th4 Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010th

4 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory andModelling, Fuel Cells, Metal Hydride Batteries, Functional Materials

The 4th symposium “Hydrogen & Energy” follows the 3rd symposium on 25. – 30.
January 2009 in Braunwald with more than 80 participants. It serves as an information
platform of the fundamental science and technology and the frontiers of research onhydrogen and energy.
The symposium consists of invited keynote lectures reviewing the key elements of thehydrogen cycle, i.e. the hydrogen production, hydrogen storage and hydrogen
combustion and fuel cells. Furthermore, contributions on the conversion of renewableenergy in general and energy carriers beside and beyond hydrogen are very welcome.
The world leading experts present the current research challenges and most importantresults in invited and contributing talks. Early stage and experienced researcherspresent their newest results and the open questions on posters as well as in a one
slide presentation.
The conference will take place in the hotel Hirschen in the beautiful small village
Wildhaus on 1'100 m above see level in the Swiss mountains. The village is the middle
of a resort, quiet and offers, beside the scientific program, relaxing moments as well as
plenty of sport activities.
The number of participants is limited to 100.

24. - 29. January 2010
Hotel Hirschen
CH-9658 Wildhaus, Switzerland
Tel. (+41) (71) 998 5454
Fax (+41) (71) 998 5455
email: info@hirschen-wildhaus.ch
URL: http://www.hirschen-wildhaus.ch/

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CONTENTS
Timetable
Abstracts
SUNDAY 24. 1. 2010
I01: Prof. Dr. Boulouchos Konstantinos
Properties, risks and potential of hydrogen as fuel for combustion engines

MONDAY 25. 1. 2010
I02: Dr. Cho Young Whan
Critical evaluation of destabilization options for high temperature metal borohydrides
O01: Dr. Friedrichs Oliver
Diborane - The key to reversible hydrogen storage
O02: Mr. Kim Ji Woo
Microstructure and its effects on the hydrogen sorption properties of solid state hydrogenstorage materials
O03: Ms. Lindemann Inge
A study of Li-Al-borohydride as a potential candidate for hydrogen storage
O04: Dr. Remhof Arndt
Rotational diffusion in MBH4 (M=Li, NA, K)
O05: Dr. Gremaud Robin
Time and frequency hydrogen dynamics in LiBH4 by infrared pump probe spectroscopy
O06: Mr. Garroni Sebastiano
Sorption properties of NaBH4/MH2 (M = Mg, Ti) systems
O07: Mr. Domènech-Ferrer Roger
Additives effect on synthesis and decomposition of magnesium borohydride
I03: Prof. Dr. Bormann Rüdiger
Tailoring Borohydrides for Reversible Hydrogen Storage
O08: Dr. Filippi Matteo
Light-weight sodium alanate thin films grown by reactive sputtering
O09: Dr. Fichtner Maximilian
Alanates - Synthesis, Transformation Mechanism and Technical State of the Art.
O10: Dr. Mauron Philippe
Borohydrides
O11: Dr. Hu Jianjiang
Li-Mg-H-N Hydrogen storage systems – composition variation, sorption properties andmechanistic dtudy
O12: Dr. Boesenberg Ulrike
Reaction pathways and role of additives in reactive hydride composites
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O13: Dr. Bellosta von Colbe Jose
System integration: From materials research to tank system
P01: Dr. Miwa Kazutoshi
Structural and thermodynamical properties of double-anion complex hydride, Mg(BH4)(NH2)P02: Dr. Walton Allan
A comparative study of porous hydrogen storage materials
P03: Dr. Stowe Ashley
Analysis of Thermal Decomposition of t-Butylamine Borane
P04: Dr. Shim Jae-Hyeok
Destabilization reaction of LIBH4 + MH compositesenhanced by hydrogen back pressure
P05: Mr. Schiavo Benedetto
Effect of nanostructuring on the hydrogen storage properties of LaNi5 systems
P06: Mr. Gorbar Michal
Porosity graded ZrO2 diaphragms for alkaline electrolysis
P07: Dr. Han Sang-Sup
Measurement and evaluation techniques of hydrogen storage/release amount for solid-statematerials

