, state-of-the art information on hydrogen storage technologies with respect 
to  experimental  methodologies,  processes, 
facilities,  but  also  safety  and 
standardisation was presented. An open discussion was generated among the participants on 
the  very  scientific  issues  raised  and  on  the  definition  of  the  associated  best  practices.  The 
event  was  complemented  by  visits  to  the  JRC-IE  testing  installations  for  hydrogen  storage 
tanks (GasTeF: Compressed Gas Tanks Testing Facility) and safety sensors (SenTeF: Sensors 
Testing Facility). The actual laboratory experience picked up on the second day of the event 
with the participants getting further involved in hands-on experiments at the Microstructural 
Analysis Laboratory and at the SolTeF (Solid-state hydrogen storage Testing Facility) for the 
micro-  and  macro-scopic  characterisation  of  solid-state  materials  and  their  potential  for 
hydrogen storage applications.  

The workshop was instrumental in helping all the participants to strengthen existing liaisons 
and establish new contacts, with a look forward to collaboration in the enlarged EU. In this 
perspective,  research  opportunities  under  the  current  EC-6th  Framework  Programme  were 
discussed, alongside training, mobility and career development possibilities with the JRC but 
also under the Marie-Curie Actions1 of the EC Human Resources and Mobility Activity. 

1 http://europa.eu.int/comm/research/fp6/mariecurie-actions/indexhtm_en.html 

11

 
 
 
 
                                                
3.  Highlights from the technical sessions presentations 

3.1. Technical Session I – Theoretical background  

The gravimetric energy density of hydrogen is about three times higher than gasoline, but its 
energy  content  per  volume  is  about  a  quarter.  Therefore,  the  most  significant  problem  for 
hydrogen (in particular for on-board vehicles) is to store it in sufficient  amounts. Hydrogen 
can  be  stored  by  high  pressure  in  gas  cylinders  (up  to  800  bar);  as  liquid  hydrogen  in 
cryogenic tanks (at 21 K); adsorbed on materials with a large specific surface area (at T< 100 
K)  –  physisorption;  absorbed  on  interstitial  sites  in  a  host  metal  (at  ambient  pressure  and 
temperature)  or  even  chemically  bonded  in  covalent  and  ionic  compounds  (at  ambient 
pressure); and finally via oxidation of reactive metals e.g. Li, Na, with water. Each  method 
has  its  specific  merits  and  limitations.  The  volumetric  energy  density  of  hydrogen  can  be 
increased by compression or liquefaction, which are both rather mature technologies. Still, the 
energy required for both compression and liquefaction is one element to be properly assessed 
in  considering  the  different  pathways  for  distribution  [10].  Hydrogen  storage  in  solid 
materials is an attractive option in view of its inherent safety. However, this technology is far 
from mature, and remains an open field for fundamental and applied research. 

·   Materials  with  a  large  specific  surface  area  like  activated  or  nanostructured  carbon  and 
carbon nanotubes (CNTs) can theoretically store significant amounts of hydrogen because 
of  their  high  surface  area  and  abundant  pore  volume.  These  are  substrates  for  and  are 
usually  related  with  hydrogen  physisorption,  which  in  turn  is  caused  by  resonant 
fluctuations  in  charge  distributions,  or  Van  der  Waals  interactions.    The  amount  of 
adsorbed  hydrogen  is  proportional  to  the  surface  area  of  the  nanostructured  carbon 
sample.      Recently,  there  is  an  increased  interest  in  a  promising  class  of  nanoporous 
materials,  namely  the  metal-organic  frameworks  which  have  an  extremely  high  surface 
area  and  allow  for  many  structural  modifications.  On  a  fundamental  level  there  are  still 
challenges on understanding the exact adsorption/desorption  mechanism and whether the 
material/hydrogen  interaction  is  different  from  the  classic  physisorption.  Significant 
drawbacks  in  using  carbon  materials  for  hydrogen  storage  include  the  required  low 
temperatures and the rather small gravimetric and volumetric hydrogen densities.  

and 

·   Reversible metal hydrides absorb hydrogen at a constant pressure, around the atmospheric 
pressure 
this 
and 
absorption/desorption behaviour can be tailored by partial substitution of the constituent 
elements in the host lattice. Their gravimetric hydrogen density is limited to less than 3 
mass% that makes them unsuitable for transport applications. 

characteristics  of 

temperature 

ambient 

actual 

the 

·   Complex hydrides are formed from the Group 1, 2, and 3 light metals, e.g. Li, Mg, B, and 
Al.  They  are  particularly  interesting  because  of  their  light  weight  and  the  number  of 
hydrogen  atoms  per  metal  atom  (e.g.  NaBH4,  LiBH4).  Their  main  difference  from  the 
metallic  hydrides  is  the  transition  to  an  ionic  or  covalent  compound  upon  hydrogen 
absorption.  This  class  of  materials  has  potential  and  NaAlH4  has  been  used  as  a  model 
system for understanding the associated mechanisms of sorption in alanates and the effect 
of  catalysts  in  improving  their  low-temperature  kinetics  and  reversibility.  The  most 
promising compound, particularly for transport applications, with the highest gravimetric 
hydrogen density at room temperature comes from the borohydride family and is LiBH4 
(18 mass%).  However, de-stabilisation and reversibility remains an open issue for future 
R&D  for  these  materials.    Finally,  equally  challenging  but  still  offering  potential  for 

12

 
 
 
hydrogen  storage  are  the  destabilised  complex  hydrides  by  nanocomposities  of  partial 
charged and partial negative hydrogen like LiNH2 and MgH2. 

·   The hydrolysis reactions of chemical hydrides, such as NaBH4 or LiBH4, have attracted a 
lot  of  attention  mainly  due  to  their  promise  for  high  material  hydrogen  capacity  and 
relative  fast  hydrogen  release  kinetics.  Nevertheless,  the  borohydride  regeneration 
reaction  must  take  place  off-board,  and  the  associated  energy  requirements,  life  cycle 
impact and costs are challenging.  

·   Fundamental and mechanistic studies require collection of experimental data.  X-ray and 
neutron scattering methods are microscopic techniques for determining crystal structures, 
the latter enabling studying of the positions of hydrogen atoms in the material, vibrations 
and diffusion, including quantum effects. They play an important role in the development 
of new materials for hydrogen storage. Neutron scattering methods may be used as unique 
probes  of  hydrogen-containing  solid  materials  because  of  their  strong  scattering  by 
hydrogen.  Neutron  diffraction  can  be  used  for  determining  micro-stresses  induced  by 
hydrogenation, while small angle scattering can follow microstructural changes that occur 
during  cycling.  At  macroscopic  level,  gravimetric  or  volumetric  determination  of  the 
amount  of  stored  hydrogen  provide  fundamental  thermodynamic  and  kinetic  data  on 
materials  and  determines  the  dynamics  of  hydrogen  sorption/desorption  which  are 
concentration-dependent and the associated enthalpy changes.  

3.2. Technical Session II – Technology and safety aspects of hydrogen storage systems 

Once  the  properties  of  a  hydrogen  storage  material  are  optimised  at  a  laboratory  scale, 
designing  and  constructing  a  tank  of  practical  use  for  stationary  and/or  mobile  applications 
remains  a  major  technological  challenge.  Taking  for  example  automotive  applications,  a 
proper storing device should, inter alia, have a limited weight, allow fast and easy refueling, 
preserve  hydrogen  from  contamination  and  work  efficiently  in  an  acceptable  temperature 
range. To achieve this result, a number of technical issues must be addressed and solved. 
·   Because of thermal effects associated with the hydrogen capture and release process, heat 
management is a key issue in designing a rechargeable tank for automotive applications.  
·   The inherent reactivity of some storage media as well as the high volatility of hydrogen 
are  cause  of  potential  concern  in  terms  of  safety,  and  must  be  accounted  for  at  design 
level.  

·   The  capability  to  withstand  an  adequate  number  of  cycles  without  a  significant  drop  in 

performances is critical for the affordability of the system. 

A further pre-condition for a consistent penetration of hydrogen into the energy market is that 
at least the same levels of safety for  industry, the environment and the public can be assured 
for hydrogen as it is for today's fuels and energy carriers. Because hydrogen is non-toxic, its 
major hazard is connected with the possibility of building up potentially explosive conditions 
due  to  an  unwanted  release.    This  in  turn  means  that  the  rapid,  reliable  and  economically 
affordable hydrogen detectors are likely to be an element of most future hydrogen systems.  
·   Whilst a certain number of technologies and related standards are available on the market, 
future  applications  such  as  those  discussed  in  the  context  of  the  workshop  are  likely  to 
bring forward a new class of needs (rapid response, low power consumption, limited need 
for maintenance and price adequate for mass production).  

13

 
 
 
 
·   Research  on  hydrogen  detection  methods  and  devices  has  been  moving  forward  in 
different  laboratories  worldwide  over  the  last  years,  alongside  dedicated  initiatives  on 
standardization. 

3.3. Technical Session III – Practical aspects of testing and hands-on experience 

The hydrogen sorption properties of materials can be determined using a number of different 
methods, and put in relation with microstructure. 

·  

·  

In  the  gravimetric  technique,  the  mass  of  the  sample  is  monitored  to  determine  the 
quantity of hydrogen absorbed.  

In the volumetric technique the quantity of hydrogen absorbed by a material is determined 
by the drop in the gas pressure in a known, fixed volume. 

·   With temperature-programmed desorption, hydrogen is desorbed into a flow of He upon 
heating  the  storage  material  at  a  controlled  ramp  rate,  and  it  is  monitored  using  mass 
spectrometry. 

·   All methods have limitations and certain degree of sensitivity to several factors, such as 
sample  contamination,  insufficient  sample  characterisation,  non-isothermal  conditions 
potentially affecting the experimental data obtained.  As a result of these, little unanimity 
has been noted between hydrogen  sorption  measurements reported for instance so far in 
literature for carbon nanotubes. Accurate, repeatable and reproducible hydrogen sorption 
data is necessary for an efficient evaluation of the hydrogen storage potential of materials 
currently being investigated. Cross checking results obtained using different techniques is 
also  important  even  within  the  same  laboratory,  and  even  more  in  the  context  of  inter 
laboratory comparisons.  

·   The  JRC-IE  hydrogen  SOLid-state  storage  TEsting  Facility  (SolTeF)  is  equipped  with 
instruments  covering  different  characterisation  techniques,  temperature/pressure  regimes 
and  sample  sizes.  It  is  currently  engaged  in  the  inter-comparison  of  techniques/ 
instruments  starting  with  a  ‘model’  system  (LaNi5-yAlyHx)  and  using  back-up 
microstructural  investigations.  This  investigation  is  to  be  extended  to  include  other 
material systems. During the practical session, the workshop attendees were trained in the 
execution  of  a  typical  hydrogen  absorption/desorption  experiment  for  the  acquisition  of 
Pressure-Composition-Isotherms, using a Gas Reaction Controller.  

·   Microstructural  characterisation 

tools, 

like  Scanning  Electron  Microscopy  and 
Transmission  Electron  Microscopy  TEM)  can  provide  information  on  the  structure 
evolution  with  hydrogen  sorption/desorption,  cycling,  of  potential  hydrogen  storage 
materials at the micrometer and nanometer scale. In both cases, the micro-volume to be 
analysed is irradiated with a finely focused electron beam, which can be swept across the 
surface of the specimen.  

In  the  SEM,  secondary  and  backscattered  electrons  are  generated  in  a  small  volume  of 
thick  samples  and  collected  by  appropriate  detectors  to  give  information  on  surface 
topography and composition. The large depth of field of the instrument provides a three-
dimensional  view  of  the  specimen.  Characteristic  X-rays  that  are  produced  when  the 
electron  beam  impinges  the  surface  provide  chemical  analysis  of  the  sample  within  the 
interaction volume of beam. 

·  

14

 
 
 
 
·  

In  the  TEM,  a  primary  electron  beam  interacting  with  a  thin  film  sample  generates 
transmission,  diffracted  and  backscattered  electrons,  yielding  different  types  of  images 
(respectively,  bright  field,  dark  field  and  phase  contrast  images),  which  are  all  used  for 
microstructural investigation on hydrogen storage materials. During the practical session, 
the  workshop  attendees  witnessed  a  demonstration  of  the  capabilities  and  ‘sampled’  the 
application  of  the  IE  microstructural  analysis  tools  in  the  research  field  of  hydrogen 
materials storage technologies. 

15

 
 
4.  References 

1 Website of the European Hydrogen and Fuel Cells Technology Platform, at https://www.hfpeurope.org 
2 Website of the International Partnership for the Hydrogen Economy, at  
3 Website of the National Hydrogen Association NHA, at www.hydrogenus.com 
4  K. Nakui,  “Fuel cell & hydrogen activities in Japan”, IPHE meeting, Washington D.C., November 19 (2003). 
5  Website of the U.S. Department of Energy, Energy Efficiency and Renewable Energy, at  

http://www.eere.energy.gov/hydrogenandfuelcells/, or National Renewable Energy Laboratory 
www.nrel.gov/hydrogen/proj_safety.html 

6  The European Integrated Hydrogen Project, at http://www.eihp.org/ 
7  HySafe: Safety of Hydrogen as an Energy Carrier http://www.hysafe.org/ 
8  ISO TC 197 Document N 231,  Business Plan of ISO/TC 197 - Hydrogen technologies, version 5 (2002) 
9  Website of the Institute for Energy of the JRC, at http://www.jrc.nl 
10 E. Tzimas, C. Filiou, S.D. Peteves and J-B. Veyret, “Hydrogen Storage: state-of-the art and future 
perspective”, EUR 20995 EN, EC-DG JRC-Institute for Energy, Petten, The Netherlands (2003). 

16

 
 
                                                
 
 
Handouts of presentations 

 
 
 
 
 
 
 
 
 
The JRC at the service of the 
European Citizen 

M. Steen 

EC- DG JRC-IE 

 
 
 
 
 
 
 
The JRC at the 
Service of the European Citizen

Institute for Energy (IE)
Petten, The Netherlands

http:// ie.jrc.cec.eu.int
email:jrc-ie-info@cec.eu.int
http:// www.jrc.cec.eu.int

JRC – IE Non tech pres. 19.03.04

Panorama of the European Union

European Court 
of Auditors

Court of Justice

European 
Parliament

The Council 
of the 
European 
Union

The Committee of 
the Regions

Economic and 
Social Committee

European Commission
(30 Commission members)

SG.

RELEX

...

...

ENTR

...

ENV

SANCO

…

...

RTD

...

JRC

IRMM

IES

IPSC

IPTS

IE

IHCP

ITU

JRC – IE Non tech pres. 19.03.04

Why JRC?

More than 25% of all EU legislation has a significant S&T basis 
(e.g. food, chemicals, environment, energy)

• advanced analytical requirements, e.g. related to nuclear safety
• harmonisation - best practice – validation;
• training.

As a service of the European Commission, the JRC provides
in-house scientific and technical support to Community 
policy making

In the last 2 years, the JRC has been  involved in over 
70 pieces of EU legislation

JRC – IE Non tech pres. 19.03.04

JRC Mission Statement

to provide customer-driven scientific and technical 
support for the conception, development, 
implementation and monitoring
of EU policies

The JRC functions as a centre 
of science and technology (S&T) 
reference for the EU 
independent of commercial 
and national interests...

JRC – IE Non tech pres. 19.03.04

The structure of the JRC

7 Institutes in 5 Member States: total staff 1635

IE - Petten The Netherlands
• Institute for Energy

IRMM - Geel Belgium
• Institute for Reference Materials and Measurements

ITU - Karlsruhe Germany 
• Institute for Transuranium elements

IPSC - IHCP - IES - Ispra Italy
• Institute for the Protection and the Security of the Citizen 
• Institute for Health and Consumer Protection 
• Institute for Environment and Sustainability 

IPTS - Seville Spain
• Institute for Prospective Technological Studies 
• DG, Scientific Strategy & Resource Directorates 

JRC – IE Non tech pres. 19.03.04

FACTS

MEASURES NEEDED

adapted from Daimler-Chrysler

JRC – IE Non tech pres. 19.03.04

Global Energy Challenge

JRC – IE Non tech pres. 19.03.04

Wider Policy Context

• Lisbon Strategy

– Growth and Employment by Technology
– Environmental Technologies Action Plan
– Ensure sustainable, affordable, non-volatile Energy 

supply 

• The EU as Global Player
– Millennium Goals
– Kyoto Protocol

• Natural Resources and the Environment

– Bio-Energy
– Emissions and Health

• Europe's Safety and Security

– Dispatch, Storage and Conversion

JRC – IE Non tech pres. 19.03.04

Energy at the JRC

to provide scientific and technical support for the conception, 
development, implementation and monitoring of community 
policies related to energy.

§ performance assessment of energy technologies: efficiency, 

safety, reliability, environmental compliance

§ new energy carriers: Hydrogen
§ solar test installation for photovoltaic devices 
§ characterisation of vehicle emissions
§ security aspects of energy infrastructures
§ techno- and socio-economic aspects in energy production, 

conversion and use

to become EC S&T reference for safer and cleaner energy 
technologies

JRC – IE Non tech pres. 19.03.04

Institute for Energy (IE)

The Institute provides scientific technical support for the 
conception, development, implementation and monitoring of 
community policies related to energy.

Special emphasis is given to the security of energy
supply and sustainable and safe energy production.

Fperformance: efficiency, safety, environmental compliance
Fnew energy carriers: e.g. Hydrogen

JRC – IE Non tech pres. 19.03.04

IE Activities

Nuclear safety

Making both existing and new 

designs of nuclear power plants in 

enlarged EU & CIS even safer

Cleaner Energies

Supporting the transition towards a 

de-carbonised, hydrogen economy

Energy Information Platform

evaluation, validation, forecasting, dissemination

High Flux Reactor

• Medical Applications

• Nuclear Safety

JRC – IE Non tech pres. 19.03.04

Clean Energies Unit Mission

Provide S&T support to EU policies on safer and cleaner energy 
technologies for sustainable development through acting as the EC in-
house reference point on selected energy technology issues

l validating, harmonising and analysing data and information on sustainable 

energy technologies 

l validating, harmonising and standardising measurement and test methods 

and procedures (forerunners to codes & standards)

l assessing, validating and benchmarking performance, efficiency, 

reliability, safety and environmental compliance of selected safer and 
cleaner energy technologies  

S&T competence, state-of-the-art facilities, competitive work

l active communication of rationale and policy-impact of the work 

programme and dissemination of its output

JRC – IE Non tech pres. 19.03.04

S&T support deliverables

(1) data and information

• techno-economic assessments, state-of-the-art reports, ... 
• S&T dimension to, and review of policy documents 
• comments to ISCs
• acting as participant, moderator, convenor, observer, … in meetings

(2) measurement and test methods and procedures

• test protocols,
• validated procedures, 
• RR reports,
• experimental benchmarks, ...