TUESAY 26. 1. 2010
I04: Prof. Dr. Kirchheim Reiner
On the hydrogen defect interaction in the framework of a defectant concept
Oxx: Prof. Dr. Orimo Shin-ichi
Lithium super (fast) Ionic conductivity (Part I)
Oxx: Dr. Matsuo Motoaki
Lithium super (fast) Ionic conductivity (Part II)
O14: Dr. Langhammer ChristophIndirect nanoplasmonic sensing applied to hydrogen stogage in nanoparticles and catalysis
O16: Dr. Er Süleyman
Improving hydrogen storage in magnesium
O17: Dr. Milanese Chiara
Cstalysis/destabilization studies on the Mg/MgH system: From lab scale to the realization of a
portable prototype.
O18: Dr. Holtappels Kai
Hydrogen storage in glass capillary arrays
P08: Mr. Martelli Pascal
NMR studies on Li2(BH4)(NH2) AND Li4(BH4)(NH2)3
P09: Mr. Agresti Filippo
Improvement of decomposition properties of LiBH4 dispersed on modified multi-walled carbon
nanotubes
P10: Mr. Pendolino Flavio
Hydrogen evolution from decomposition of borohydrides: The “Boron Effect”

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P11: Dr. Matsuo Motoaki
Litihum fast-ion conduction in LiBH4
P12: Dr. Corno Marta
Thermodynamic properties of AlH3/AlF3 and MgH2/MgF2 systems as hydrogen storage
materials: A computational approach
P13: Dr. Chung Moon-Sun
R&D status on hydrogen production, storage, and utilization technologies in Korea
P14: Mr. Wiedenmann Daniel
Impact of multi-scale pore structure on ion conductivity of asbestos gas separation diaphragms
for alkaline water electrolysis
P15: Dr. Bielmann MichaelHydrogen powered APU for mobile rail catering service: The IHPOS-E project

WEDNESDAY 27. 1. 2010
I06: Dr. Ronnebro Ewa
Light-weight metal-boron-nitrogen systems for high-capacity hydrogen storage
I07: Prof. Dr. Gregory Duncan
Developments in nitridic hydrogen storage materials
O19: Dr. Cakir Deniz
Reaction pathways in the reactive composite Mg(NH2)2 + LiH
O20: Dr. Hu Jianjiang
Catalytic effects of LiBH4 in the hydrogen sorption reaction of 2LIH-Mg(NH2)2 system
O21: Mr. Pistidda Claudio
Reaction mechanisms of formation of 2NaBH4+MgH2 by hydrogenation of 2NaH+MgB2
O22: Ms. Rongeat Carine
Study of the decomposition of CA[BH4]2 prepared by reactive ball milling

THURSAY 28. 1. 2010
O15: Dr. Borgschulte Andreas
From microspots to hydrogen storage by vibrational spectroscopy
O23: Mr. Kato Shunsuke
Roles of surface oxide layer in hydrogen desorption processes
I09: Prof Centi Gabriele
Towards solar fuels by novel photoelectrocatalytic approach
O24: Dr. Laurenczy Gabor
Carbon dioxide as hydrogen vector in H2 storage and delivery
O25: Prof. Dr. Berke Heinz
New catalysts and processes for amine boranes as chemical hydrogen storage materials
O26: Dr. Kozlov Alexey
KEMERIT – Carbon material for energy application

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O27: Dr. Muller Jiri
A multidisciplinary, biological approach using solar energy to capture CO2 while producing H2
and high value products
O28: Prof. Dr. Züttel Andreas
From Hydrides to Synthetic fuels
I10: Prof. Dr. Akiba Etsuo
Investigation of hydrogen storage alloys and their application to on board storage tank
I11: Prof. Dr. Harris Rex
A metal hydride as a means of energy storage in a canal boat
O29: Dr. Vogt Ulrich
Hydrogen technology for a self-sufficient accommodation unit
O31: Dr. Gil Bardají Elisa
Synthesis and properties of LIBH4-Mg(BH4)2 nanocomposites
O32: Prof. Dr. Principi Giovanni
Pellets of MgH2-based composites as practical material for solid state hydrogen storage