(3) work programme deliverables (S&T competence and facilities)

(4) dissemination

• workshops (training, enlargement)
• publications, ...

JRC – IE Non tech pres. 19.03.04

Experimental Activities

no development of new technologies, but

1) “enabling” activities in areas of:  

•

•

process issues related to alternative fuels and 
hydrogen from biomass
characterisation and performance assessment of
•
fuel cells, stacks and systems
• hydrogen storage technologies
• hydrogen sensors

2) techno-economic assessment of energy technology issues

through own research and networking with EU stakeholders  

JRC – IE Non tech pres. 19.03.04

(1) Alternative Fuels from 
Waste and Biomass

Objective:

to establish best available options for the 
production of biofuels/bio-hydrogen from 
waste and biomass through the evaluation 
of primary production processes and 
methods of fuel cleaning. 

JRC – IE Non tech pres. 19.03.04

Capabilities:

• thermogravimetric facilities for 

characterisation of fuels and process 
generated condensed phases in simple 
process simulated atmospheres

• laboratory-scale process simulation rigs 
for durability testing of process probes, 
sensors & monitors as well as catalysts 
and filters for flue/fuel gas cleaning 
systems

• gas analysis techniques for process 

monitoring

JRC – IE Non tech pres. 19.03.04

(2) Fuel Cell Systems Testing and Standardisation

Objectives: 

• to develop and harmonise

testing procedures 
(forerunners to codes & 
standards) applicable to fuel 
cells stacks & systems

• to provide direct 

comparisons of competing 
fuel cell technologies in 
terms of performance & 
operational characteristics

JRC – IE Non tech pres. 19.03.04

(2a) unique 100 kW test facility

Ø Six degrees of freedom vibration table

Ø Environmental chamber

Ø Fully integrated Fuel Cell Automated Test Station

Ø Gas feed and analysis equipment

Ø Geothermal cooling system

JRC – IE Non tech pres. 19.03.04

Capabilities of the facility

§ short and long term testing of fuel cells, stacks and 

systems up to 100 kW

§ simulation of vibrations typical for stationary, marine and 

surface transport and applications in aviation

§ ambient temperatures in the range –40 to +60 ºC and up 

to 95 % humidity

§ load profile and fuel flow transient simulations

§ hydrogen production on demand (~ 60 m3/h at 7 bar, <10 

ppm CO)

§ analysis of the inlet & outlet gases of the fuel cells

JRC – IE Non tech pres. 19.03.04

(2b) other activities

§ FCTESTNET: A FP5 Thematic Network 

funded by the European Commission  (55 
Participating Organisations):

Ø development of harmonised testing 
procedures applicable to: stationary 
power sources, portable fuel cells, 
transport applications

Ø focusing on: fuel cells, fuel cell 
stacks & fuel cell systems

§ FC MODELLING:

to support & complement the experimental activities è better 
understanding of FC systems performance

JRC – IE Non tech pres. 19.03.04

(3) Systems for Alternative Fuels 

Objective: 
to harmonise, validate and standardise test procedures 
for safety and operational performance of hydrogen 
storage and systems 

JRC – IE Non tech pres. 19.03.04

(3a) High Pressure Storage

• pressure testing of hydrogen and natural gas tanks, mainly 

for vehicle applications

• permeation  measurements  and  load-cycling  at  controlled 

temperature 

• development of test procedures for performance testing
• support to pre-normative research & standardization

• development & validation of risk assessment methodologies

bunker 
for high 
pressure 
facilities 

JRC – IE Non tech pres. 19.03.04

Hydrogen Safety / Risk

Application of expertise and tools developed and used in nuclear safety

JRC – IE Non tech pres. 19.03.04

Hydrogen Explosion / Distribution

Explosion accident in 
Explosion accident in 
a refueling station
a refueling station

Flow path in streets 
Flow path in streets 
with South-West winds
with South-West winds

JRC – IE Non tech pres. 19.03.04

H2 release from a bus tank in a tunnel
H2 release from a bus tank in a tunnel
- pressure distribution on an iso surface 
- pressure distribution on an iso surface 
of 350 K
of 350 K

(3b) On-board vehicle hydrogen safety sensors

Objective: 
to establish unified testing 
procedures for H2- safety 
sensor performance (lifetime, 
sensitivity, accuracy, reaction 
time..) under real service life 
conditions 

The challenge:
sensors that can sense leaks within the target timeframe at the 
desired detection level, assess the hazard, trigger an alarm or 
activate a protective device

Type of sensors:
electrochemical, semi-conductor, catalytic pellistor, thermal 
conductivity and field effect transistor.

JRC – IE Non tech pres. 19.03.04

(3c) Solid-State Storage

Objective:
to reduce uncertainties in hydrogen sorption measurement 
techniques for reliable assessment of potential and of 
fitness for purpose

• laboratory investigations 

• using different characterisation techniques/instruments
• covering different temperature and pressure regimes
• repeatable and reproducible results on well-characterised

materials

• ‘round robin’ exercises
• unified testing procedures

JRC – IE Non tech pres. 19.03.04

PCT Gas Reaction Controller Unit

• Volumetric  – pressure difference measurement
• dynamic (at a constant hydrogen mass flow rate) 

Pressure-Composition-Temperature (PCT) 
measurements

• p = 0 to 200 bar, T = RT to 500oC 
• Cryostat  -60 to 60oC
• fully automated

Intelligent Gravimetric Analyser

• equilibrium adsorption data (weight increase) 
• p=0 to 20 bar; T= -196oC to 500oC (at 1 bar)
• fully automated
• custom-made features giving flexibility & allowing extra 
measurements, (e.g. mass spectrometer, features for 
catalysis etc..)

Temperature Programmed Reduction/Reaction Spectroscopy 

JRC – IE Non tech pres. 19.03.04

(4) The Sustainable Energy Technologies Reference 
& Information System (SETRIS)

Objectives: in collaboration between JRC institutes

•
•
•

to collect, harmonise and validate information on energy technologies
to perform related techno-economic assessments 
to establish, in collaboration with all relevant national partners, the 
S&T reference required for the debate on a Sustainable Energy 
strategy in an enlarged EU & in the context of global sustainable 
development

Other activities
• Secretariat of the European H2 & Fuel Cell Technology Platform
• ExCo of IEA Hydrogen Implementation Agreement
• Implementation and Liaison Committee of International Partnership 

for the Hydrogen Economy

JRC – IE Non tech pres. 19.03.04

Vision

EC H/FC Project Team
(Inter-service Group)

H2/ FC TECHNOLOGY PLATFORM
H2/ FC TECHNOLOGY PLATFORM

Member States’ 
Mirror Group

Advisory Council
(incl. Executive Group)

TP Secretariat
Information Office
IT Support Service

Steering 
Panels :

Strategic 
Research Agenda

Deployment 
Strategy - LHP

Initiative 
Groups :

H2/ FC 
Roadmap

Public 
awareness

Safety, codes 
& standards

Business 
development

Education & 
training

PLATFORM OPERATIONS
PLATFORM OPERATIONS

New and on-going projects and initiatives (EC + MS national, regional and local)

JRC – IE Non tech pres. 19.03.04

GENERAL ASSEMBLY

(Bi-)annual Technology Platform Forum

International Partnership for the 
Hydrogen Economy (IPHE)

‘’…To serve as a 
mechanism to organize 
and implement 
effective, efficient, 
and focused 
international research, 
development, 
demonstration and 
commercial utilization 
activities related to 
hydrogen and fuel cell 
technologies…” 

RCS scoping paper

JRC – IE Non tech pres. 19.03.04

International Energy Agency

• ExCo H2 Implementing Agreement 
• HIA Task 17 Solid and Liquid State Hydrogen Storage Materials
• HIA Task 18 Assessment of Integrated Systems
• HIA Task 19 Hydrogen Safety
• ExCo FC Implementing Agreement 
• Bioenergy Task 36 Integrated Waste Management
• Bioenergy Task 37 Biogas

CEN/CENELEC

• CEN/TC 343 (Solid Recovered Fuels)
• CEN/BT/WG/ 149 “Liquid and Gaseous Alternative Fuels”
• CEN/CENELEC mandate

Others: ISO-TC 105, US Fuel Cell Council, …

JRC – IE Non tech pres. 19.03.04

from FP6 to FP7

JRC – IE Non tech pres. 19.03.04

Ore

Coal

Nuclear 
Fuel Processing

Nuclear Fission

H2

syngas

H2

performance assessment – verification – R&D

H2
Catalytic/Steam 
Reforming

H2

Hydrogen
Fuel Cell

hydrogen 
storage

H2

Crude Oil

Refinery
Gasoline /Diesel

HT Fuel Cell

Steam Turbine

Natural Gas

Biomass/Waste 
Energy Crops

H2

H2

GTL

BTL

Combustion
Combustion
Combustion

Solar Thermal
Geothermal

(co-)fuel, syngas, synfuel
processing, incl. CO2 capture

cycling

Gas 
Gas 
Gas 
Turbine
Turbine
Turbine

Reciprocal Eng

Combined 
Heat Power

Electricity
Generation

Electricity 
storage

Heat

Mech. Energy
Propulsion

Wind
Wave Tide

Solar Electric

JRC – IE Non tech pres. 19.03.04

+ process-flow modelling

Wind Turbines

ZEFPP

hypogen

HFP

Photovoltaic 
Conversion

IE  work FP7

Contact Points for H2+FC related activities at JRC-IE

production of hydrogen from syngas

David.Baxter@jrc.nl - Tel/Fax: (31) 224565227/5630

hydrogen storage technologies, performance and safety assessment

Pietro.Moretto@jrc.nl - Tel/Fax: (31) 224565269/5630

harmonisation of test procedures for fuel cells, stacks and systems
Georgios.Tsotridis@jrc.nl - Tel/Fax: (31) 22456 5122/5630

techno-economic assessment of energy technologies

Estathios.Peteves@cec.eu.int - Tel/Fax: (31) 22456 5245/5630

Cleaner Energies Unit 

Marc.Steen@cec.eu.int - Tel/Fax: (31) 224565271/5630

JRC – IE Non tech pres. 19.03.04

 
 
 
 
 
The JRC Enlargement & 
Integration Action 2005 

R. Hurst,  

Presented by  

C. Filiou 

EC- DG JRC-IE 

 
 
 
 
 
 
 
The JRC Enlargement and Integration Action 2005

JRC – IE Enlargement&Integration 2005

The JRC and Enlargement & Integration

Strategic Objectives:

To help speed up the integration of New Member States

To  help  the  CC’s  and  other  potential  MS  in  dealing  faster 
with the “EU acquis” in areas of JRC competence

To contribute to the development of the “European Research 
Area” 

Main Target:

full  working 

To  achieve 
the 
NMS/CCs/PMSs and  the  JRC,  consistent  with  the  level 
enjoyed by older MS

involvement  between 

JRC – IE Enlargement&Integration 2005

JRC Enlargement & Integration  Action

Main Instruments:

1. Extend JRC core projects to focus on 

specific NMS/CC/PMS needs 

2. Involve NMS/CC/PMS organisations in JRC networks 
3.  Host visiting scientists, seconded experts, fellows
4. Advanced training courses and workshops
5. Information and awareness actions

JRC – IE Enlargement&Integration 2005

Graph 1. Share of organisations from NMS and CC in the total number 
of JRC partners in Indirect Action and in Institutional Networks  

25%

20%

15%

10%

5%

0%

24%

13%

16%

7%

during FP5

during FP6 (first data)

Indirect Action partners

Institutional Networks
partners

JRC – IE Enlargement&Integration 2005

Presence of Temporary Staff from Enlargement 
Countries (end of years)

180

160

140

120

100

80

60

40

20

0

2000

2001

2002

2003

2004

JRC – IE Enlargement&Integration 2005

Nationalities of Temporary Staff from 
Enlargement Countries (Dec. 04)

11

27

5

14

24

22

3

19

21

62

BG

CZ

EE

HU

LT

LV

PL

RO

SI

SK

TR

JRC – IE Enlargement&Integration 2005

JRC Enlargement & Integration  Action

Main Instruments:

1. Extend JRC core projects to focus on 

specific NMS/CC/PMS needs

2. Involve NMS/CC/PMS organisations in JRC networks
3.  Host visiting scientists, seconded experts, fellows
4. Advanced training courses and workshops
5. Information and awareness actions

JRC – IE Enlargement&Integration 2005

Partners in EU funded Projects & Networks 

• JRC applies to FP6  calls on “equal footing” and on 
“competitive basis” ‘equal to all other organisations

• Since January 1st 2003, the JRC has been involved in more 
than 350 research proposal submitted to various FP6 calls

• Over 70% of these proposals include one or  more partners 

from NMS and Candidate Countries.

JRC – IE Enlargement&Integration 2005

NMS / CC Partners in JRC Projects & Networks

Network Partners in NMS / Candidate Countries 

CZ 

PL 

HU 
SK 

SL 

RO 
EE 

BG 

LT 
TR 

LV 

CY 
MT 

0 

10 

20 

30 
Institutionals 

40 

50 

60 

Indirect actions 

JRC – IE Enlargement&Integration 2005

JRC Enlargement & Integration  Action

Main Instruments:

1. Extend JRC core projects to focus on 

specific NMS/CC/PMS needs 

2. Involve NMS/CC/PMS organisations in JRC networks 
3.  Host visiting scientists, seconded experts, fellows
4. Advanced training courses and workshops
5. Information and awareness actions

JRC – IE Enlargement&Integration 2005

 
Distribution of IE statutory staff by nationality

Nb already some temporary contract staff from 4 NMS/CC

35

30

25

20

15

10

5

0

BE DE DK ES FR FI GB EL

IE IT LU NL PT AT SE CZ HU BG SK

BE DE DK ES FR FI GB EL

IE IT LU NL PT AT SE CZ HU BG SK

Total 157

f
f
a
t
s

f
o
r
e
b
m
u
N

35

30

25

20

15

10

5

0

Distribution of IE non-statutory staff by nationality

JRC – IE Enlargement&Integration 2005

f
f
a
t
s

f
o
r
e
b
m
u
N

15

10

5

0

BE BG CZ DE FI

FR GB GR HU IT NL PL RO SE SI SK

Total 58

JRC – IE Enlargement&Integration 2005

 
 
 
 
E&I STAFF and FELLOWS at IE 2005

Name
NAGY Miklos
MACIEJEWSKA Anna
SIEWIOREK Aleksandra
WIECZOREK Kamila
ROCA  Antoaneta
ZEMAN Andrej
NEOV Dimitar
KALIVODOVA Jana
NOVOTNY RADEK
TUCEK Kamil
PRVAKOVA Slavka
KUBANYI Jozef
LOFAJ Frantisek
PATRIK Milan
SALYK Ota
SVOBODA Karel
GYENES Gyorgy
ROBAK Zgibniew
BUJAN Albert
MITEVA, Rossitza
SRODA Symon
KAVALOV Boyan 
BRACISIEWICZ, Marek
RANGUELOVA, Vesselina
DUCHAC, Alexander
TOTH, Bela
BURCL, Rudolf

Nationality
HU
PL
PL
PL
RO
SK
BG
CZ
CZ
CZ
SK
SK
SK
CZ
CZ
CZ
HU
Pl
SK
BG
PL
BG
PL
BG
CZ
HU
SK

Gender
M
F
F
F
F
M
M
F
M
M
F
M
M
M
M
M
M
M
M
F
M
M
M
F
M
M
M

Grade
20
20
20
20
20
30
30
30
30
30
30
40
40
40
40
40
40
40
VS
DNE
A II/2
A II/2
GFIV 13
A*   06
A*   11
A*   06
A*   06

Project
DMD
SETRIS
CLEANWEB
CLEANWEB
BNCT
SAFELIFE
NET
SUNASPO
SAFELIFE 
AMA
SAFECASK
AMA
SAFELIFE
AMA
SYSAF
CLEANWEB
PHEBEN2
CLEANWEB
Phebus
NESC
CLEANWEB
ACE-TECH
CLEANWEB
TSSTP
TSSTP
AMA
TSSTP

JRC – IE Enlargement&Integration 2005

JRC WEB PAGE

FOR 2005

JRC – IE Enlargement&Integration 2005

JRC Enlargement & Integration  Action

Main Instruments:

1. Extend JRC core projects to focus on 

specific NMS/CC/PMS needs 

2. Involve NMS/CC/PMS organisations in JRC networks 
3.  Host visiting scientists, seconded experts, fellows
4. Advanced training courses and workshops
5. Information and awareness actions

JRC – IE Enlargement&Integration 2005

Institute for Energy, Petten, the Netherlands

New and Renewable Energies

Cogeneration

107 JRC Workshops 

14 Workshops at IE

71 posts in the JRC

13 posts at IE

Nuclear Energy

Health

Fuels from Waste and Biomass

Fuels Cells Performance 
Testing
Hydrogen Storage Technologies

Plant Life Management for Safe 
Operation
How safe is it? 
Valorisation on Tacis / Phare 
results
Techniques for Characterisation 
of Repair Welds
Nuclear Waste Packages
Management of Accident s

Non Destructive Testing of 
Nucle ar Components
Advanced Techniques for 
Assessment of Thermal Fatigue 
Damage
Safety of Eastern European 
Nuclear Facilities
Casks for High -Level Nuclear 
Waste
Ageing Issues of key Nuclear 
Power Plant Components
Boron Neutron Capture Therapy

JRC – IE Enlargement&Integration 2005

Data and Document 
Conservation 

On line data & Information 
network for Energy

IE -J08

IE-J09
IE-J10

IE-J02

IE-J03
IE-J04
IE-J05

IE-J06

IE-J07

IE-J11
IE-J12
IE-J13

IE-J01

IE -W01
IE -W02
IE -W04
IE -W05
IE -W 06

IE -W07

IE -W08

IE -W09
IE -W10

IE -W11

IE -W03

IE -W1 2
IE -W13

IE -W14

JRC Enlargement Action IE Workshops 2005

• Cogeneration (2x)
• Fuels from Waste and Biomass (2x)
• Fuels Cells Performance Testing
• Hydrogen Storage Technologies

• Plant Life Management for Safe Operation
• How safe is it? 
• Valorisation of Tacis / Phare results
• Techniques for Characterisation of Repair Welds
• Nuclear Waste Packages

• Boron Neutron Capture Therapy (2x)

• Online data & Information network for Energy

JRC – IE Enlargement&Integration 2005

JRC Enlargement & Integration  Action

Main Instruments:

1. Extend JRC core projects to focus on 

specific NMS/CC/PMS needs 

2. Involve NMS/CC/PMS organisations in JRC networks 
3.  Host visiting scientists, seconded experts, fellows
4. Advanced training courses and workshops
5. Information and awareness actions

JRC – IE Enlargement&Integration 2005

Information and Awareness (Examples)

Place 

Budapest, Hungary 
Sofia, Bulgaria 
Warsaw, Poland 
Bratislava, Slovak Rep. 
Riga, Latvia 
Prague, Czech Rep. 
Ljubljana, Slovenia 
Sofia, Bulgaria 
Budapest, Hungary 
Brussels (JRC stand) 
Warsaw  (JRC workshop) 
Valletta, Malta 

Date 
March 2000 
May 2000 
November 2000 
April 2001 
June 2001 
September 2001 
January 2002 
June 2002 
October 2002 
November 2002 
November 2002 
December 2002 

Sofia, Bulgaria 
Prague, Czech Rep 
Cyprus  
Bucharest, Pitesti, Romania 
Ljubljana, Slovenia 
Warsaw, Krakow, Poland 
Tallin, Vilnius, Riga 
Istanbul, Ankara, Turkey 
Valletta, Malta 
Warsaw, Poland 
Bratislava, Kosice Slovakia  March 2004 
Bucharest, Iasi Romania 

January 2003 
January 2003 
February 2003 
April 2003 
May 2003 
June 2003 
October 2003 
October 2003 (plan) 
Dec 2003 
Dec 2003 

April 2004 

Type 

Info-day 
Info-day 
Info-day 
Info-days (two) 
Info-day 
Info-day 
Info-day 
Info-day 
Info-day 
FP6 launch 
FP6 launch 
FP6 launch 

FP6 launch 
FP6 launch 
FP6 launch 
Info days (two) 
Info-day 
Info days (two) 
Info days (three) 
Info days (two) 
Info day 
Info day 
Info day (two) 
Info day (two) 

Participants 
60 
70 
200 
140 
20 
270 
100 
80 
200 
200 
350 
100 

250 
600 
250 
500 
200 
400 
200 
550 
120 
80 
400 
400 
5740 

JRC – IE Enlargement&Integration 2005

Marie Curie Training Schemes

JRC institutes can host  Fellows

· Recent publications on 

www.cordis.lu/improving/fellowships/home.htm

· Research Training Networks  

Intra-European Fellowships  

· Application directly to Marie Curie scheme

JRC – IE Enlargement&Integration 2005

 
 
 
 
·
·
Whom to contact, where?

Gateway: http://www.jrc.cec.eu.int./enlargement

Who to contact 
at the Institutes:

IPSC  carmelo.addabbo@cec.eu.int
IES
arwyn.jones@jrc.it
IHCP   michael.hoffmann@jrc.it
IPTS   andries.brandsma@jrc.es
IE        roger.hurst@cec.eu.int
IRMM doris.florian@irmm.jrc.be
ITU victor.esteban-gran@cec.eu.int

JRC – IE Enlargement&Integration 2005

JRC, DSS (coordination):
giancarlo.caratti@cec.eu.int

jiri.burianek@cec.eu.int

 
 
 
 
 
Overview of the Solid State 
Hydrogen Storage and related 
R&D Issues 

A. Züttel 

Universität Fribourg, Switzerland; Vrije 
Universiteit van Amsterdam, Netherlands 

 
 
 
 
 
 
 
OVERVIEW OF THE SOLID STATE HYDROGEN 
STORAGE AND RELATED R&D ISSUES

ANDREAS ZÜTTEL

Institute for Renewable Energy Switzerland (IfRES)
Physics Department
UNIVERSITY of FRIBOURG
SWITZERLAND

Solid State Physics of Energy Storage Systems
Faculty of Sciences
Division of Physics and Astronomy
VRIJE UNIVERSITEIT  Amsterdam
The Netherlands

CONTENTS

• MOLECULAR HYDROGEN

• INTERACTIONS OF MOLECULAR HYDROGEN

• METAL HYDRIDES

• COMPLEX HYRIDES

• CHEMICAL HYDRIDES

• FUTURE R&D

• CONCLUSION

1

Andreas Züttel, IfRES (2005)

PRIMITIVE PHASEDIAGRAM OF HYDROGEN

RT

Ref: W. B. Leung, N. H. March and H. Motz, Physics Letters 56A (6) (1976), pp. 425-426

2

2

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

MOLECULAR HYDROGEN

)V(p

=

××
TRn
×
bnV

a

2

2

n
×
V

3

3

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

LENNARD-JONES POTENTIAL 

Van der Waals interaction

)r(V

×e×=
4

12
-÷

r

6
÷

r

Pauli repulsion

dipole

r = s

r0 = 21/6 s

-e

4

4

s = collision distance
e = binding energy

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

-
-
ú
ú
û
ù
ê
ê
ë
é
ø
ö
ç
è
æ
s
ø
ö
ç
è
æ
s
ATOMIC VIEW OF PHASE TRANSITIONS

u

Consider the collision of a single 
molecule with a bound pair of molecules

To separate the two molecules requires 

the dissociation energy

This means the single molecule, of 
mass m, travelling at the temperature T
with a average velocity u:

u 2

=

×

Tk8
×
m

½·m·u2 <<  e

virtually no collisions will cause the 
molecule pair to dissociate

The phase will be SOLID

½·m·u2 >>  e

virtually all collisions will cause the 
molecule pair to dissociate

The phase will be GASEOUS

½·m·u2 »

some collisions will cause the 
molecule pair to dissociate, others 
will not

The phase will be LIQUID

Andreas Züttel, IfRES (2005)

HYDROGEN STORAGE

Hydrogen gas

Liquid hydrogen

Physisorption

Metalhydride

Complex hydrides

Chemical hydrides

Andreas Züttel, IfRES (2005)

5

6

e
e
p
HYDROGEN STORAGE

Hydrogen gas

Material

Aluminium Alu 6061-T4
AISI 4140 Steel
Spider silk (protein)
Kevlar (polyaramid)
Basic Carbon Fiber Composite
Hexcel® Carbon Fiber AS4D 
(12,000 Filaments)

Density 
[kg m-3]
2700
7850
1300
1440
1570

Tensile breaking 
stress  [GPa]
0.145
1.650
1.3
2.76
0.2

1790

4.280

Ref.: F. Vollrath & D. P. Knight, NATURE 410 (2001), pp. 541-549

d
d

w

a

=

p
D+×
v

s2

p

da

(
Vp

)

=

××
TRn
×
bnV

a

2

2

n
×
V

di

dw

Dynatek

R = 8.314 J·K-1·mol-1
a(H2) = 2.476·10-2 m6·Pa·mol-2, b(H2) = 2.661·10-5 m3·mol-1

Andreas Züttel, IfRES (2005)

HYDROGEN STORAGE

Liquid hydrogen

75% Orthohydrogen

at RT 

25% Parahydrogen

D H(T<77K)
523 kJ·kg-1

D Hvap(T=21.2K)
452 kJ·kg-1

Energy use for liquefaction:
Wth = 3.92 kWh·kg-1
Wprac = 10 kWh·kg-1

Density (H2 liq.) = 70.8 kg·m-3

Andreas Züttel, IfRES (2005)

7

8

D
-
-
HYDROGEN STORAGE

Physisorption

n
n

m

=

(
1

b×

c
(
(
)
-+×b
1
c

)
1

)b×

H
V
×
Tk

e

k
×=b
F
k

0
a
0
d

=

p
p

0

H

V

H

ads

×
Tk

=

c

e

Ref.: A. Züttel et al., Int. J. of Hydrogen Energy 27 (2002), 
pp. 203-212
M.G. Nijkamp et al., Appl. Phys. A 72 (2001), pp. 619–623
S. Brunauer, P. H. Emmett und E. Teller, J. Amer. Chem. 
Soc. 60 (1938), p. 309

theoretical
calculation
32 K

el. chem.
at 298K

gas phase
at 77 K

9

Andreas Züttel, IfRES (2005)

BINARY HYDRIDES

Ref.: Gottfried Brendel, “Kapitel: Hydride”, Ullmanns Encyklopädie der technischen 
Chemie, 4. neubearbeitete und erweiterte Auflage, Band 13 (1977), pp. 109-133, Verlag 
Chemie Weinheim New York

10

1
0

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

-
D
-
D
D
STATES OF HYDROGEN

E / eV

H2

® H+ + H-

+17.37

H0 ® H+ + e-

+13.60

20.0

10.0

D EA

0.0

-0.75

H0 + e- ® H-
-4.52

D EI

H0

D Edis
2 H0 ® H2

Ref.: Wojciech Grochala and Peter P. Edwards, Chem. Rev. 104 (2004), pp. 1283-1315

11

1
1

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

HYDROGEN ABSORPTION IN METALS

Hydrogen & metal

Physisorption

Chemisorption

Subsurface hydrogen

Solid solution (a-phase)

Hydride (b-phase)

12

1
2

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

LENNARD-JONES POTENTIAL

Ref.: J. E. Lennard-Jones, Trans. Faraday Soc. 28 (1932), pp. 333. 
L. Schlapbach, Chapter 1,  L. Schlapbach (Ed.) in Intermetallic Compounds I, Springer Series Topics in Applied 
Physics, Vol. 63, Springer–Verlag, 1988, p. 10.

13

Andreas Züttel, IfRES (2005)

EFFECTIVE MEDIUM THEORY

Ref.: P. Nordlander, J. K. Norskov, and F. Besenbacher, J. Phys. F. Metal Phys. 16:9 (1986), pp. 1161-1171, 
J.K. Norskov and  F. Besenbacher, J. of the Less-Common Metals 130 (1987), pp. 475-490

14

Andreas Züttel, IfRES (2005)

ELECTRONIC STRUCTURE

Bandstructure of 
LaNi5 and LaNi5H7

1)  Lattice  expansion  reduces  the  band-
width.

2) Attractive potential of the proton affects 
the  metal  states  and  leads  to  the  metal-
hydrogen band 5 to 8 eV below EF.

3)  The  H-H  interaction  results  in  new 
features in the lower part of the density of 
states  for  systems  with  more  than  one  H 
atom per unit cell.

4) An upwards shift of EF results from the 
balance  between  the  additional  electrons 
brought in by hydrogen and the number of 
new states below EF.

The  balance  between  the  ‘exothermic’ 
lowering  of  occupied  states  and 
the 
‘endothermic’  upwards  shift  of  EF
the 
determines 
metalhydride.

stability 

the 

of 

Ref.: L. Schlapbach, F. Meli, and A. Züttel, Chap. 21: “Intermetallic Hydrides and their Applications” in 
Intermetallic Compounds: Vol. 2, Practice, J. H. Westbrook and R. L. Fleischer (1994) John Wiley & Sons Ltd.

15

1
5

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

HYDROGEN ABSORPTION IN METALS

SD
R

HD
R

ln

=÷÷

p
p

0

0

H
×
TR

0

S
R

a -Phase: Solid Solution

b -Phase: Hydride Phase

MHx        (0 < x < 0.1)
H      H, D V/V = k·cH

x = {1, 2, 3,…}

MHx
H      H

16

Andreas Züttel, IfRES (2005)

D
-
D
ø
ö
ç
ç
è
æ
EMPIRICAL MODELS: GEOMETRY

1) Size of interstitial site:
r > 0.37 Å

Westlake criterion
Ref.: D. G. Westlake, J. Less-Common Metals 91 (1983), pp.275-292

2) Distance between hydrogen atoms:
d > 2.1 Å

Ref.: A. C. Switendick, Z. Phys. Chem. N.F. 117 (1979), pp. 89

V < 245 kg m-3

Number of hydrogen atoms:

Number of interstitial sites for which 1) and 2) applies.

17

Andreas Züttel, IfRES (2005)

EMPIRICAL MODELS: STABILITY

1) Reversed stability (global)

DH(ABnH2m) = DH(AHm) + DH(BnHm) - (1-F)·DH(ABn)

Miedema Model
Ref.: H.H. Van Mal, K.H.J. Buschow and A.R. Miedema, J. Less-Common Met. 35 (1974), pp. 65

2) Imaginary binary hydrides (local)
AmBn + xH ®

(AmBnHx)

interstitial site

DH([AaBb]H) = DH(AmHx·a/(a+b)) + DH(BnHx·b/(a+b))
binary hydrides
Ref.: I. Jacob, J.M. Bloch, D. Shaltiel and D. Davidov, Solid State Comm. 35 (1980), pp. 155.

18

Andreas Züttel, IfRES (2005)

r
SEMI-EMPIRICAL MODEL FOR THE STABILITY

The Local Band-Structure Model

H

D×=

RWEa

å×

×

a = 18.6 kJ·mol-1HÅ4eV-3/2
b = -90 kJ·mol-1H

j

4

+

b

j

Rj

W

DE

19

1
9

Ref.: R. Griessen, Phys. Rev. B 38 (1988), pp.3690-3698 
and  V.L. Moruzzi, J. F. Janak, A.R. Williams, „Calculated 
Electronic Properties of Metals“, Pergamon, New York 
(1978)

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

THERMODYNAMICS OF HYDRIDES

p

D H0 < 0
D S0 < 0

G

MH

G

H

2

D=

G

==
0

G

0
MH

G

0
H

2

0

G

=

××

TR

ln

÷
D=÷

0

H

D×
ST

0

p
p
0

××

TR

ln

x M + H2                 x MH2/x
Equilibrium D G = 0

÷
÷

p
p

0

Elements

Alloy

ln

÷
=÷

p
p
0

0

H
1
-×
TR

0

S
R

for p = p0

T

dec

=

per H2

0
H
0

S

D H0
Hydride

D H0
Complex

D S0 = S0(H2) = 130 J K mol-1

20

Andreas Züttel, IfRES (2005)

D
-
¥
D
D
ø
ö
ç
ç
è
æ
-
ø
ö
ç
ç
è
æ
D
D
D
ø
ö
ç
ç
è
æ
-
-
-
PHASE TRANSITION

SD
R

HD
R

ln

p
p

0

=÷÷

H
×
TR

S
R

21

2
1

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

STABILITY OF HYDRIDES: VAN’T HOFF PLOT

Tdec

22

Andreas Züttel, IfRES (2005)

-
D
-
D
ø
ö
ç
ç
è
æ
HYDRIDES

Metal hydrides

MgH2, AlH3

XAlH4, XBH4

-NH2, =NH

Hd + and Hd -

T

dec

=

)

0
H
dec
(
0
HS
2

(
H
2
)

Material

H2 [mass%]

Tdec [°C] 1 bar

LaNi5H6
TiMn1.5H2.5
FeTiH2
ZrH2
TiCr1.8H3.5
Mg2NiH4
VH2
TiH2
NaH
CaH2
Li2NH + LiH
LiNH2 + LiH
NaAlH4
MgH2
AlH3
LiAlH4
NaBH4
LiH
Al(BH4)3
NH3
LiBH4

1.49
1.76
1.86
2.16
2.43
3.62
3.81
3.98
4.20
4.79
5.50
6.50
7.46
7.66
10.07
10.62
10.66
12.86
16.90
17.75
18.51

15
-61
-10
696
-120
300
-10, 
780
430
1000
600
300
30, 120
320
<RT
-93
620
900
<100
-32
230

23

Andreas Züttel, IfRES (2005)

STABILITY OF HYDRIDES

24

Andreas Züttel, IfRES (2005)

D
METAL HYDRIDES

COMPLEX HYDRIDES

+

-

H

s

B
p

Li
s

Ref.  K. Miwa, N. Ohba, S. Towata, Y. Nakamori, 
S. Orimo, Phys. Rev. B 69 (2004), 245120

2/3 ABH4

T

dec

2/3 AH + 2/3 B + H2
0
H
0

=

)

0

(
=
pp

S

x MH2/x               x M + H2

ln

p
p

0

-=÷÷

0
H
R

1
+×
T

0

S
R

25

Andreas Züttel, IfRES (2005)

STABILITY OF NaAlH4

ln

=÷÷

p
p

0

0

H
×
TR

0

S
R

Ref.: B. Bogdanovic et al., J. Alloys and Comp. 302 (2000), pp. 36-58

26

Andreas Züttel, IfRES (2005)

D
D
ø
ö
ç
ç
è
æ
D
D
D
-
D
ø
ö
ç
ç
è
æ
-
MECHANISM OF THE THERMAL DECOMPOSITION (NaAlH4)

3 NaAlH4

Na3 AlH6 + 2 Al + 3 H2

+

3-

+

+

Na3 AlH6

® Al + 3 NaH + 3/2 H2

+

+

-

-

-

+

+

3-

+

+

27

Andreas Züttel, IfRES (2005)

ENERGY LEVELS OF NaAlH4

NaAlH4

1/3 Na3 AlH6 + 2/3 Al + H2  

® Al + NaH + 3/2 H2

D H

Na, Al, 2H2

2/3 Al + H2

1/3 Al + 1/2 H2

0

D Hf
113.05 kJ

D H
76.1 kJ

0

D Hf
56.48 kJ

1/3 Na3AlH6

NaH
D Hdec
23.5 kJ

D Hdec
37.0 kJ
NaAlH4

D H
56.52 kJ

Ref.: 

Smith and Bass, J. Chem. Eng. Data 8 (1963), pp. 342; 

Arroyo y de Dompablo M E, Ceder G, J. of Alloys and Compounds 364 (2004), pp. 6–12

28

Andreas Züttel, IfRES (2005)

®
®
COMPLEX HYDRIDES

COMPOUND   

mass.%

Reference

LiAlH4

NaAlH4

Mg(AlH4)2

LiBH4

NaBH4

Mg(BH4)2
Al(BH4)3

NaMgH3

10.6

7.4

9.3

18.5

10.6

14.9

16.9

6.0

Dymova 1994

Bogdanovic 1997

Fichtner 2003

Züttel 2001

Schlesinger 1953

Ashby 1972

Almenningen 1968

Ronnebro 2001

29

Andreas Züttel, IfRES (2005)

THERMAL DESORPTION OF H2 FROM OF LiBH4

I

II

III

IV

50% of H2
desorption

1.5 mol H2
LiH + B

fusion

Polymorphic 
transformation

H2
desorption

Ref.: D. S. Stasinevich and G. A. Egorenko, Russian J. of Inorganic Chemistry 13(3) (1968), pp. 341-343

30

Andreas Züttel, IfRES (2005)

STABILITY OF LiBH4

LiH + B + 3/2H2

LiBH4
D H = -68.9 kJ mol-1 H2
D S = 99.9 J·K-1mol-1 H2

IV

III

II
Measurement
D H = -177.4 kJ mol-1 H2
D S = 238.7 J·K-1mol-1 H2

I

Li + B + 2H2

LiBH4
D H = -97.0 kJ mol-1 H2
D S = 109.7 J·K-1mol-1 H2

Ref.: D. S. Stasinevich and G. A. Egorenko, Russian J. of Inorganic Chemistry 13(3) (1968), pp. 341-343

31

Andreas Züttel, IfRES (2005)

PHASETRANSITIONS LiBH4

32

Andreas Züttel, IfRES (2005)

THERMAL H2 DESORPTION FROM LiBH4

into vacuum

catalyzed

pure

Ref.: W. G. Brown, L. Kaplan, K. E. Wilzbach, J. Amer. Chem. Soc. 74 (1952), pp. 1343-1344

33

Andreas Züttel, IfRES (2005)

ENERGY LEVELS OF LiBH4

LiBH4

LiH + B + 3/2 H2

D H

Li, B, 2H2

0

D Hf
-194.15 kJ

D Hm
7.56 kJ

LiBH4
P63mc

LiBH4
liq.