FRIDAY 29. 1. 2010
O33: Ms Utz Inga
Experimental results and simulation of a lab-scale hydrogen storage tank based on NaAlH4
O34: Dr. Balog Sandor
Correlation between morphology, water uptake, and proton conductivity in radiation grafted
proton exchange membranes
O35: Dr. Zakaznova-Herzog Valentina
XPS study of materials for membranes in alkaline electrolysis
O37: Prof. Dr. Park NoejungFirst-principles investigations of hydrogenation process of graphene: In the context of hydrogenstorageO38: Prof. Dr. Jhi Seung-Hoon
Optimization of metal dispersion and hydrogen adsorption in doped graphitic materials forhydrogen storage
O38: Mr. Churchard Andrew
A brief review of cyclam and related complexes of nickel: Hydrogenation reduction and carbon
fixation
O39: Ms. Banach Ewa
Al in ZIF-8: encapsulating magic

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SCIENCE OF HYDROGEN & ENERGY AWARD
List of Participants
Information
Notes

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Timetable

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Abstracts

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PROPERTIES, RISKS AND POTENTIAL OF HYDROGEN AS
FUEL FOR COMBUSTION ENGINES
Konstantinos Boulouchos
Laboratorium für Aerothermochemie und Verbrennungssysteme, Institut für Energietechnik,
ETH Zürich, CH-8092 Zürich, Switzerland

The future prospects for H2 asenergy carrier depend on its
competitive position along the wholeenergy conversion chain fromprimary energy sources through H2generation, its storage and finally tothe conversion to useful energy.
Although H2-generation (based onelectrolysis or other routes) andstorage will be of decisive
importance in the future, the focus of
this talk will be on the energy
conversion part.
Here the electrochemical conversion
on the basis of fuel cells, with its – atleast in principle – higher efficiency,
serves as benchmark, against which
future developments of H2-based
combustion systems will compete. In
terms of applications we will discuss
recent research results with pure H2
or H2-containing fuels on one handfor IC engines in transportation andon the other hand for gas turbine
combustion in power generation.
Althoughrequirements
forcombustion optimization in the two
applications are different, identicalimportant characteristics of H2 as
combustion fuel are the source ofsignificant
advantages
againstconventional hydrocarbon fuels inboth cases. On the basis of recent
experimental results we will showthat in addition to the very highlaminar flame speed of H2-air
mixturesthemselves,
boththermodiffusive and hydrodynamic
instabilities
inhigh-pressure
turbulent flow fields result in
extraordinaryhigh
H2-turbulent
flame speeds. These lead to highignition stability and very robust
flame propagation even with verylean or otherwise diluted mixtures.
Therefore high conversion efficiency
together with virtually zero pollutant
isemissions(incl.
NOX)
demonstrated not only in thelaboratory but also in real-worldengines.
Of course important disadvantages
still persist, which may limit theapplicability of H2 in high power
density applications. They refermainly to self-ignition (in IC engines)
and flashback (in gas turbines) due
to the high reactivity of H2-air
mixtures at high pressures andtemperatures. Ongoing research
activities do indeed focus onpromising methods to overcome
these potential drawbacks.
The talk will conclude with a briefsummary concerning factors that willaffectthefuturecompetitive
standing of H2 as energy carrier forengine combustion.

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MONDAYMORNING12

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CRITICAL EVALUATION OF DESTABILIZATION OPTIONS FORHIGH TEMPERATURE METAL BOROHYDRIDESJi Youn Lee, Jae-Hag Lim, JiWoo Kim, Yoonyoung Kim, Young-Su Lee, JaeHyeok Shim, Young Whan Cho
Advanced Functional Materials Research Center, Korea Institute of Science and Technology,
PO Box 131, Cheongryang, Seoul 130-650, Republic of Korea
There are several options to reduce the dehydrogenation temperature of these borohydrides and they
include: i) alloying including cation or anion exchange, iii) size reduction, and iv) mutual destabilization
reaction. Each of them has its own merits and demerits, but a practical solution would be emerged byproper combination of these options. Here, both thermodynamic and kinetic parameters which have strong
influence on dehydrogenation and hydrogenation reactions of these destabilized systems will becomprehensively evaluated using DFT calculations together with some experimental observations. In
addition, some plausible explanations why the predictions do not match quite well with experimental observations will also be presented.