D HStruc
4.18 kJ

LiBH4
Pnma

Li, B, 2H2

D H
90.73 kJ

LiH + B + 3/2 H2

D H
91.68 kJ

D Hdec
103.42 kJ

Ref.: Smith and Bass, J. Chem. Eng. Data 8 (1963), pp. 342

34

Andreas Züttel, IfRES (2005)

®
-
STABILITY OF BHn AND BHn

Gradient Corrected 
Density Functional Theory

Energy gain in adding a H atom
BHn-1 + H ®
BHn

Ref.: Puru Jena , Virginia Commonwealth University, Richmond, VA (to be published).

35

Andreas Züttel, IfRES (2005)

STABILITY OF ABH4 AND AAlH4

decomposition temperature

for p = p0

T

dec

=

0
H
0

S

Ref.: Orimo S; Nakamori Y; Züttel A, “Material properties of MBH4 (M = Li, Na, and K)”, Materials Science 
and Engineering B108 (2004) , pp. 51–53

36

Andreas Züttel, IfRES (2005)

D
D
MECHANISM OF THE THERMAL DECOMPOSITION (LiBH4)

+

+

+

-

-

-

37

Andreas Züttel, IfRES (2005)

REVERSIBILITY OF H2 SORPTION FROM LiBH4

38

Andreas Züttel, IfRES (2005)

REVERSIBILITY OF LiBH4

Ref. A. Züttel et al., to be published

39

Andreas Züttel, IfRES (2005)

SYNTHESIS OF LiBH4 FROM THE ELEMENTS

1958
1958

40

Andreas Züttel, IfRES (2005)

Li + B + 2H2
p = 150 bar H2, T = 650°C

LiBH4

FORMATION OF LiBH4

LiH + B + 3/2 H2 

LiBH4

D H

Li, B, 2H2

0

D Hf
-194.15 kJ

Li, B, 2H2

D H
90.73 kJ

LiH, 1/2 B2H6

H-

D H
17.8 kJ

D S0 = -79.2 J K-1

LiH + B + 3/2 H2

LiH

BH3

D Hm
7.56 kJ

LiBH4
P63mc

D HStruc
4.18 kJ

LiBH4

Pnma

D H
91.68 kJ

D Hdec
103.42 kJ

LiBH4

liq.

Ref.: Smith and Bass, J. Chem. Eng. Data 8 (1963), pp. 342

41

Andreas Züttel, IfRES (2005)

MECHANISM OF THE FORMATION (LiBH4)

B + LiH + 3/2 H2

BH3 + LiH

+

-

+

-

-

+

BH3 + LiH  ®

LiBH4

+

-

42

Andreas Züttel, IfRES (2005)

®
®
CHEMICAL HYDRIDES

NaBH4 + 2 H2O ® NaBO2 + 4 H2
LiBH4 + 2 H2O ®
NaBH4 + 3 H2O ® NaBO3+ 5 H2
LiBH4 + 3 H2O ®

LiBO2 + 4 H2

LiBO3+ 5 H2

21.3 mass%

37.0 mass%

35.7 mass%

45.5 mass%

43

Andreas Züttel, IfRES (2005)

FUTURE R&D IN SOLID HYDROGEN STORAGE

1) Nanoporous materials like MOF's
Is the interaction different from physisorption?

2) Destabilized complex hydrides by nanocomposites of partiall positive
charged and partially negative hydrogen like LiNH2 + MgH2
How is the stability changed of the composite changed? What are the potentially 
interesting systems?

3) Stabilization of unstable hydrides like AlH3, Al(BH4)3, NH3 (subnano thin
surface layers)
How to change the stability of unstable hydrides?

4) Destabilization of hydrides by nanocomposits and alloy formation like
MgH2 + 1/3 MgCu2 -> 2/3 Mg2Cu + H2 or LiH + Si -> LiSi +1/2H2
What are the potentially interesting systems?

5) Tank system design including the thermal management and the phase
separation problem with complex hydrides.
What is the ideal tank system and which performane can be expected?

44

Andreas Züttel, IfRES (2005)

DESTABILISATION OF MgH2
2.5 LiH + Si            Li2.5Si + 1.25H2

2 MgH2 + Si            Mg2Si + 2H2

Ref.: J. J. Vajo, F. Mertens, C. C. Ahn, R. C. Bowman Jr, B. Fultz, J. Phys. Chem. B 108 (2004), 13977-13983

45

Andreas Züttel, IfRES (2005)

METASTABLE MgH2
Ti and TiO2
Ti

Rutile

Ref.: Z.  Xiao Guo, Department of Materials, Queen Mary, University of London, UK

Anatase

TiO2(II)

a=0.45845 nm, c=0.29533 nm
P42/mnm, 136
y
x
Ti   2a 0             0
O    4f 0.3049   0.3049

z
0
0

a=0.3733 nm, c=0.9370 nm
I41/amd, 141

x

y

z

a=0.4563 nm, b= 0.5469 nm, c=0.4911 nm
Pbcn, 60

x

y

z

Ti   4a 0.5         0.75     0.375
O    8e     0.5        0.75     0.1598

Ti           0            0.171    0.25
O            0.286     0.376   0.412

Mg and MgH2
Mg

a -MgH2
DHf = -71.149 kJ/molH2

T-MgH2 ?
DHf = -58.033 kJ/molH2

g -MgH2

?

a=0.4501 nm, c=0.3010 nm
P42/mnm, 136

y
x
Mg  2a 0             0
H    4f 0.3040    0.3040

z
0
0

a=0.3840 nm, c=0.9415 nm
I41/amd, 141
x        y

z

Ti     0.5    0.75    0.375
H      0.5    0.75    0.1647

a=0.4505 nm, b= 0.54197 nm c=0.49168 nm
Pbcn, 60

x

y

z

Mg   4c   0            0.3313    0.25
H     8d   0.2727   0.1089    0.0794

Andreas Züttel, IfRES (2005)

46

THERMAL DECOMPOSITION OF AlH3

Particle size

m = 10.1 mass%
V = 149 kg m-3
D H = 7.6 kJ mol-1 H2

AlH3-LiH

Al2O3

AlH3

Ref.: G. Sandrock, J. Reilly, J. Graetz, W.-M. Zhou, 
J. Johnson, J. Wegrzyn, Appl. Phys. A 80 (2005), 
pp. 687–690 

47

Andreas Züttel, IfRES (2005)

AMIDES (LiNH2)
LiNH2 + 2LiH ®

Li3N + 2H2  (10.3 mass%, D H = 40 kJ mol-1 H)

3 LiNH2
LiNH2 + 2 LiH ®
Li3N + 2 H2

NH3 + 3 LiH + N2

Li2NH + LiH + H2 

i) pure LiNH2
ii) LiNH2 + LiH
iii) LiNH2 + 2 LiH

LiNH2 + 2 LiH

Li3N

Ref.: Chen P; Xiong Z R; Luo J; Lin J; Tan K L, “Interaction of Hydrogen with Metal Nitrides and Imides”, 
Nature 420 (21 November  2002), pp. 302-304

48

4
8

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

r
r
®
®
AMIDES (LiNH2)

MECHANISM OF THE THERMAL DECOMPOSITION

d +

-

d +

d +

-

d +

d +

d +

3 LiNH2

NH3 + 3 LiH + N2

-

d +

d +

d +

-

d +

d +

d +

d +

d +

d +

-

-

-

LiNH2 + 2 LiH ®

Li2NH + LiH + H2 

Li3N + 2 H2

d +

d +

-

-

d +

d +

-

d +

d +

d +

-

d +

Ref.: Chen P; Xiong Z R; Luo J; Lin J; Tan K L, "Interaction between Lithium Amide and Lithium Hydride", J. 
Phys. Chem. B (2003), pp. 10967-10970

49

Andreas Züttel, IfRES (2005)

HYDROGEN STORAGE

Storage Media

Volume

Mass

Pressure Temperature

max. 33 kg H2·m-3

13 mass%

800 bar

298 K

Composite cylind.

2
H

established

l

r
a
u
c
e
o
m

l

71 kg H2·m-3

100 mass%

1 bar

21 K

Liquid hydrogen 

20 kg H2·m-3

4 mass%

70 bar

65 K

Physisorption

max. 150 kg H2·m-3

2 mass%

1 bar

298 K

Metalhydrides

i

H
c
m
o
t
a

150 kg H2·m-3

18 mass%

1 bar

298 K

Complex hydrides

reversibility ?

>100 kg H2·m-3

14 mass%

1 bar

298 K

Alkali + H2O

50

5
0

Andreas Züttel, Switzerland, 1/29/2006

Andreas Züttel, IfRES (2005)

®
d
®
d
d
d
d
d
d
d
d
d
d
 
HYDROGEN DENSITY

H±

H2

Hcov

Ref: A. Züttel, “Materials for hydrogen storage”, materialstoday, Septemper (2003), pp. 18-27 

51

Andreas Züttel, IfRES (2005)

HYDROGEN FOR MOBILITY

Hindenburg (1937)

Austin A40 (1966)

Tupolev 155 (1988)

Space Shuttle
(1981-)

Necar 1 (1994)

NuBus, 250kW (2002)

Saturn
(1963-)

52

BMW (1978-)

Necar 4 (2002)

SAM (2005)

Andreas Züttel, IfRES (2005)

ACKNOWLEDGEMENT

Ronald Griessen, Bernard Dam, Robin Gremaud, Andreas Borgschulte ...

Vrije Universiteit Amsterdam, The Netherlands

Shin-ichi Orimo, Yuko Nakamori

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Geert-Jan Kroes, Terry Frankcombe

LIC / Theoretical Chemistry, University of Leiden, The Netherlands

Kazutoshi Miwa, Shin-ichi Towata

Toyota Central Research & Development Laboratories, Inc., Nagakute, Aichi 480-

1192, Japan

Gary Sandrock, Terry Udovic

Financial Support by the Swiss Federal Office of Energy and NEDO

53

Andreas Züttel, IfRES (2005)

CONTACT

Institut for Renewable Energy Switzerland
URL: http://www.ifres.ch

University of Fribourg, Physics Department
Condensed Matter Physics
URL: http://www.unifr.ch/physics/

Vrije Universitet Amsterdam, Faculty of Sciences
Condensed Matter Physics
URL: http://www.nat.vu.nl/CondMat/

HYDROPOLE
Swiss Hydrogen Association
URL: http://www.hydropole.ch

54

Andreas Züttel, IfRES (2005)

 
 
 
 
 
Micro- and Macro-scopic 
Characterisation Techniques 
and Modelling 

K. Ross 

University of Salford, Institute for Materials 
Research, UK 

 
 
 
 
 
 
 
JRC Workshop 
Characterising hydrogen storage systems

Micro- and macro-scopic methods of 
characterisation and theoretical 
modelling techniques

X-ray and Neutron Diffraction
for determining crystal structure

o X-rays or thermal neutrons or electrons are diffracted 

from a crystal lattice if their wavelength is similar to the 
atom spacing in the crystal;

o Lattice represented by lattice vectors 
Rn,l = n1a + n2b +n3c + ? l

q Diffraction is given by 

q ds/dO = |Sl al (Q)exp( i Q.l)|2 d(Q-t)
q Q = k’ – k0 and t is a reciprocal lattice vector 
The d function defines the direction of the diffracted 
beam and the |    |2 represents the intensity of the 
reflection where the summation is over all the atoms l in 
the unit cell

Constant wavelength versus time-of-
flight diffraction for powder samples

o In modern XRD and ND-const ? spectrometers 
(on a nuclear reactor source), ? is selected 
with a crystal monochromator. 
n Now Q = (4p/?) sin ? B

o ? B is the Bragg Angle which is varied

o In a pulsed neutron source, we determine 
the wavelength from the time of flight (t)  of 
the neutron from the source to the detector 
(distance Lf) for given ? B
n ?= 2p? t/mLf

Determining the Structure

o The values of t define the space group of the lattice
o The intensity term is the Fourier Transform of the atomic 

positions in the unit cell, each weighed by the factor      
al(Q)which is different for X-rays and neutrons
o For X-rays, al (Q) increases smoothly with Z and 

decreases with Q because it is the electrons that are 
scattering the X-rays (the atom is large)

o For neutrons, al(Q) is nearly independent of Q but varies 

in a random way with Z because the neutrons are 
interacting with the nuclear potential

o Hence, use neutrons for particular cases eg hydrogen or 

differentiating between two adjacent Z values

o Neutrons are also diffracted from magnetic (unpaired) 

electrons

Coherent and Incoherent Scattering

o Because neutrons interact with the nucleus, the amplitude of 
the scattered beam can vary between different nuclei of the 
same element. 

o Also, the interaction depends on whether the neutron spin is 

parallel or anti-parallel to the nuclear spin

o Hence <al

2> ?   <a l>2 and the diffraction intensity depends 

only on <al>2

incoherent

coherent

o ds /dO = (<al

2> - <al>2 )  

+  |Sl <al>(Q)exp( i Q.l)|2 d(Q-t)

q <a2> ˜  zero for hydrogen so have to use deuterium 

for determining hydrogen positions

Finding the positions of atoms in 
the unit cell

o Direct Fourier Transformation of peak intensities does 

not work because we cannot measure the phase of the 
diffracted radiation

o Hence have to use indirect methods (i.e. trial and error) 

known as structure refinement

o Assume the structure with atom in the position

xl, yl and zl  according to the symmetry of the space 
group and calculate the intensities of the reflections.
q Then calculate the mean square difference between 

theory and experiment 

q Then adjust the positions of the atoms to reduce the 

msd until the msd is a global minimum

Reitfeld’s Profile Refinement Method

o In modern diffractometers, patterns are recorded in 
equal intervals of theta (or time-of-flight) and each 
diffraction peak has a finite width and can overlap other 
peaks

o Hence it is best to compare the data on a measured 

point by point basis rather than using integrated peak 
areas

o This means that the theoretical version has to correctly 

include the resolution function of the instrument

o Now the fit of the theory to the data is known as “Profile 

Refinement”

o Use standard data analysis packages such as GSAS

Neutron diffraction pattern for YCo3D1.2 measured 
on the OSIRIS time of flight spectrometer at ISIS
Bottom trace shows error between measured and 
fitted diffraction pattern

Diffraction studies of Materials

o In studies of materials, diffraction can yield much more 

than just the average crystal structure

o Small crystallites and various forms of lattice strain such 

as dislocations can cause line broadening. 

o Variation of line broadening changes from line to line. 
Analysis yields information on which are the important 
effects causing broadening

o Variations in the line intensity can be caused by 

preferred orientation of the crystallites

o Any stress present can cause the peaks to shift from 

their normal position. By measuring spatial variation, we 
can map the strain in the object

Small Angle Scattering (neutron or X-ray) 
and micro-scale inhomogeneities

o For small Q values, we get information on 

structures larger than the interatomic spacing
o Technique works for both neutrons and X-rays
o Defects include voids, dislocations, 
precipitates, magnetic inclusions

o Samples include high surface areas and porous 

solids

o SANS is proportional top changes in local 

scattering density. Can use changes in isotopic 
compositions (H2O/D2O) in pores to “match” 
bulk scattering density in studies of porosity

Inelastic Neutron scattering from 
Hydrogen

o Scattering from hydrogen is very strong and is 

incoherent (no interference)

o Neutron can exchange energy with a hydrogen 

mode of vibration (like Raman scattering)

o But no selection rules so peak areas are 

directly proportional to the number of modes
o Hence we can calculate the inelastic neutron 

scattering directly from an ab initio calculation 
(see below)

o Particularly useful for studies of molecular 

hydrogen on surfaces

Quantum Effects with Hydrogen

o As hydrogen is the lightest atom, its wave 
function extends over the largest area.

o Classical calculations of the H vibrations are 
only correct if the potential energy surface 
is harmonic

o Hydrogen wave function samples potential 

energy surface well away from the potential 
energy minimum

o Hence very likely to be influenced by 

anharmonic effects

o Example Palladium Hydride

Inelastic neutron scattering from H in a 
single crystal of palladium for different 
crystal orientations
Kemali et al. PRL 84 (2000)  1531

0.10

0.08

)

0.06

,w

Q
S

(

0.04

0.02

0.00

0

40

80

160

120
200
280
Energy transfer (meV)

240

[111]

[110]

[001]

320

360

400

Observed energy levels in PdH
Two expts at different H concentrations 
compared with ab initio theory

Energy state 

e1,|001>=e1,|010>=e1,|100> 

e2,|011>=e2,|101>=e2,|110> 

e2,|C> 

e2,|A>=e2,|B> 

e3,|111> 

Theory 
(meV) 
62 

PdH1.0 
(meV) 
55.8 

PdH0.85 
(meV) 
57 

117 

132 

147 

164 

112 

115.5 

135 

148 

139± 2 

155± 3 

- 

~170 

 
 
Ground state wave function for H in Pd
H is sited at the (1.2,1/2,1/2) site in fcc palladium
Contour plot is half way up the unit cell

H wave functions in PdH
First excited state: (1,0,0) energy level

Inelastic neutron scattering from molecular 
hydrogen adsorbed on surfaces

o Hydrogen molecules are either ortho- (nuclear 

spins parallel) or para-(nuclear spins 
antiparallel)

o Para-hydrogen has angular momentum states 

of l=0,2,4..

o Ortho-hydrogen has angular momentum states 

of l =1,3,5..

o Energy difference between l=0 and l=1 is 14.7 

meV

o Only significant scattering from para=H is from 

L=0 to l=1,3…

Inelastic neutron scattering from H2
on carbon nanotubes

S(Q,w )

(

0 . 5

1.0

1.5

2.0

0

1 0 0
Neutron energy loss, meV

3 0 0

2 0 0

4 0 0

5 0 0

6 0 0

Expanded plot of the inelastic peaks showing structure in the 
peak due to the quantum states on the surface of the 
nanotubes. As hydrogen is added to the surface, new sites 
can be seen Georgiev et al Carbon 43 (2005) 895-906

a

1.0

0.8

0.6

0.4

0.2

0.0

S(
Q,
)

b

1.0

0.8

0.6

0.4

0.2

0.0

S(
Q,
)