Introduction
Some group I and II metal borohydrides
such as LiBH4, Mg(BH4)2, and Ca(BH4)2 havequite high hydrogen storage capacity andhave recently been shown to be reversible, atleast partially, with or without catalytic additives. However, these borohydrides are thermodynamically too stable to be used formany applications where the required operation temperature is well below 300℃.

Destabilization options
There are several options to reduce thedehydrogenation temperature of theseborohydrides and they include: i) alloying
with other metals (mixed cation borohydrides) or halogen group elements (mixed
anion borohydrides), ii) size reduction, and iii)
mutual destabilization reaction. There arereports on the existence of some mixed1)
cation borohydrides such as LiZn2(BH4)5 as
well as mixed-anion alanates such as
Na3AlH6-xFx.2) However,thermodynamic
stability of these complicated structure andtheir reversibility have yet to be confirmed.
The particle or grain size reduction could
bring both positive and negative effects on
the hydrogen sorption behaviour of metal
hydrides and these include fast reaction

kinetics,
possibledecreaseindehydrogenation temperature with reduced
reaction enthalpy as well as rather poor
3)cycle property and thermal conductivity.
A more complicated but probably effective
way of destabilizing high temperatureborohydrides would be mixing them withother hydrides to drive the dehydrogenation
reaction further down4) and this so-called“reactive hydride composite” concept mightprovide a practical solution for storage
applications as long as both inherently slow
reaction kinetics and rather poor reversibility
issues are solved.

References[1] D. Ravnsbæk, Y. Filinchuk, Y. Cerenius,
H.J. Jakobsen, F. Besenbacher, J.
Skibsted, and T.R. Jensen; Angew.
Chem. Int. Ed. 2009, 48, 6659 –6663.
[2] H. Brinks, A. Fossdal, B. Hauback;
Journal of Physical Chemistry. C, 2008,
112, 5658-5661.
[3] V. Berube, G. Radtke, M. Dresselhaus,
G. Chen; Int. J. Energy Res., 2007, 31,
637–663.
[4] Y. Cho, J. Shim, B. Lee; Calphad, 2005,
30, 65-69.

Corresponding author: Young Whan Cho, email: oze@kist.re.kr, Tel. (+82) (2) 958 5465

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DIBORANE - THE KEY TO REVERSIBLE HYDROGEN STORAGE
IN BOROHYDRIDES
O. Friedrichs1, A. Remhof1, A. Borgschulte1, F. Buchter1, S.-I. Orimo2, A. Züttel1
1

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
2
Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan
We show that diborane (B2H6) plays a key role in reversible hydrogen storage in borohydrides. Therefore
we identified the crucial role of diborane in the formation and decomposition mechanism of borohydrides
and present a model explaining the mass transport during these processes. Based on these insights, wedeveloped a new method for the solvent-free synthesis of borohydrides at room temperature anddemonstrate its feasibility with the synthesis of the following alkali and earth alkali borohydrides: LiBH4,
Mg(BH4)2 and Ca(BH4)2. This method makes possible the preparation of a wide range of different
borohydrides, or even mixed borohydride systems, with tuneable sorption properties.

Introduction
The influence of diborane on the sorption
kinetics of borohydrides has widely been
neglected so far. Partly due to the toxicity ofdiborane, hydrogen emitting borohydrides
have
been
widelystudied.
Theseborohydrides work at higher temperatures,
where diborane decomposes to boron andhydrogen. In this work we demonstrate thatdiborane plays a key role for the sorption
mechanism for all borohydrides. Based on
this understanding we present a new,general and solvent-free synthesis ofborohydrides at room temperature.