10

12

14

16

18

20

10

12

14

16

18

20

Neutron energy loss, 
meV

Neutron energy loss, 
meV

Macroscopic studies of hydrogen 
absorption in solids

o Use either gravimetric or volumetric methods. 
o Gravimetric best where there is possible 

outgassing from the solid needing high vacuum 
and baking
n We use the IGA or Intelligent Gravimetric Analysis 

method where gas pressure and sample temperature 
are controlled by computer

o Volumetric best at high pressures and 

temperatures
n Sievert’s apparatus, using calibrated volumes and 
Boyle’s law to calculate gas absorbed by solid

w
w
The IGA instrumental set up

IGA data for a hydrogen battery 
AB5 alloy

10000

1000

100

r
a
B
m

,

e
r
u
s
s
e
r
P

10

1

32C
40C
50C
60C
70C
70C

0.0

0.2

0.4

0.6

0.8

1.0

H/M

 
Comparison of the gradient of the isotherm with the time 
constant for the absorption process showing that the time 
constant is dominated by the Chemical Diffusion Coefficient

140

120

100

80

60

40

20

0

c
d
/
)

P
n
L
(
d

 32 oC
 40 oC
 50 oC
 60 oC
 70 oC

t
i

m
e

c
o
n
s
t
a
n
t
,

m
i
n

3

2

1

0

0.0

0.2

0.4

H/M

0.6

0.8

Neutron scattering to study 
microscopic diffusion

o If the H atom is diffusing when the neutron is 

scattered, there is a kind of Doppler Effect that 
spreads out the neutron energy. This is known 
as Quasi-Elastic Scattering

o Incoherent scattering tells us about the self 

diffusion process which is related to Einstein or 
Tracer Diffusion

o Coherent scattering (scattering from D is 
mainly coherent) is related to Fick’s Law 
Diffusion or diffusive current in a concentration 
gradient

 
 
Macroscopic and microscopic diffusion

o Einstein theory shows that in tracer diffusion

<? x2> = 6Dt? t

q This assumes a large number of jumps in ? t
q This model yields Lorentzian Broadening of the 

elastic peak with half width at half height 

? E = ?DtQ2

q But if 1/Q is ~ jump length between individual 
interstitial sites in the lattice, we need to use a 
random walk model

Chudley-Elliott Model

o ? E(Q)= ?(1/nt )Sl(1-exp(iQ.rl))
Here rl is one of n vectors representing the jumps 
to the set of n nearest neighbour sites and t (c) 
is the mean residence time for a proton on a 
given site

q This model can be elaborated for more 
complex microscopic diffusion processes

q Alternatively, the diffusion can be described by 
a Monte Carlo process and the corresponding 
quasi-elastic scattering derived

Comparison of a Monte Carlo simulation of the peak 
broadening as a function of Q with the Chudley Elliott Model 
at different concentrationsfor an fcc lattice (Thesis:D.J.Bull)

)

Q

(
f

 c = 0.01
 c = 0.1
 c = 0.5

1.5

1.0

0.5

0.0

0.0

0.2

0.4

0.6

0.8

1.0

h

Hydrogen Storage Tank: 
Design and Heat Transfer 
Principles 

T. Stubos 

NCSR Demokritos, Environmental Research 
Laboratory, Greece 

 
 
 
 
 
 
 
DEMOKRITOS""
NCSR ""DEMOKRITOS
NCSR 
INSTITUTE OF NUCLEAR TECHNOLOGY & RADIATION PROTECTION
INSTITUTE OF NUCLEAR TECHNOLOGY & RADIATION PROTECTION
ENVIRONMENTAL RESEARCH LABORATORY
ENVIRONMENTAL RESEARCH LABORATORY

Hydrogen Storage Tanks: Design and Heat 
Transfer Aspects

A.K. Stubos

“Experimental Aspects of R&D on Hydrogen Storage Technologies”, 

JRC-IE, Petten (NL), October 17-18, 2005

DEMOKRITOS""
NCSR ""DEMOKRITOS
NCSR 
INSTITUTE OF NUCLEAR TECHNOLOGY & RADIATION PROTECTION
INSTITUTE OF NUCLEAR TECHNOLOGY & RADIATION PROTECTION
ENVIRONMENTAL RESEARCH LABORATORY
ENVIRONMENTAL RESEARCH LABORATORY

Presentation Outline

•Targets and Requirements for Hydrogen Solid Storage Systems

•Stationary vs. Mobile Applications

•Heat Management: Design Principles 

•Conventional Hydride Tanks

•Complex Hydride Tanks: Base Case SAH

•Concluding Remarks

••

••

••

••

Metal Hydride Tank Challenges
Metal Hydride Tank Challenges

üHigh Hydrogen Capacity (mass hydrogen per mass of tank)

üHigh Hydrogen Density (mass hydrogen per volume of tank)

üFast  Hydrogenation  /  Dehydrogenation  Kinetics – release 

the  hydrogen  at  the  same  rate  as  it  is  consumed  in  the  engine. 

Fast kinetics at sufficient low temperatures and pressure

üCyclic Stability – long lifetime; no loss of reversible hydrogen 

capacity

üCost

Stationary vs. Mobile
Stationary vs. Mobile

Stationary Applications

Mobile 
(cars)

Mobile (vehicles) –
considerably greater challenge 
than stationary!

••

••

••

••

Tank Design Requirements for Automobiles
Tank Design Requirements for Automobiles

ü Fast refueling  

ü Hydrogen for fuel cell at elevated pressure

ü Short response time

ü Light weight 

ü Low volume

ü No hydrogen contamination by storage system

ü Freeze start: like Diesel engine

ü Working temperature: -40–85°C

ü No leakage

Satisfy all the above accounting for safety and costs

Hydrogen Storage System: Challenges & Targets (cars)
Hydrogen Storage System: Challenges & Targets (cars)

Challenge: Store  hydrogen  on-board  meeting  performance  (wt,  vol, 
kinetics, etc.), safety and cost requirements and enabling > 450 km range

Targets: Developed through

These are 
System 
Targets

Material 
Capacities 
must be 
Higher

2010

2015

System Gravimetric 
Capacity = Specific 
Energy (net)

System Volumetric 
Capacity = Energy 
Density (net)

2.0 kWh / kg
(7.2 MJ / kg)
(6 wt%)

1.5 kWh / L
(5.4 MJ / L)
(0.045 kg / L)

3.0 kWh / kg
(10.8 MJ / kg)
(9 wt%)

2.7 kWh / L
(9.7 MJ / L)
(0.081 kg / L)

Storage System Cost

$ 4 / kWh

$ 2 / kWh

••

••

••

••

Hydrogen Storage System: Challenges & Targets (cars)
Hydrogen Storage System: Challenges & Targets (cars)

Parameter
Specific Energy net
Energy Density net
Storage System Cost
Cycle life (25-100%)

Cycle life variation

Max delivery temp.
Min delivery pressure of H2
from tank, FC=fuel cell, I=ICE
Start time to full flow @ 20 °C
System fill time (for 5 kg)

Loss of useable H2

Units
kWh / kg

kWh / L

$ / kWh

cycles
% of mean (min)
@ % confidence
°C

atm (abs)

sec

min
(g/h) / kg H2
stored

Permeation and leakage

Scc / h

Toxicity

Safety

2005
1.5

1.2

6

500

2010
2.0

1.5

4

1000

N/A

90/90

85

85

8 FC
10 ICE

4 FC
35 ICE

4

3

4

10

1

C
u
r
r
e
n

t

F
o
c
u
s

2015
3.0
2.7
2
1500

99/90

85
3 FC
35 ICE
0.5
2.5

0.1

0.05

Federal enclosed-area safety 
standard
Meets or exceeds applicable 
standards
Meets or exceeds applicable 
standards

Heat Management:  Basic Concepts (N. 
Heat Management: 

, GKSS)
Basic Concepts (N. EigenEigen, GKSS)

Fueling

H2

Starting

H2

Driving

H2

Cooling configuration,
temperature, etc.

Warm up-
characteristics  

Loading configuration

Warm up-concept 

Heating 
configuration for 
desorption

Efficient Heat Management Concept and System is Required!

 
••

••

Heat Flow During Fueling
Heat Flow During 

Fueling (adapted from N. 

, GKSS)
(adapted from N. EigenEigen, GKSS)

Example:
4 kg H2 tank
10 min. filling time
sodium alanate
linear heat release
Q(hyd)=125 kW

External cooling 
during filling??

Need for internal heating 
during H2 supply

Example of quick adoption of cooling / heating supplies 
(Texaco Ovonic in a demonstration car based on Toyota Prius)

••

••

Heat Management Design Principles
Heat Management Design Principles

Heat Transfer Modeling and Simulation in 
Hydrogen Storage Tanks

H2, feed

Cooling 
System

Adsorbent 
Material

••

••

••

••

Heat Management Design Principles
Heat Management Design Principles

Main Features

• Two dimensional model

• Improvement of storage performance by adding an 
inner concentric tube and an annular ring, both 
containing cooling fluid, inside the tank. 

• Energy balance is included in each of these 

compartments to determine the temperature of the 
cooling fluid. 

• Dynamic optimization features. 

Heat Management Design Principles
Heat Management Design Principles

General Assumptions

• Ideal gas law in the gas phase.

• Solid and fluid temperatures are equal.

• Axial - radial dispersion included in fluid mass 

balances.

• Axial and radial pressure drop in the bed depends 

linearly on the superficial velocity through Darcy’s 
law.

••

••

••

••

Heat Management Design Principles
Heat Management Design Principles

Governing Equations

A. H2 storage in a metal hydride reactor bed

vMass balance of hydrogen in the gas phase (bulk of the reactor)

ˆ
r
t

1
(
×Ñ+
e

)

ˆˆ
u
r

1
mPe

Ñ×÷÷

2

ˆ
r

+

W
0

×

ˆ
r
s
t

=

0

vPressure Drop Equation

-=

ˆ
u

z

K

z

ˆ
P
z

-=

ˆ
u

r

K

r

ˆ
P
r

vEnergy Balance Equation

(

+
ˆ
ˆ
rr

×
L
e

s

)

×

+

q
t

1
e

Ñ××÷
ˆ
u

q

1
tPe

Ñ×÷÷

2
q

×

W
0

ˆ
r
s
t

b

-+
1(

C

C

ps

pg

)
q

=

0

Heat Management Design Principles
Heat Management Design Principles

Governing Equations

A. H2 storage in a metal hydride reactor bed

vMass balance of hydrogen in metal phase

(
1

)

×

e

ˆ
r
s
t

=

×
tC
a

res

×
exp

(

e

a

/

q

)

×
ln

ˆ
P
ˆ
P
eq

(
×
ˆ
r

÷
÷

sat

)

ˆ
r

s

vDefinition of Equilibrium Pressure (PCT curve)

¶
¶
¶
¶
ú
ú
û
ù
ê
ê
ë
é
¶
¶
-
ø
ö
ç
ç
è
æ
-
ø
ö
ç
è
æ
¶
¶
¶
¶
ø
ö
ç
ç
è
æ
-
¶
¶
-
ø
ö
ç
ç
è
æ
-
¶
¶
-
••

••

••

••

Heat Management Design Principles
Heat Management Design Principles

Governing Equations

A. H2 storage in a metal hydride reactor bed

vIdeal gas Law

/ˆ
ˆ P=
r

q

The total amount of hydrogen stored in the tank is calculated by the 
following dimensionless expression:

1

1

ˆ(
r

s

)1

rdrdz

=

0

0

M

t

1

1

0

0

rdrdz

Heat Management Design Principles
Heat Management Design Principles

Two dimensional H2 storage with inclusion of energy 
balances for the cooling fluid

Energy balance equations

1

q

f
t

1
Pe

h

1

×÷÷

2

q

f

1

2

z

+

ˆ
u

f

1

q

f
z

1

+

B

iM

(
×
q

f

1

q

rz
,(
0

)

) 0
=

2

q

f
t

1
Pe

h

2

×÷÷

2

q

f

2

2

z

+

ˆ
u

f

2

q

f
z

2

+

B

iM

(
×
q

f

2

q

,(
rz
1

)

)

+

(
q

f

2

Bi

M

q

)2,(
rz

) 0
=

ò
ò
ò
ò
-
-
¶
¶
¶
¶
ø
ö
ç
ç
è
æ
-
¶
¶
-
-
¶
¶
¶
¶
ø
ö
ç
ç
è
æ
-
¶
¶
••

••

••

••

Heat Management Design Principles
Heat Management Design Principles

Boundary and Initial Conditions

At the tank inlet (z=0):

At the tank outlet (z=1):

ˆ =r

1

1=q

For the case of 
pressure
we have:

ˆ =P

1

ˆ =
r
z

0

=

zBi

(
qq

)

c

q
z

ˆ
u

z

=

ˆ
u

r

=

0

Heat Management Design Principles
Heat Management Design Principles

Boundary and Initial Conditions

At the tank center (r=0):

At the tank radius (r=1):

ˆ =
r
r

0

0=

q
r

=

ˆ
u
z
r

ˆ
u
r
r

=

0

ˆ =
r
r

0

=

rBi

(
qq

)

c

q
r

=

ˆ
u
z
r

ˆ
u
r
r

=

0

¶
¶
-
¶
¶
-
¶
¶
¶
¶
¶
¶
¶
¶
¶
¶
-
¶
¶
-
¶
¶
¶
¶
••

••

••

••

Heat Management Design Principles
Heat Management Design Principles

Two dimensional H2 storage with additional heat exchangers 
at a concentric inner tube and annular ring inside the reactor

BCs at r=r0
q
(
qq
r

rBi

=

c

)

BCs at r=r1
ˆ =
r
r

0

=

rBi

(
qq

)

c

q
r

=

ˆ
u
z
r

ˆ
u
r
r

=

0

BCs at r=r2
ˆ =
r
r

0

=

rBi

(
qq

)

c

q
r

=

ˆ
u
z
r

ˆ
u
r
r

=

0

Heat Management Design Principles
Heat Management Design Principles

Initial Conditions (t =0)

•The  metal  hydride  bed  is  assumed  initially  to  be  at  a  constant 
temperature  equal  to  the  inlet  temperature  (although  this  is  not
necessary).

•The  metal  hydride  bed  is  assumed  to  contain  no  hydrogen  in 
the gas phase.

¶
¶
-
¶
¶
-
¶
¶
¶
¶
-
¶
¶
¶
¶
-
¶
¶
¶
¶
¶
¶
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Heat Management Design Principles
Heat Management Design Principles

gPROMS*

The modeling and simulation of the hydrogen storage process was 
carried out using gPROMS*, a software package for the modeling 
and simulation of processes with combined discrete and 
continuous characteristics. 

* Trademark of Process Systems Enterprise

www.psenterprise.com

Heat Management Design Principles
Heat Management Design Principles

Metal hydride bed

Equilibrium input data for the system LaNi5-H2

T=293 K
T=303 K
T=313 K

)
r
a
b
(
q
e
P

8

7

6

5

4

3

2

1

0

0

0.2

0.4

0.6

0.8

1

(H/M)/(H/M) s

••

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••

••

Heat Management Design Principles
Heat Management Design Principles

Standard two dimensional H2 storage simulation
Time-space evolution of temperature in the bed
(T0=290 K, Tc=313K)

Heat Management Design Principles
Heat Management Design Principles

Time-space evolution of the metal hydride density in the 
bed (T0=290 K, Tc=313K)

••

••

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••

Heat Management Design Principles
Heat Management Design Principles

Effect of Tc, on the time evolution of the total mass of H2
absorbed

)
y
o

l
l
a

r
g
/
r
g
(
d
e
b
r
s
o
b
a
2
H

f
o
t
n
u
o
m
a
l
a
t
o
T

0.014

0.012

0.01

0.008

0.006

0.004

0.002

0

0

Tc=313 K
Tc=290 K

1000

2000

3000

4000

Time (sec)

Heat Management Design Principles
Heat Management Design Principles

Time-space evolution of the temperature in the bed when an 
inner tube and annular ring with heat exchange cooling fluid 
are employed (T0=Tc= 290K)

 
 
 
 
 
 
 
••

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••

Heat Management Design Principles
Heat Management Design Principles

Time evolution of the total H2 mass stored in the metal hydride 
reactor for three different heat exchange configurations 
(Tc=290 K)

0.014

0.012

0.01

0.008

0.006

0.004

0.002

)
y
o

l
l
a
g
k
/
g
k
(
s
s
a
m

2
H

l
a
t
o
T

0

0

Case 1
Case 2
Case 3

500

1000

1500

2000

Time (sec)

Heat Management Design Principles
Heat Management Design Principles
Time-space evolution of the temperature of the cooling fluid 
along the inner tube of the reactor (T0=290 K, Tf =Tc=290 K at 
t=0, for all z, and at z=0 for all t)

 
 
 
 
 
••

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••

Heat Management Design Principles
Heat Management Design Principles

Time scheduling of the cooling flow velocity and resulting H2
mass uptake in the metal hydride reactor as a result of the 
optimization procedure

)
s
/
m

(

f

u

4

3

2

1

0

t=1281.7 sec

0

500

1000

Time (sec)

1

0.8

F
r
a
c
t
i
o
n
a
l

0.6

H
2

0.4

0.2

s
t
o
r
a
g
e

c
a
p
a
c
i
t
y

0

1500

Heat Management Design Principles
Heat Management Design Principles

Time evolution of the pressure drop in the heat exchanger and 
the total volume of cooling fluid required as a result of the 
optimization procedure

0.01

0.008

)

m

t
a
(
f

p
Ä

0.006

0.004

0.002

0

0

30

25

20

15

10

5

V

f

(

m

3
)

500

1000

Time (sec)

0
1500

 
 
 
 
 
••

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Hydrogen Storage Tanks: Conventional Hydrides
Hydrogen Storage Tanks: Conventional Hydrides

ü Small and Large Scale tanks (made by Treibacher Industrie AG, 
Austria) for stationary fuel cell applications (AB2 alloy with 1.8 
wt% capacity)

ü Present example: Capacity 15 Nm3 = 1.35 kg of hydrogen
ü Weight of tank ~220 kg (excl. water hull and water: 130 kg) 
ü Capacity 80% after 2000 cycles

ENK6-CT-2002-00600: Hydrogen Storage in Hydrides for Safe Energy Systems - HYSTORY

Which type of hydrides??
Which type of hydrides??

of fuel cell waste heat limits
Availability of fuel cell waste heat limits
Availability

Consideration to low – temperature hydride storage

Medium – Temperature Hydride (MTMH)

Low – Temperature Hydride (LTMH)

• H2 desorption T > stack coolant T

• H2 desorption T < stack coolant T

• Must burn H2 to liberate H2 from MTMH
• 15 – 25% penalty in system efficiency

• Waste heat to liberate H2 from LTMH
• Reduction in radiator heat duty

••

••

••

••

Base Case SAH
H2 Storage Tanks: Complex Hydrides –– Base Case SAH
H2 Storage Tanks: Complex Hydrides 

DoE project: Anton et al., UTRC

Design,  construct and  evaluate prototype hydrogen storage

systems initially utilizing catalyzed NaAlH4,  but capable of 

being modified to use “any”  reversible hydride with higher

gravimetric and/or volumetric hydrogen storage capacity with

minimal redesign.

Develop, construct & test an in-situ rechargeable 1 kg hydrogen
storage system.

H2 Storage Tanks: Base Case SAH (Anton et al., UTRC)
H2 Storage Tanks: Base Case SAH (Anton et al., UTRC)

••

••

••
••

Anton et al., UTRC
SAH Tank: Component Masses –– Anton et al., UTRC
SAH Tank: Component Masses 

Actual storage tank

• 19 kg hydride in the system

• 0.44 g/cc average hydride density

• 100 atm tank

Projected storage tank

•Achieve density of 0.6 g/cc for entire vessel 
resulting in 26 kg hydride

•Achieve gravimetric efficiency of 48% 

Gravimetric engineering efficiency of ~ 50% achieved

SAH Tank Design Assumptions (S. Lasher, TIAX)
SAH Tank Design Assumptions (S. Lasher, TIAX)

Main design assumptions for the NaAlH4 tank system based on literature, 
developer feedback and TIAX experience 

Media

Design Parameter

H2 Storage Capacity
NaAlH4 H2 Capacity

Catalyst

Value

5.6 kg

4 wt%

TiCl3

Heat of Decomposition

Min. Temperature

41 KJ/mol H2
100 °C

Thermal

Max. Temperature

Media Conductivity

186 °C

< 1 W/m K

Source

ANL drive-cycle modeling

UTRC (Anton, Merit Review, 
May 04)

Bogdanovic & Schwickardi, 
JACS 97

Reaction Thermodynamics

SNL (Wang, Merit Review, 
May 04)

SNL (Gross, JAC 02)

SNL (Wang, Merit Review, 
May 04)

Media (hydrided) Specific 
Heat

1.418 J/Kg K

SNL (Dedrick, JAC 04-draft

Mechanical

Max. Pressure

100 bar 

UTRC (Anton, Merit Review, 
May 04)

••
••

••

••

Other Design Issues (S. Lasher, TIAX)
Other Design Issues (S. Lasher, TIAX)

System-level issues that must be addressed by the on-going R&D

Issues

Comments

Start-up

Material

Safety

Thermal 
Integration

Refueling

• Almost 5% of 5.6 Kg H2 required to heat media from 0 °C
• Secondary H2 storage (or battery/electric heater) may be needed 
for start-up

• Limited cycling data available
• SAH powder and catalyst can segregate and lose effectiveness

• SAH powder is highly explosive, reacts with water or air
• Inert atmosphere needed for vehicle refueling and tank 
manufacturing
• About 25% of stored 5.6 kg H2 required for dehydriding heat
• Possibility to use waste heat from power unit??

• Sufficient cooling (external??) is required
• Long refueling times (minutes or hours??)

Weight Comparison (S. Lasher, TIAX)
Results –– Weight Comparison (S. Lasher, TIAX)
Results 

Sodium alanate will not meet the DOE weight target. Materials with greater than 
7wt% may be required to meet even the 2005 target

System Weight 
(Kg)

Sodium 
Alanate Tank

TIAX Base 
Case

Compressed 
H2 Storage

350 bar

700 bar

325

83

92

2007 Target = 4.5 wt%

1.7 wt%

6.7 wt%

6.3 wt%

••

••

••

••

Volume Comparison (S. Lasher, TIAX)
Results –– Volume Comparison (S. Lasher, TIAX)
Results 

The sodium alanate system will likely be about 40% larger than the 700 bar 
compressed hydrogen storage system

System Volume 
(L)

Sodium 
Alanate Tank

TIAX Base 
Case

Compressed 
H2 Storage

350 bar

700 bar

290

310

213

2007 Target = 1.2 kWh/L

Factory Cost Comparison (S. Lasher, TIAX)
Results –– Factory Cost Comparison (S. Lasher, TIAX)
Results 

The assessment indicates that the manufactured cost of a sodium alanate system 
will be comparable with that of 700 bar compressed gas

Sodium 
Alanate Tank

TIAX Base 
Case
350 bar

Compressed 
H2 Storage

700 bar

System Cost 
($/kWh)

12.9

10.3

11.2

2007 Target = $6/kWh

••

••

Concluding Remarks
Concluding Remarks

Major issues for study / improvement in H2 storage tanks:

• weight efficiencies 

• heat management 

• upscaling aspects (life cycling, costs) 

• safety considerations

Still a long way to go! Collaboration at international level is necessary!

 
 
 
 
 
Testing of Hydrogen Safety 
Sensors at JRC  

H. Crutzen 

EC- DG JRC-IE 

 
 
 
 
 
 
 
TESTING OF HYDROGEN SAFETY SENSORS 
AT JRC

P. Castello, O. Salyk and H. Crutzen
European Commission – Joint Research Centre - Institute for Energy, P.O. Box 2, 1755 ZG Petten, Nl

The interpretations and opinions contained in this document are solely those of the authors, and do not necessarily represent the view of the European Commission.

Any object, system or device which is not the property of JRC and that is presented here alongside a description of its base functioning principle is shown exclusively for 
illustrative purposes. Comments are of general nature, and do NOT specifically refer to that particular object/system/device. 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Contents

1. Why Hydrogen detectors?

2. Hydrogen detection in industrial environments

- Legal base and main standards
- Most common detectors

3. Expected applications within the H2 economy

- Technical requirements
- Less common/emerging technologies

4. Testing

- Test methods
- JRC Testing equipment
- Present activities and future developments

5. Conclusions

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Why H2 detectors?

• H2 Properties

- lighter than air
- fastest diffusing gas
- permeates easily through most materials

• H2 Limits in air

- Flammability: 
- Detonation:

4 – 75 % 

18 – 59% (Scale dependent) 

•H2 Autoignition Temperature

- 585 ºC

• Colourless, odourless gas

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Ignition energies of hydrogen/air and 
methane/air mixtures as a function of 
composition
(R.F. Cracknell  et al. "Future Car Congress, June 2002, Hyatt Crystal 
City, VA, USA, Session: Gaseous Fuel Technology Proceedings

Legislative background

“Where necessary, workers must be 
given optical and/or acoustic warnings 
and withdrawn before the explosion 
conditions are reached”

Directive 1999/92/EC of 16 December 1999 on “Minimum 
requirements for improving the safety and health 
protection of workers potentially at risk from explosive 
atmospheres”

“Concentrations in the vicinity of a plant can be monitored e.g. by 
means of gas alarms”. […] The substances likely to be present, the 
location of the sources, maximum source strength and dispersion 
conditions must be adequately known, and the instrument performance 
must be appropriate to the conditions of use, especially as regards 
response time, alarm level and cross-sensitivity. 

Non-binding guide of good practice for implementing Directive 1999/92/EC, COM(2003) 515 final, Bruxelles (B), 
25.08.2003. 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Standards

There are standards in Europe that give guidelines for the selection, 
installation, use and maintenance of flammable gas detectors, e.g. EN-50073; 
IEC 61779-6………….. 

Plus other standards in the IEC 61779 series, e.g.  

EN-IEC 61779-1 on guidelines for sensor performance testing, 

EN-IEC 61779-4 on performance req. for group II gas sensors up to 100% LEL

EN -IEC 61779-5 on performance req. for group II gas sensors up to 100% Vol.

Plus

ANSI/UL 2075 Gas and Vapor Detectors and Sensors (2004) – U.S.

CSA – C22.2 No 152-M1984 Combustible gas detection and instruments - CAN

Plus

Internal codes of practice (not necessarily public), e.g.

NASA Safety Standard for H2 & H2 Systems (NSS 1740.16, 1997 & updates)

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Most common hydrogen detectors – 1 

Catalytic Bead (Pellistor) Sensors

2 beads surrounding wire heated to 450ºC, 
one coated with a catalyst. The beads form 
2 legs of Wheatstone bridge

H2 ? oxidation ? ? temp. ? ? resistance ?
alter bridge balance ? signal

Signal ? [H2] in 0-100% range of LEL

Semiconductor Sensors

Mostly metal oxide which detect gases via 

variations in their resistance

H2 ? oxidation ? ? temp. ? ? resistance ?

alter bridge balance ? signal

Signal ? [H2] in 0-100% range of LEL

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: Dräger Safety AG & Co. KGaA

Most common hydrogen detectors – 2 

Electrochemical Sensors

Consists of a sensing, a counter 
and a reference electrode.  

H2 gas diffuses thro the 
membrane and oxidises at the 
sensing electrode. This results in 
a change in the sensing electrode 
potential w.r.t. reference which is 
? [H2] .

Thermal conductivity sensor

Based on high thermal conductivity of H2.
Sensing element has a ‘hot’ and çold’
element with known ? T which is 
maintained.  Heat is transferred from hot 
to cold element via thermal conductivity 
through investigated gas.  Power to 
maintain ‘hot’ element is direct measure of 
gas conductivity.

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: Dräger Safety AG & Co. KGaA

Most common hydrogen detectors – 3 

Typical 
measuring 
ranges 

Relative 
response 
time 

Interferences 
from non 
combustible 
gases 

Poisoning 

"Advantages" 

"Disadvantages" 

Catalytic 
sensor 

£ LFL 

Depends on 
species 

No 

-  Commercially available 
with acceptable lifetime 
-  Wide temperature range   

Si, 
Alogenated 
compounds, 
H2S, Pb 

Thermal 
conductivity 
sensor 

(0)-100% 

medium 

CO2, freons 

no 

-  Wide range   
-  No O2 to work 
-  Long term stability  
-  Resistant to poisoning  

Solid-state 
sensor 

£ LFL 

depends on 
species 

SO2, NOx, H2O 

-  Commercially available 
with acceptable lifetime 
-  Wide temperature range 

Si, 
Alogenated 
compounds 
SO2 

Electrochemical 
sensor 

£ LFL 

Medium  

SO2, NOx 

no 

-  Selective to H2 
-  Sensitive down to 

100ppm  

-  Low power consumption 
-  Resistant to poisoning  

-  Not H2 selective  
-  High power consumption 
-  Requires 5-10% O2  
-  Susceptible to poisoning 

by Pb, Si, P, S   

-  Short expected lifetime 
-  Not as sensitive as 

electrochemical/MO 
sensors 

-  Sensitive to He 

-  Not H2 selective  
-  High power consumption 
-  Sensitive to humidity and 

temperature 

-  Gets saturated easily 

-  Narrow temp range 
-  Short expected lifetime 
-  Needs regular calibration 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

 
 
 
 
 
 
Applications in the hydrogen economy

Hydrogen 
chain stage 

Area of Application 

Specific technological goal 

Production   Process plants [1] 
Distribution 
& Storage 

Pipeline monitor [1] 
Pipeline, refuelling and underground storage [2]  As above  
Storage tanks [1] 

Large area physical sensing 
In-situ sensing of leaks  

Innovative concept/materials 
integrated into the  system to 
indicate permeation, leaks or 
critical damage  
 as above 
Yet to be specified 

Safe operation of CGH2 systems [2] 
Hydrogen supply cartridges for micro-mini fuel 
cells [2] 
Vehicle passenger compartments/boots [1] 
Stationary fuel cells [2] 
Device-integrated power supply [2] 
Permeation [1] 
Personnel monitor [1] 
Emissions monitoring (environmental impact) [2]   Yet to be specified 

Rapid reaction response 
Lower cost 
Low-power miniature electronics 
See storage tanks 
 Innovative technologies 

Utilization 

Cross-
cutting 
issues 

[1] Hydrogen Safety, Codes and Standards Research, Announcement of funding opportunity DE-PS36-04GO94000, 2004

[2] Strategic Research Agenda - European Hydrogen and Fuel Cell Technology Platform, 2005

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Performance targets - 1

Measurement range: 0.1–10% H2 in air

Operating temperature: -30–80 °C

Response time: <1 s

Accuracy: 5%

Gas environment: ambient air, 10–98% RH range

Lifetime: 5 y

Interference resistant (e.g., hydrocarbons)

DOE-sponsored Workshop on Sensor Needs and Requirements for Proton- Exchange Membrane Fuel 
Cell Systems and Direct- Injection Engines, January 25 and 26, 2000, Lawrence Livermore 
Laboratories Publ., UCRL-ID-137767,  Livermore (CA), 2000 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

 
 
 
  
  
  
  
 
Performance targets - 2

On-going project: 

STORHY: Hydrogen Storage Systems for Automotive Applications – Coord. Magna Steyr (A)
Sub-project SAR: (Safety Assessment and Requirement – Coord. BAM (D)

WP SA2: Safety sensors and surveillance electronics: CIDAUT (WP leader), JRC-IE (NL), Magna Steyr (A), BAM (D)

Subproject SAR (Safety Assessment & Requirements), Task SA2.2: General 
requirements and tests concerning quality and reliability of hydrogen detectors for 
hydrogen-fuelled vehicles (CIDAUT/JRC/Magna Steyr)

Scope:

• Definition of a test protocol for H2 sensors for automotive use (inputs from both 

end users and sensor manufacturers)

• Experimental trials on feasibility of tests

• Resulting validated guideline document on sensor testing

Storhy (http://www.storhy.net)is an Integrated Project within the EU 6th Framework Programme (http://fp6.cordis.lu/fp6/home.cfm)

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Market survey (list not exhaustive)

Average environmental temperature range of commercial 
hydrogen detectors (preliminary survey)

)

C
o

(

e
r
u
t
a
r
e
p
m
e
T

100

75

50

25

0

-25

-50

TCD

Catalytic

Electrochemical

MOS

Sensor functional type

DoE targets

A r e a  o f  A p p l i c a t i o n  

P r o c e s s  p l a n t s  

P i p e l i n e  m o n i t o r 
S t o r a g e  t a n k s  

V e h i c l e  p a s s e n g e r  
c o m p a r t m e n t s / b o o t s  
P e r m e a t i o n  
P e r s o n n e l  m o n i t o r 

O p e r a t i n g  
T e m p e r a t u r e  ( oC ) 
-3 0  t o  1 2 0  

-5 0  t o  8 0  
-5 0  t o  8 0  

-3 0  t o  8 0  

-5 0  t o  8 0  
0  t o  4 0  

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

 
 
 
Market survey (list not exhaustive)

Average response time of commercial hydrogen 
detectors (preliminary survey)

)
s
(

e
m

i
t

e
s
n
o
p
s
e
R

MOS

Electrochemical

Catalytic

TCD

0.1

1

10

100

Sensor functional type

Area of Application 

Process plants 

Pipeline monitor 
Storage tanks 

Response Time 

0.1 – 3 sec for 50% response to step change 

3 sec response to changing  conditions 
3 sec response for 50% of the step change 

Vehicle passenger compartments/boots  0.1 – 1 sec for 70% response to step change 
Permeation 
Personnel monitor 

1 sec response to changing conditions 
0.1 - 0.6 sec for 75% response to step change 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

DoE 
targets

Less common / emerging technologies-1

Gate-field effect

Based on the field effect generated by gases in metal oxide semiconductor 
field-effect transistor (MOSFET) devices with catalytic metals. The 
charging of the gate contact by the gas molecules results in a voltage 
change in the sensor signal (http://www.appliedsensor.com/)

H2 adsorption on the catalytic metal gate ? induces dipoles or charges ?
Alters gate contact voltage
• Issues:

Source: AppliedSensors GmbH

Saturates for high concentrations
• Advantages:

High sensitivity

Miniaturization

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

 
 
 
 
Less common / emerging technologies-2

Ultrasonic – 1

Based on sound-velocity measurements subsequent to short-pulse irradiation 
of a sensitizer (J.K.S. Wan et al. Sensors and Actuators B 32 (1996) 233-237; Shuh-Haw-Sheen et al.,UCRL-ID-137767,  
Livermore (CA), 2000)

Sound velocity in N2 = 353 m/s; in H2 = 1315 m/s
• Issues:

substantial amount of electronics required
•Advantages

Very wide detection range (0.1-100% Vol.) 

In-line measurement and rapid response < 1 s

Low power consumption 

Long-term stability

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: Neodym

Less common / emerging technologies-3

Ultrasonic – 2

A surface acoustic wave sensor detects changes in the velocity of acoustic 
waves propagating across a palladium-coated substrate caused by reversible 
hydrogen absorption (S Lomperski et al. – JRC-ISIS, Meas. Sci. Technol. 11 (2000) 1–8.) 

H2 bulk absorption ? Diffuses into bulk ? Alters mechanical properties
• Issues:
Temperature limitations

Somewhat slow response, f(T): 

30 s at 180?C and 8 s at 380?C
• Advantages:
Wide range (0.1-100% Vol.)

Works at high T (200–4400?C)

Independent of environment

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Less common / emerging technologies-4

Thermoelectric micromachined sensors

A platinum film is applied as a catalyst that oxidizes hydrogen selectively. 
The exothermal heat of the oxidation of hydrogen results in the 
temperature gradients across the sensor, and this gradient is converted into 
the voltage by the thermoelectric element. (Kazuki Tajima, Sensors and Actuators B 108 (2005) 
973–978; Naoya Sawaguchi et al., Sensors and Actuators B 108 (2005) 461–466)

• Issues: needs oxygen; at room temperature, humidity decreases the 

signal/noise ratio. 

• Advantages:

High Hydrogen selectivity

Miniaturization

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: Elsevier

Less common / emerging technologies-5

Resistors

It uses a Wheatsone bridge architecture, with two Pd/Ni sensor legs whose
resistivity changes reversibly in the presence of H2.

H2 surface adsorbtion ? Diffuses into bulk ? Alters electrical properties
• Issues:

Affected by total gas pressure

Poisoned by – CO, SO2, H2S
• Advantages:

Very wide detection range

Rapid response

Independent of environment

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: B.S. Hoffheins, et al, Proceedings of the 1999 U.S DOE Hydrogen Program 
Review NREL/CP-570-26938

Less common / emerging technologies-6

Optic sensors

Optic sensor consists of coatings (V2O5/WO3) at the end of an optical fibre 
that sense the presence of hydrogen in air. When the coating reacts with 
the hydrogen, its optical properties are changed. Light from a central 
electro-optic control unit is projected down the optical fibre to an optical 
detector.
• Issues:

Contamination, cyclic instability, effect of temperature and RH
• Advantages:

Immune to electromagnetic interference

Inherently safe 

for potentially explosive environments

Low power consumption

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

S. Sekimoto et al., Sensors and Actuators B 66 2000 142–145 (Source Elsevier)

Less common / emerging technologies-7

TiO2 nanotubes
Hydrogen  entering  an  array  of titania  nanotubes flows  around  all  the 
surfaces,  but  it  also  splits  into  individually  charged  atoms  and permeates 
the  surface  of  the nanotubes.  These  hydrogen  ions  provide  electrons  for 
conductivity.  The  change  in  conductance  signals  that  hydrogen  above  the 
background level is present. (Oomman K. Varghese et al., Sensors and Actuators B 93 (2003) 338–344)
• Issues:

Technology to be developed
• Advantages: 

Apparently Immune to poisoning

High sensitivity (1 ppm)

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Testing methods - 1

Principle

To expose sensors to a test gas of known composition and measure response

Test methods

1. Test mask

2. Test chamber

Source: Manning

Source: IEC-61779-1, Annex B

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Testing methods - 2

Non-exhaustive list from IEC 61779-1
• Preparation and verification: Calibration, Response time, Flow rate
• Stability of response: Short term, long term
• Climatic: temperature; pressure; humidity; air velocity
• Environmental: high gas concentration, dust, poisons 
• Mechanical: Vibration, Drop test
• Orientation

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

A detector has two response ranges, the dynamic range and the linear dynamic range.