Experimental
The synthesis of different borohydrides isperformed by milling the corresponding metal
hydrides in a diborane/hydrogen atmosphere.
The synthesis is monitored by the pressure
decrease in the system during the reaction
with diborane and the final products arecharacterized by XRD. LiZn2(BH4)5 is used
as a diborane source, which desorbs
diborane and hydrogen when heated to
100°C:

Results
Milling of metal hydrides in a diborane
atmosphere leads to the formation of thecorresponding borohydrides as can be seenin Figure
Mg(BH4)2.

1

for

LiBH4,Ca(BH4)2

andFig. 1. Mechanism of the Li[BH4] formation.

The method shows a high yield for thetransformation (LiBH4: 94%, Ca(BH4)2: 91%,
Mg(BH4)2: 73%) which is assumed to follow
the reaction:MHx + x/2 B2H6 → M(BH4)x(M: metal, x: valence of the metal)

References[1] Friedrichs et al; Chem-Eur. J. 15 (2009) 5531
[2] Schlesinger et al; J. Am. Chem. Soc. 75(1953) 1[3] Ravnsbæk et al; Angew. Chem. Int. Ed. 48(2009) 6659

Corresponding author: Oliver Friedrichs, email: oliver.friedrichs@empa.ch, Tel. (+41) (44) 823 4153

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MICROSTRUCTURE AND ITS EFFECTS ON THE HYDROGENSORPTION PROPERTIES OF SOLID STATE HYDROGEN
STORAGE MATERIALSJi Woo Kima,b,*, Jae-Pyoung Ahnb, Oliver Friedrichsc, Ki Bum Kima, Jae-Hyeok
Shimb, Arndt Remhofc, Andreas Züttelc, Young Whan Chob, Kyu Hwan OhaaSeoul National University, Dept. Materials & Engineering, Seoul, Korea

b

Korea Institute of Science and Technology, Advanced Functional Materials Research Center,Seoul, Korea
c

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
Microstructural changes of metal hydrides (MgH2) and thermodynamically destabilized complex metal
hydride systems (LiBH4+MH) are investigated by electron microscopes (Focused Ion Beam, Scanning andTransmission Electron Microscopes). The strong relationship between microstructures and hydrogen
sorption kinetics are discussed based on the results.

Introduction
In order to have a better understanding of thehydrogen sorption behavior of MgH2 andthermodynamically destabilized LiBH4+MHx(M = Mg, Al, Y) systems microstructures areobserved by electron microscopes.

sorption behavior and roles of catalytic
additives are proposed.

Experimental
TEM specimens are prepared by focused ion
beam technique. Crystallographic information
is obtained by high resolution TEM
micrographs and selected area electron
diffraction patterns, followed by analysis withthe software package. Chemical compositionof the sample is obtained using electronenergy dispersive spectroscopy and electronenergy loss spectroscopy.

Results
Hydrogen sorption properties such as
reversibility, decomposition temperatures andsorption kinetics are significantly governed by
the crystallite size, distribution of catalysts
and induced defects by high energy ball
milling. Possible model for the hydrogen

Fig. 1. Formation of free Boron phase during H2cycling of 2LiBH4+Al system

References[1] O.Friedrichs et al; Phys. Chem. Chem. Phys.
11 (2009) 1515.
[2] J.W. Kim et al; J. Power Sourc. 178 (2008)373.
[3] J.W. Kim et al; Scripta Mater. 60 (2009) 1089.

Corresponding author: Ji Woo Kim, email: nvoel04@snu.ac.kr, Tel. (+82) (2) 880 8306

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A STUDY OF LITHIUM-ALUMINUM-BOROHYDRIDE
I. Lindemanna, R. Domènech Ferrera, Y. Filinchukb, R. Cernyc, H.Hagemannc,
L. Schultza, O. Gutfleischaa

IFW Dresden,P.O. Box 270016, D-01171 Dresden, Germany
Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble, Francec
Crystallography and Department of Physical Chemistry, University of Geneva, 1211 Geneva,
Switzerlandb

The double-cation borohydride Li-Al-borohydride was successfully synthesised by high energy ball millingof AlCl3 and LiBH4. The crystal structure was obtained from high-resolution synchrotron powder diffraction
data which reveals a primitive cubic cell of this very complex structure. The compound shows a very low
decomposition temperature (~ 70°C) combined with an high gravimetric hydrogen density of 17.2 wt.%.