Testing methods - 3

The dynamic range is that concentration 
range over which a concentration 
dependent output is produced. The minimum 
of this range is the concentration at which 
the output is equivalent to twice the noise 
level, while the maximum is that 
concentration where the detector no longer 
responds to a concentration increase.

The linear dynamic range of a detector is 
that concentration range over which the 
detector output is linearly related to solute 
concentration, i.e. y= Ac

A Calibration function must be determined and applied

Source: Nemoto

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Testing methods - 4

Temperature effects

Cross-sensitivity

Source: City Technology

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Source: UMT 

DiMeo et al. Proc. 2002 U.S. DOE H2 Program Review NREL/CP-610-32405 

JRC Sensor Testing Facility (SenTef)

A – gas inlet and mixing
B – liquid inlet and mixing
C – gas buffering system
D - vapour control system
E – test chambers 
F – gas analysis 
G – exhaust
H – argon purging
F – gas analysis system

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

JRC Sensor Testing Facility (SenTef)

TEST 
PARAMETER 

INSTRUMENT 
TYPE 

N. OF 
ITEMS 

OPERATING 
PRINCIPLE 

RANGE 

ACCURACY 

Varying between 1.2-60 ml/min to 
60-3000 ml/min  

0.1 to 0.5 % full 
scale 

0-10 g/h 

0.2% full scale 

Thermal 

Thermal 

Mass flow controllers  

Liquid mass flow 
controllers  

Controlled evaporator 
mixer  

3-columns gas 
chromatograph  

Circulating bath  

PT100 

Liquid mass flow 
controllers  

Atmosphere 
composition 

Temperature 

Humidity 

Controlled evaporator 
mixers  

Pressure 

(Gas buffers) 

Pressure 

(Test chamber)  

Hygrometer  

Transducer 

Transducer 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

4 

1 

1 

1 

2 

2 

1 

2 

1 

Heat exchange 

10 g/h liquid, 1 l n/min gas  

0.2% full scale 

TCD (PDD) 

H2 :  from 10 ppm; (0.1 , PDD) 

5% at 2 ppm 

CO: 2 ppm (with PDD)  to 100%  

 5% at 2 ppm 

CO2: 5 ppm to 100% 

H2S: 10 ppm to 100%  

SO2: 10 ppm to 100%  

5% at 5 ppm 

5% at 10 ppm 

5% at 10 ppm 

NH3: 200 ppm to 100%  

20% at 200 ppm  

TCD  

FID 

1 

5-6 

Heat exchange 

Resistance 

Alcohols/alcanes: 1 ppm to 100%  
- 40 to 140oC 
-200 to 500oC 

Thermal 

0-5 g/h 

0-100 g/h 

1% at 10 ppm 
± 0.05 oC 
± 0.1oC 

0.2% full scale 

0.2% full scale 

Heat exchange 

Chill mirror  

10 g/h liquid, 1 l n/min gas  

0.2% full scale 

100 g/h liqu id, 10 ln/min gas 
Dew/frost point: –50 to 100oC 

0.2% full scale 
±0.2oC 

Strain gage 

0-10 bar abs 

0.15% full scale  

Strain gage 

0-1.6 bar abs  

0.1 % full scale 

 
 
JRC Sensor Testing Facility (SenTef)

Pressure regulators/transducers

Outlet 
flow

Test 
chamber 
temperature 
setting

GMFC

LMFC

CEMs

Labview® - operated system 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

JRC Sensor Testing Facility (SenTef)

20000

15000

Cal. Gas: 100 ppm H2 in N2

s
t
l
o
V
m

L
A
C
1
0
1
0

L
D
B
0
0
0
0

.

0

)
2
O

(

.

0

2
H

200

100

0

8 10 12 14 16

TCD

L
A
C
1
0
1
0
.
0

2
H

L
D
B
0
0
0
0
.
0

)
2
O

(

L
A
C
0
0
0
1
.
9
9

2
N

Gas analyser:

3-columns GC

Detectors:

2 TCD (H2), (SO2, NH3)

s
t
l
o
V
m

10000

5000

1 FID (CxHy, R-OH, H2S)

Next: PDD (H2 ppm, CO)

0

0

5

10

15

20
Seconds

25

30

35

40

s
t
l
o
V
m

15

10

5

a
P

2
8

.

e
n
a
h
e
M

t

a
P

0
7

.

S
2
H

a
P

2
8

.

e
n
a
t
c
o
o
s
I

Cal. Gas:
100 ppm CH4
100 ppm H2S
100 ppm C8H18
100 ppm MetOH
100 ppm EtOH
100 ppm IPA
Bal. N2

a
P

9
8

.

l

o
n
a
h

t

e
M

a
P

5
8

.

l

o
n
a
p
r
p
o
s
I

a
P

L
A
C
1
.
0
1

S
2
H

a
P

L
A
C
0
.
0
1

e
n
a
h
t
e
M

a
P

L
A
C
0
.
0
1

e
n
a
t
c
o
o
s
I

4.5

4.0

3.5

50

60

70

s
t
l
o
V
m

a
P

5
8

.

l

o
n
a
h
E

t

FID

50

60

70

80

100

90
Seconds

110

120

130

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
JRC Sensor Testing Facility (SenTef)

Test types

Environmental  tests. They  consist  of  assessing  the  response  dependence  on 
temperature,  pressure,  humidity,  interfering  species,  or  contaminants,  in  quasi-
static conditions. Variability of ambient conditions: 
temperature variation between –40 and 140oC; 
relative humidity (r.h.) change between 10 and 90%; 
pressure excursion between 0.8 and 1.3 bar (altitude changes). 
Contaminant species: CO, CO2, H2S, SO2, NOx, CxHy, NH3, Et-OH, Met-OH, IPA. 

Dynamic response tests both to gas compositional changes, i.e. to rapid switches 
of atmosphere composition, simulating sudden gas releases, and to environmental 
changes, i.e. rapid changes of temperature, humidity and pressure, simulating the 
sudden displacement of a detector mounted on a vehicle or on a portable device.

Fatigue tests. They include environmental fatigue, which could cause signal drift 
due  to  poisoning  and/or  temperature  cycling,  and  mechanical  fatigue,  typically 
due to vibrations and particularly important in view of mobile applications.

·

·

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Present activities - 1

Dynamic response of 
a commercial 
electrochemical 
sensor 

Dynamic response of 
a commercial 
catalytic sensor 

Sensor mounting for the response time test. Appropriate test masks can be fitted on top of the gas inlet/outlet orifice. 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

·
a

Present activities - 2

b

Influence of impinging flow rate on sensor dynamic response: a) EC; b) CAT

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Present activities - 3

Influence of the 
sensor itself (catalytic)  
on temperature during 
a test

Chamber temperature

Sensor temperature

)

C
o

(

e
r
u
t
a
r
e
p
m
e
T

140

120

100

80

60

40

20

0

Large-capacity (2.5 liters) environmental test chamber

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

0

50

100

150

200

250

300

Time (min)

 
Future developments

Multiple chamber for dynamic & 
environmental cycling test
Based on then applicator method concept 
(International Standard IEC 61779-1:1998 
(E) Annex B, paragraph B 2.2) 

Sensor to be mounted on a temperature (T) - controlled support inserted into the case floor  

By means of appropriate actuators, two applicators at different T flushed with gases at 
different composition will be alternated on top of the sensor, while the support will provide 
temperature equilibration with the test gas. The rapid switch will take place without 
interruption in data transfer to and from the sensor under test

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Conclusions

• JRC scope

To operate an independent facility for testing and validating the performance 
of H2 safety sensors
• Objectives
• Test performance of sensors under influence of environmental conditions 

representative of those expected during its use.

• Provide assistance to developers, participate to collaborative projects and 

round-robin exercises 

• Support the development of a standard procedure for testing the 

performance of H2 sensors in a controlled environment

• Accelerate the transition to safe and sustainable, hydrogen based, energy 

technologies. 

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Thanks for your attention

For questions please contact

Dr. Paolo Castello

Scientific Officer, EC-DG JRC-IE

paolo.castello@jrc.nl

JRC E/I Workshop on Experimental techniques on Hydrogen Storage 17/18.10.05

Hydrogen Sorption 
Measurements 

D. Broom 

EC- DG JRC-IE 

 
 
 
 
 
 
 
Hydrogen Sorption Measurements

Darren Broom
Clean Energies Unit
18th October 2005

JRC – IE Petten on 18.10.05

1

JRC – IE Petten on 18.10.05

2

Contents

1.

Introduction

2. Our facilities

3. Test materials – LaNi5-yAlyHx

4. Our work at Petten

5. Summary

1. Introduction

The hydrogen sorption properties of materials can be 
determined using a number of different methods.

In our hydrogen storage material testing laboratory we 
currently have four different instruments for the gas phase
characterisation of materials.

We are using three techniques: gravimetric, volumetric (or 
Sieverts’ Method) and temperature-programmed desorption.

Our preliminary measurements are being made on materials 
from the LaNi5-yAlyHx system.

JRC – IE Petten on 18.10.05

3

2. Our Facilities

We currently have three commercial instruments:

• Intelligent Gravimetric Analyser from Hiden 
Isochema, UK

• HTP1-S from Hiden Isochema, UK

• Gas Reaction Controller from Advanced 
Materials Corporation, USA

In addition, we are building our own volumetric system.

JRC – IE Petten on 18.10.05

4

Gravimetric vs Volumetric

In the gravimetric technique, the mass of the sample is 
monitored to determine the quantity of hydrogen absorbed.

In the volumetric technique, the quantity of hydrogen absorbed 
by a material is determined by the drop in gas pressure in a 
known, fixed volume.

Consider a system with a reference volume V1, and a sample 
cell of volume V2, held at a constant temperature T. 

The reference volume is filled with hydrogen to a pressure
of P1 and a valve between the 2 volumes is then opened.

JRC – IE Petten on 18.10.05

5

The system is then allowed to reach equilibrium with a pressure 
P2 throughout the system (V1 + V2).

The total number of moles of hydrogen absorbed by the 
sample, assuming ideal gas behaviour, is then given by,

=
nn
1

=

n

2

VP
11
RT

JRC – IE Petten on 18.10.05

6

+

2

(

VVP
1
2
RT

)

-
-
D
Intelligent Gravimetric Analyser

A fully automated gravimetric
instrument supplied by Hiden 
Isochema.

It can operate at hydrogen 
pressures of up to 20 bars 
and temperatures of 
between –170°C and 900°C.

Generally, sample sizes < 200 mg.

The sample sits in a pyrex bulb and the mass is monitored 
as a step change in pressure is applied.

Can be used for determining pressure-composition 
isotherms and for determining sorption kinetics.

JRC – IE Petten on 18.10.05

7

174.70

174.65

174.60

174.55

174.50

g
m

/

i

t
h
g
e
W

3400

3350

3300

3250

3200

r
a
b
m

/
e
r
u
s
s
e
r

P

 LaNi4.9Al0.1, step 21, "cycle 2"

1910

1920

1930

1940

1950

1960

1970

1980

1990

2000

2010

Time / minutes
Kinetic data for an absorption step in a LaNi4.9Al0.1 sample, 
measured using the Intelligent Gravimetric Analyser.

JRC – IE Petten on 18.10.05

8

 
 
 
 
 
 
 
 
HTP1-S  

A fully automated temperature-programmed desorption
(TPD) instrument supplied by Hiden Isochema.

In this case, rather than determine equilibrium pressure-
composition isotherms, we determine the total H2 storage 
capacity and the temperature at which desorption occurs.

It can operate at hydrogen pressures of up to 100 bars 
and temperatures of between –170°C and 500°C.

Sample sizes > 1mg.

Samples are hydrogenated in-situ, at the required 
temperature and H2 pressure.

JRC – IE Petten on 18.10.05

9

The temperature is then lowered to trap in the hydrogen.

The temperature is then increased, at a controlled ramp 
rate, and the quantity of hydrogen desorbed is monitored 
using a mass spectrometer.

The hydrogen is desorbed into a flow of He and the 
desorbed quantity is determined by performing a 
calibration run with a 1%H2/99%He mixture.

The instrument is particularly well suited to small sample 
sizes (we have data from a 3mg Pd sample).

Data is in the form of thermal desorption spectra, which can 
either be integrated to determine the total quantity of 
desorbed H2 or analysed in terms of the positions of 
desorption peaks.

JRC – IE Petten on 18.10.05

1
0

Gas Reaction Controller

A fully automated volumetric instrument supplied by 
Advanced Materials Corporation.

It can operate at hydrogen pressures of up to 200 bars 
and temperatures of between -80°C and 500°C.

Sample sizes > 1g.

Two sample chambers: one for use with the furnace and 
one for the low temperature bath.

Primarily for determining pressure-composition isotherms 
but can used for crudely determining absorption and
desorption kinetics.

JRC – IE Petten on 18.10.05

1
1

3. Test materials – LaNi5-yAlyHx

To test our instruments we have chosen this well known and
characterised system, based on LaNi5.

This is an intermetallic compound that absorbs atomic 
hydrogen into the bulk of the material.

One of the practical considerations for a storage material is the
desorption pressure and temperature.

By varying the Al content, the H2 ab/desorption pressure at a 
given temperature can be varied allowing the material to be 
‘tuned’ to required conditions.

JRC – IE Petten on 18.10.05

1
2

Sorption Behaviour

a + b

E a

R
U
S
S
E
R
P
N
E
G
O
R
D
Y
H

COMPOSITION (H/M)

The diagram shows a typical absorption isotherm. At low 
hydrogen concentration, there is a ‘solid solution’ a phase; 
at high concentration, there is an ordered hydride b phase.

JRC – IE Petten on 18.10.05

1
3

In the mixed phase region, there is a large increase in the 
hydrogen concentration for a relatively small increase in the 
hydrogen pressure.

E
R
U
S
S
E
R
P
N
E
G
O
R
D
Y
H

a + b

Plateau
region

COMPOSITION (H/M)

The hydrogen pressure at which the plateau occurs is an 
important practical parameter. We have materials of the 
composition LaNi5-yAlyHx, where y = 0.1, 0.3 and 0.5.

JRC – IE Petten on 18.10.05

1
4

 
b
 
a
b
10

1

0.1

0.01

m
t
a
/
e
r
u
s
s
e
r
p

l

a
i
t
r
a
p

2

H

 LaNi4.9Al0.1, absorption, 42°C, IGA
 LaNi4.9Al0.1, absorption, 40°C, AMC
, absorption, 40°C, IGA
 LaNi
, absorption, 40°C, AMC

 LaNi

Al

Al

0.5

4.5

4.5

0.5

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

H content / weight %

Absorption pressure-composition isotherms for LaNi4.9Al0.1
and LaNi4.5Al0.5, measured volumetrically (AMC) and 
gravimetrically (IGA).

JRC – IE Petten on 18.10.05

1
5

4. Our work at Petten

A major problem with the measurement of hydrogen sorption 
characteristics is the sensitivity of the measurements to the 
experimental conditions and sample history.

A number of factors can affect results:

• Contamination of the sample (surface) and the hydrogen gas

• Insufficient sample characterisation

• Non-isothermal conditions (exothermic absorption 
reaction) or imprecise temperature measurement

• Leaks (including through powder contamination)

JRC – IE Petten on 18.10.05

1
6

 
 
 
 
 
 
We intend to contribute to progress on increasing the certainty 
of hydrogen sorption measurements/characterisation and 
hence assessing a material’s suitability for practical use:

• Set up a laboratory with instruments covering different 
characterisation techniques and different temperature 
and pressure regimes

• Ensure that the instruments produce repeatable and 
reproducible results on well characterised materials

• Help co-ordinate ‘round robin’ exercises with 
collaborating laboratories

JRC – IE Petten on 18.10.05

1
7

For example, one aspect of our work will be to directly compare 
results from volumetric and gravimetric measurements to 
identify the most significant sources of errors and their relative 
importance at different measurement temperatures and 
pressures.

• There are limits to the pressures at which gravimetric 
instruments can operate

• Errors due to the compressibility of hydrogen are greater 
at higher pressures, which may cause more problems 
with high pressure volumetric measurements

• Errors due to thermal gradients in the system may 
(or will) be greater when measurements are made at 
sample temperatures vastly different from the 
temperature of the system

JRC – IE Petten on 18.10.05

1
8

5. Summary

• In the hydrogen storage material laboratory we have four 
different instruments.

• We are using three techniques: gravimetric, volumetric 
and temperature-programmed desorption.

• Our preliminary measurements are being made on 
materials from the LaNi5-yAlyHx system.

• Our work at Petten primarily involves the investigation of 
the repeatability and reproducibility of hydrogen sorption 
measurements.

JRC – IE Petten on 18.10.05

1
9

Microscopical characterisation 
of H2 storage materials using 
Scanning Electron Microscopy 

P. Moretto 

EC- DG JRC-IE 

 
 
 
 
 
 
 
Pietro  Moretto

Microscopic techniques – SEM 

E Introduction to electrons – matter interaction
E SEM, X-ray Spectroscopy and TEM
E Application examples

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

1

Particle beams fundamentals (1)

Louis de Broglie (1925)

=l

=

h
mv

h
2
mE

Where:

h is the Planck constant

m is  the relativistic mass

m0 is the rest mass 

=

1

m
0
2
v

2

/

c

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

2

h = 6.63x10-34 J s

m0 (e-) = 9.1 x 10-31 Kg
1 eV = 1.6 x 10-19 J

-
Particle beams fundamentals (2)

For electrons, and E < 105 eV

=l

h
2
mE

=

26.12
E

(l in Å, E in eV)

E (eV) 

102  
104 
105 
106 

l (Å) 
no rel. correction 
1.226 
0.1226 
0.0387 
0.0122 

l (Å) 
with rel. correction 
1.226 
0.1220 
0.0370 
0.0087 

Wavelength associated with electrons as a function of energy 

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

3

Particle beams fundamentals (3)

m
m
1

m
m
1

Real world dimensions

m
n
1

m
n
1
0

.