Introduction
Recently double-cation systems haveattracted great interest. It was found that thedesorption temperature of the borohydrides
decreases with increasing electronegativity of
the cation [1]. Therefore the decomposition
temperature of the compound is adjustableby combining appropriate cations. Li-Alborohydride was found to show desorption at
a temperature suitable for applications (e.g.
PEM fuel cell). In this work the structure of LiAl-Borohydride is presented as well as thethermal characterisation of the compound inrespect to decomposition pathway of thecompound.

shows a primitive cubic cell. Decompositionof the compound was found at a very low
temperature of about 70°C. In-situ Raman
measurements show the formation of LiBH4
during decomposition (see Fig.1). The highobserved mass loss of about 20% points to
the release of not only hydrogen but also
diborane. This is the main drawback forapplications because it hinders reversibility.

Experimental
AlCl3 and LiBH4 were milled in Ar withdifferent molar ratios in order to synthesise
Li-Al-Borohydride by a metathesis reaction.
High resolution synchrotron radiation powder
diffraction data was collected at ESFR
(Grenoble)
and
used
for
structure
determination. TG, DSC, in-situ Raman andthermal desorption measurements werecarried out to study its decomposition
behaviour.

Fig. 1. In-situ Raman measurement in Ar at RT.

References[1] Nakamori et al., J. Phys. Chem. Solids 69(2008) 2292–2296

Results
We could demonstrate the successful millingof Li-Al-Borohydride. The complex structure
Corresponding author: Inge Lindemann I.Lindemann@ifw-dresden.de, Tel. (+49) (351) 465966

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ROTATIONAL DIFFUSION IN MBH4 (M = Li, NA, K)
Arndt Remhof#, Zbigniev Lodziana#, Pascal Martelli#, Oliver Friedrichs#, JanPeter Embs+, Thierry Strässle+, Andreas Züttel#+ Laboratory for Neutron Scattering, ETH Zürich & Paul Scherrer Institute, CH-5232 Villigen,
Switzerland#

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
We present a combined experimental and theoretical study on the rotational diffusion of (BH4)- ions inalkaline tertrahydroborides MBH4, M=(Li, Na, K). The motions are thermally activated and characterized by
12an activation energies in the order of 0.1 eV, typical frequencies are in the 10 Hz range. In the cubic
NaBH4 and KBH4 phases the motion of the (BH4) ion is dominated by 90° reorientations around thefourfold symmetry axis of the cubic crystal, while it displays a three-fold jump behaviour in the lowtemperature phase of LiBH4. The experimental results are discussed on the basis of DFT calculations,revealing the potential energy landscape of a (BH4) subunit in the crystalline matrix and relating thehydrogen dynamics to the structural properties of the respective compounds.

Introduction
The four hydrogen atoms surrounding thecentral atom in the (BH4)- ion form a regulartetrahedron. At ambient temperatures, thetetrahedra are not fixed in space. They
perform thermally activated jumps about
specific axes. Thereby the crystal structure,i.e. the electrostatic interaction, determines
the rotational axis and the frequency of therotational jumps.

reorientations dominate, while 120° rotational
jumps about the c3 axes are observed for the
low temperature phase of LiBH4. The
different behaviours will be discussed on thebasis of DFT calculations, revealing theelectron distribution and the electrostatic
potential energy landscape of a BH4
tetrahedron in the crystalline matrix. [1,2]10

LiBH 4 (LT)
LiBH 4 (HT)NaBH 4KBH 4The measurements were carried out using
the time-of-flight neutron spectrometer
FOCUS located at the continuous spallation
source SINQ at the Paul Scherrer Institute in
Villigen, Switzerland.

Results
The dwell times of the rotational motion of
the BH4 subunits in MBH4 are in the ps-range
and vary with temperature as displayed in
fig.1. The data can be fitted to the Arrhenius
equation, yielding activation energies about
0.1meV.
The
rotational
axes
were
determined by modelling the elastic
incoherent structure factor. Within the cubic
phases of NaBH4 and KBH4, 90°

 (ps)

Experimental
1

0.1
0.00150.00200.00250.00300.00350.0040-1

1/T (K )Figure 1:Arrhenius behaviour of the rotationalmotion of the BH4 – units in alkaline borohydrides.