Visible light
Visible light

X-rays & n
X-rays & n

105 eV e-
105 eV e-

m
m
m
m
1
1

m
m
m
m
1
1

m
m
n
n
1
1

m
m
n
n
1
1
.
.
0
0

m
m
n
n
3
3
-
-
0
0
1
1

Wavelengths
Wavelengths

Eye
Eye

Optical microscopy
Optical microscopy

SEM
SEM

TEM
TEM

Diffraction techniques
Diffraction techniques

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

4

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Electron-matter interaction (1)

Physical quantities of a wave: Intensity, Energy and wave vector k (vector modulus k = 1/l )
For particles also Cross-Section and Mean Free Path
The overall cross-section of particle-matter interaction is much greater than the corresponding 
value for X-rays. The interaction effect of a particle with an atom depends further on its 
interaction distance r from the atom.

Elastic scattering
Elastic scattering

If r >> r0 => elastic scattering

Incident 
Incident 
electron
electron

ATOM
ATOM

r
r

r0
r0

Scattered primary 
Scattered primary 
electron
electron

Inelastic scattering
Inelastic scattering

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

5

Incident 
Incident 
electron
electron

Ejected 
Ejected 
electron
electron

Scattered primary 
Scattered primary 
electron
electron

Electron-matter interaction (2)

Elastic scattering

Interaction effects:

Zµs
E

2

2
0

§ Thermal effect (heating of target)

§ Chemical effect (breaking molecules)

§ Displacement effect (light elements, high 

energies)

Where: 

s is the event cross section

Z is the atomic number

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

6

Electron-matter interaction (3)

Inelastic scattering

Interaction effects: 

Zµs
2
0E

•Excitation of Valence & Conduction band

•Excitation of Atomic Core Levels

•Conversion to Electromagnetic Energy

Ejected 
Ejected 
electron
electron

Bremstrahlung  
Bremstrahlung  
radiation
radiation

Scattered primary 
Scattered primary 
electron
electron

Incident 
Incident 
electron
electron

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

7

Electron-matter interaction (4)

Ejection of orbital electron
Ejection of orbital electron

Electron relaxation & photon 
Electron relaxation & photon 
generation
generation

Option 1

Option 2

Photon internally converted 
Photon internally converted 
and Auger electron emitted
and Auger electron emitted

Photon emitted

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

8

Electron-matter interaction (summary)

Primary Electron

Signals from scattering: 

•Diffraction of primary e-

•Secondary e- with a continuous 
energy distribution

•Auger e- with characteristic 
energies

•Characteristic x-rays

•Cathodoluminescence radiation

•Lattice vibration

•Primary electrons with 
characteristic energy losses. 

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

9

Microscopy and Spectroscopy

SEM = scanning Electron Microscopy

TEM = Transmission Electron Microscopy

EDS/WDS = X-ray Spectroscopy

AES = Auger Electron Spectroscopy

SIMS = Secondary Ions Mass Spectroscopy

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

10

SEM, TEM 
and X-ray Spectroscopy

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

11

Signals in SEM

BSE
BSE

SEII
SEII

Primary Electron
Primary Electron

5lSE
5lSE

SEI
SEI

SE
SE

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

12

Backscattered Electrons (BSE):

•Phase contrast 
•Characteristics of a depth of 1 m m.

2
0

2

Zµs
E

Secondary Electrons (SE):

•Morphology contrast 

•Characteristics of a depth of few 
nm.

BSE and SE

SE

Auger

BSE

y
t
i
s
n
e
t
n
I

BSE = Backscattered Electrons

Elastic scattering due to Coulomb forces 
between e- and nuclei

e- Energy E/E0

1

Intensity depends on atomic number

Energy distribution of electrons emitted from a thick target

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

13

SEM overview

Applications: 

•Morphology observation of 
surface by Secondary 
Electrons

•Phase contrast by 
Backscattered Electrons

•Chemical analysis by 
characteristics X-rays.

SE detector

BSE detector

X-rays detector

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

14

SE versus BSE 
Example: fracture surface of cast iron

Inelastic scattering
Inelastic scattering
Few nm depth.  Mainly surface 
Few nm depth.  Mainly surface 
information
information

Elastic scattering
Elastic scattering
mm depth. Phase contrast
mm depth. Phase contrast
(black spots are graphite nodules)
(black spots are graphite nodules)

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

15

SEM optics

Resolution: r = K· l3/4                               Depth of Field: d =r/a
Resolution: r = K· l3/4                               Depth of Field: d =r/a

l=wavelength    r=resolution       a=angular aperture
l=wavelength    r=resolution       a=angular aperture

Comparison between depth of focus of an optical microscope (left), and a SEM microscope (right)
Comparison between depth of focus of an optical microscope (left), and a SEM microscope (right)
JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

16

Energy Dispersive Spectroscopy (EDS)

Si(Li) solid-state 
detector

e-

X-ray

sample

Electronics:
Pre-amplifier 
Amplifier
ADC

Fe Ka

Fe Kb

Energy [KeV]

spectrum

Energy resolution: approximately 130 eV

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

17

Wavelength Dispersive Spectroscopy (WDS)

Analysing crystal

Proportional 
counter

e-

X-ray

sample

Pulse-height 
analyser

Energy resolution: approximately 5 eV

Fe Ka

Fe Kb

Energy [KeV]

spectrum

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

18

Signals in TEM

Primary Electron
Primary Electron

Diffracted
Diffracted

BSE
BSE

Transmitted
Transmitted

Backscattered e- (BSE):
•Phase contrast 
•Experienced elastic multi-
scattering (high angle collection).

Transmitted e-:
•Bright field imaging (diffraction 
contrast). 
•EELS spectroscopy & imaging.

Diffracted e-:
•Dark field imaging (diffraction 
contrast). 
•Quantitative phase analysis.

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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TEM overview

Applications: 

•High resolution Morphology

•Phase analysis by E- diffraction.

•Phase contrast by Backscattered 
Electrons

•Chemical analysis by 
characteristics X-rays.

•Chemical analysis by Electrons 
Energy Loss Spectroscopy.

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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Application examples

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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TEM & dislocation (1)

B. Décamps, J.-M. Joubert, R. Cerny and A. Percheron-Guégan
TEM study of the dislocations generated by hydrogen absorption/desorption in LaNi5 and derivatives 

Journal of Alloys and Compounds, In Press, Corrected Proof, Available online 14 July 2005

LaNi4.6Mn0.4 compound after 15 hydrogen absorption/desorption cycles. 
Dislocations in bright.

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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TEM & nanomaterial (2)

Ming Au 
Hydrogen storage properties of magnesium based 
nanostructured composite materials

Materials Science and Engineering B, Volume 117, 
Issue 1, 25 February 2005, Pages 37-44 

(a) TEM image of the 30 h ball milled material Mg 

50 wt.% + Ni 50 wt.%. The material shows the composite 
structure. The nanoscale grains (A) are surrounded by the 
amorphous intergrain region (B). 

(b) The electron diffraction pattern of the area A shows that 

magnesium is in nano-crystalline state with average grain 
size about 13 nm. 

(c) The electron diffraction pattern of the area B shows that 

the nickel is in amorphous state. 

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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TEM  & nanotubes (3)

M. M. Shaijumon and S. Ramaprabhu
Synthesis of carbon nanotubes by pyrolysis of acetylene using alloy hydride materials as catalysts and 
their hydrogen adsorption studies

Chemical Physics Letters, Volume 374, Issues 5-6, 18 June 2003, Pages 513-520 

Conventional SEM image

TEM bright field, showing a precursor 
embedded in the nanotube.

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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AES  & MH surface

M. Jurczyk, K. Smardz, W. Rajewski and L. Smardz
Nanocrystalline LaNi4.2Al0.8 prepared by mechanical alloying and annealing and its hydride 
formation

Materials Science and Engineering A, Volume 303, Issues 1-2, 15 May 2001, Pages 70-76 

Auger electron spectrum of polycrystalline LaNi4.2Al0.8 alloy versus sputtering time, as converted 
to depth. Shown are the peak-to-peak intensities of nickel, lanthanum, aluminium, oxygen and 
carbon. 

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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SIMS & surface

H. Züchner, J. Kintrup, R. Dobrileit and I. Untiedt
Chemical structure and bonding characteristics of metal hydrogen systems studied by the surface 
analytical techniques SIMS and XPS

Journal of Alloys and Compounds, Volumes 293-295, 20 December 1999, Pages 202-212 

Negative secondary ion mass spectrum of LaNi4.15Al0.85 charged in situ with D2. 
The cluster ions NiD2
nickel-deuterium clusters ions exceed those of the deuterium-free nickel ions, which indicates a strong nickel-
deuterium bond in LaNi5Dx materials.

- and Ni2D- contain 90% of all metal bound deuterium atoms. The intensities of these 

JRC – IE Petten 17-18.10.2005 SYSAF E&I Workshop

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Literature

J. P. Eberhart 
Structural and chemical analysis of materials
J. Wiley & Sons (1991)

J. I. Goldstein et al. (ed.)
Scanning Electron Microscopy and X-ray Microanalysis
Plenum Press (1992)

S. Amelinckx et al. (ed.)
Handbook of Microscopy (3 volumes)
a(1997)

Oxford Instruments Microanalysis Group
The principles and practices of X-ray microanalysis 
Multimedia tools

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Appendices 

 
 
 
 
 
 
 
 
 
 
JJRRCC--IIEE  SSYYSSAAFF  EEnnllaarrggeemmeenntt  &&  IInntteeggrraattiioonn  
WWoorrkksshhoopp  
“EExxppeerriimmeennttaall  aassppeeccttss  ooff  RR&&DD  oonn  HHyyddrrooggeenn  
SSttoorraaggee  TTeecchhnnoollooggiieess” 
1177--1188//1100//22000055,,  JJRRCC--IIEE,,  PPeetttteenn  ((NNLL)) 

FFIINNAALL  PPRROOGGRRAAMMMMEE  

MMoonnddaayy  1177//1100//22000055  
08:45   Arrival & Registration 

09:30 – 10:30      Introductory Session 

09:30 – 09:50     Welcoming Address & Presentation of the JRC-Institute for 

Energy 

M. Steen - European Commission, DG Joint Research Centre, IE 

09:50 – 10:30 

The JRC Enlargement & Integration Action 2005 

C. Filiou - European Commission, DG Joint Research Centre, IE  

10:45 – 12:15   Technical Session I 

10:45 – 11:30   Overview of the Solid-State Hydrogen Storage and related R&D  

A. Züttel - Universität Fribourg, Switzerland; Vrije Universiteit van Amsterdam, Netherlands 

11:30 – 12:15   Micro- and Macro-scopic Characterisation Techniques and 

Modelling 

K. Ross – University of Salford, Institute for Materials Research, UK 

12:30   Lunch 

13:30 – 15:00   Technical Session II 

13:30 – 14:15   Hydrogen Storage Tank: Design and Heat Transfer Principles 

T. Stubos - NCSR Demokritos, Environmental Research Laboratory, Greece  

14:15 – 15:00  

Testing of Hydrogen Safety Sensors at JRC 

H. Crutzen - European Commission, DG Joint Research Centre, IE 

15:15 – 16:45   Laboratory Visits 

15:15 – 16:00  

Visit to the Sensors Testing Facility – SenTeF  

16:00 – 16:45  

Visit to the High-Pressure Gas Tank Testing Facility – GasTeF 

19:00 

Dinner in Bergen 

 
  
 
 
 
 
 
 
TTuueessddaayy  1188//1100//22000055  
08:45  

Arrival 

09:00 – 10:00   Technical Presentations 

09:00 – 09:30   Hydrogen Sorption Measurements 

D. Broom – European Commission, DG Joint Research Centre, IE 

09:30 – 10:00   Microstructural Characterisation of H2 Storage Materials using 

Scanning Electron Microscopy 

P. Moretto – European Commission, DG Joint Research Centre, IE 

10:00 – 13:00  Laboratory Sessions 

Laboratory exercises running in parallel- split to two groups that will alternate: 
1st exercise: Microstructural Analysis of Hydrogen Storage Materials (90 minutes);  
2nd exercise: Hydrogen Sorption Measurements (90 minutes) 

13:00 – 14:00   

Lunch  

14:00 – 14:30  Wrap-up Session & Conclusions 
15:00   End of Workshop - Departure of attendees: transfer to Airport & Hotel

 
 
LIST OF PARTICIPANTS 

Keynote lecturers 

University of Salford, 
Institute for Materials 
Research, UK 
National Centre for 
Scientific Research 
'Demokritos', Greece 
Universität Fribourg, 
Switzerland; Vrije 
Universiteit, Netherlands 

Bulgaria 

Bulgarian Academy of 
Sciences, Electrochemistry 
& Energy Systems Institute 

Croatia 
University of Zagreb, 
Faculty of Chemical 
Engineering & Technology  
F.Y.R.O.M. 

Sts.  Cyril and Methodius 
University, Faculty of 
Technology & Metallurgy 

Hungary 
Budapest University of 
Technology and Economics, 
Department of Automobiles 
Latvia 

University of Latvia, Solid 
State Physics Institute 
Riga Technical University, 
Energetics & Electrical 
Engineering Faculty 
Lithuania 

Vytautas Magnus University; 
Lithuanian Energy Institute 

Prof. Keith ROSS  

d.k.ross@salford.ac.uk 

Dr. Thanos STUBOS 

stubos@ipta.demokritos.gr  

Prof. Andreas ZÜTTEL 

andreas.zuettel@unifr.ch 

Mr. Stoyan BLIZNAKOV 

sbliznakov@mail.bg  

Mr. Franjo JOVIC 

fjovic@fkit.hr  

Mr. Perica PAUNOVIK 

pericap@ian.tmf.ukim.edu.mk  

Mr. Orce POPOVSKI 

orcepop@freemail.com.mk  

Mr. Dávid KLUG 

david@klug.hu  

Mrs. Liga GRINBERGA 

Mr. Ingars STEIKS  

Liga.Grinberga@cfi.lu.lv  

ingarssteiks@inbox.lv  

Mr. Irmantas BARNACKAS  

irmantas@mail.lei.lt  

Lithuanian Energy Institute  Mr. Lelis  MARTYNAS 

martynas_lelis@fc.vdu.lt 

Poland 

Warsaw University of 
Technology, Faculty of 
Materials Science & Eng 

Mr. Krystian PARADOWSKI 

kparadowski@inmat.pw.edu.pl  

Mr. Tomasz PLOCINSKI 

tplocinski@inmat.pw.edu.pl  

 
 
 
 
 
 
 
 
 
 
 
Romania 

BSUN - Center for Advanced 
Engineering Sciences" Ovidius" 
University of Constantza 

Serbia & Montenegro 

University of Belgrade, Faculty of 
Physics 

Slovakia 
Comenius University, Division of 
Environmental Physics, Dept. of 
Astronomy 
University of P. J. Safarik, Dept. 
Physical & Analytical Chemistry 
Slovenia 

Joseph Stefan Institute, Dept. for 
Nanostructured Materials  

Turkey 

Middle East Technical University, 
Department of Metallurgical & 
Materials Engineering 

TUBITAK-Marmara Research 
Centre, Energy Institute 

Greece 

Prof. Dr. Eden MAMUT 

emamut@univ-ovidius.ro  

Mr. Borivoje DAKIC 

daka_b@yahoo.com  

Ms. Marcela MORVOVA  

mmorvova@zoznam.sk  

Ms. Lenka LÖRINCOVA 

lenka_l@atlas.sk  

Mr. Andraž KOCJAN 

andraz.kocjan@ijs.si  

Mr. Hasan AKYILDIZ  

akhasan@metu.edu.tr  

Mr. Alper SARIOGLAN  

Alper.Sarioglan@mam.gov.tr  

National Centre for Scientific Research 'Demokritos' 

Dr. Georgia CHARALAMBOPOULOU 

European Commission – DG JRC-IE Petten 

Dr. Darren BROOM 

Dr. Hugues CRUTZEN 

Ms. José DRUPSTEEN 

Mr. Michel HONSELAAR 

Dr. Pietro MORETTO 

Dr. Ota SALYK 

Dr. Marc STEEN 

Dr. Constantina FILIOU 

Apologies 

Dr. Paolo CASTELLO (JRC-IE) 

Prof. Roger HURST (JRC-IE) 

darren.broom@jrc.nl 

hugues.crutzen@jrc.nl 

jose.drupsteen@jrc.nl 

michel.honselaar@jrc.nl 

pietro.moretto@jrc.nl 

ota.salyk@jrc.nl  

marc.steen@cec.eu.int 

constantina.filiou@jrc.nl 

paolo.castello@jrc.nl  

roger.hurst@cec.eu.int 

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
European Commission 

EUR22177EN  –  DG  JRC  –  Institute  for  Energy  -  Enlargement  & 
Integration  Workshop  “Experimental  Aspects  of  R&D  on  Hydrogen 
Storage Technologies” 

C. Filiou, P. Castello and P. Moretto (Editors) 

Abstract 

The  workshop  "Experimental  aspects  of  R&D  on  Hydrogen  Storage 
Technologies" was organised by the Institute for Energy (IE) of the Directorate 
General  Joint  Research  Centre  (JRC)  of  the  European  Commission,  in  the 
frame of the JRC Enlargement & Integration Action.  

Held  at  the  Institute  in  Petten  (NL),  it  was  conceived  as  a  training/teaching 
event  targeted  at  an  international  audience  of  young  researchers  and 
university students from new EU member states, EU Acceding and Candidate 
Countries  and  Associated  States.  Invited  experts  from  all  over  Europe  held 
lectures  concerning  the  present  and  future  challenges  of  R&D  on  hydrogen 
storage, and on related industrial and experimental technologies. 

Open  discussion  among  the  participants  was  complemented  by  visits  to  the 
JRC-IE testing installations for hydrogen storage tanks (GasTeF: Compressed 
Gas  Tanks  Testing  Facility)  and  safety  sensors  (SenTeF:  Sensors  Testing 
Facility). and hands-on experiments at the Microstructural Analysis Laboratory 
and  at  the  SolTeF  (Solid-state  hydrogen  storage  Testing  Facility)  for  the 
micro- and macro-scopic characterisation of solid-state materials for hydrogen 
storage.  

 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
The mission of the JRC is to provide customer-driven scientific and technical support for the 
conception, development, implementation and monitoring of EU policies. As a service of the 
European  Commission,  the  JRC  functions  as  a  reference  centre  of  science  and  technology 
for  the  Union.  Close  to  the  policy-making  process,  it  serves  the  common  interest  of  the 
Member States, while being independent of special interests, whether private or national.