References[1] Remhof et al.; JPCC, 113 16834 (2009).
[2] Buchter et al., PRB 78, 094302 (2008).

Corresponding author: Arndt Remhof, email: arndt.remhof@empa.ch, Tel. (+41) (44) 823 4369

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TIME AND FREQUENCY HYDROGEN DYNAMICS IN LiBH4 BY
INFRARED PUMP-PROBE SPECTROSCOPY
Robin Gremaud,1 Esben Ravn Andresen,2 Andreas Borgschulte,1 Peter Hamm2
and Andreas Züttel1
1Empa, Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
Physikalisch-Chemisches Institut, Universität Zürich, Switzerland

2

We study deuterated LiBH4, focusing on the B-H (B-D) stretching vibrations, by infrared (IR) and IR-pumpprobe spectroscopy. We report on anharmonicity and vibrational lifetimes of the B-H and B-D vibrations, aswell as on the BH4 orientational relaxation by polarization-dependent IR-pump-probe measurements. We
then discuss the potential of further development in pump-probe spectroscopy to study structural changes
in real time in complex hydrides.

Introduction
Despite considerable research effort, theconditions for hydrogen uptake and releaseby LiBH4 remain harsh.[1] Fundamental
studies of the BH bond yield valuable
understanding to relate the microscopic tomacroscopic parameters. Such studies were
hitherto done by NMR and vibrational(Raman, IR, inelastic) spectroscopy.

Method2D-IR spectroscopy, which measures signal
against two frequency axes (IR-pump and IRprobe), directly provides information onanharmonicity, Fermi resonances, vibrational
lifetimes, spectral diffusion, and energy
exchange that is not accessible byconventional vibrational approaches.[2]functional theory calculation[3,4] allows us toisolated any particular isotopomer. We find auniversal 1.5 ps vibrational lifetime,
independently of the isotopomer type. The
anharmonicity, nonetheless, increases withlocalization of the BD vibration i.e. with thedecrease of the number of BD bonds per
BH4-nDn. Furthermore, polarization-dependentmeasurements make it possible to follow inreal time the orientational relaxation of thetetrahedral units in the compound. The
BH2D2 tetrahedral unit remains static for up to
5 ps after pump-excitation, confirming theslow rotational relaxation and thermal
disorder of the BH4 unit in the lowtemperature phase.[5] We plan extend ourmeasurements to the high-temperaturephase, where reorientations and thermal
effects play a major role.

References

Results
We study the stretching vibrations in thevarious BH4-nDn isotopomers (n=0…4) ofpartially deuterated LIBH4 by 2D-IR. The
detailed understanding of the BH (BD)stretching modes provided by Raman[3],infrared
spectroscopy[4]anddensity[1] O. Friedrichs et al. Chem. Eur. J. 15, 5531
(2009)[2] P. Hamm et al. Phys. Chem. B 102, 6123
(1998).
[3] R. Gremaud et al. Phys. Rev. B 80, 100301(R)(2009).
[4] E. R. Andresen et al., J. Phys. Chem A 113,
12838 (2009)[5] R. Gremaud et al., MRS Fall Meeting
proceeding (2009)

Corresponding author: R. Gremaud, email: robin.gremaud@empa.ch, Tel. (+41) (44) 823 4933

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SORPTION PROPERTIES OF NaBH4/MH2 (M = Mg, TI) SYSTEMS
S. Garroni1,*, C. Milanese2, A. Marini2, A. Girella2, G. Mulas3, E. Menéndez4, M.
Dornheim5, C. Pistidda5, S. Suriñach1, M.D. Baró1
1

2

Departament de Física, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain, C.S.G.I.,
Dipartimento di Chimica Fisica "M. Rolla", Università di Pavia, Viale Taramelli 16, 27100 Pavia,
Italy,3Dipartimento di Chimica, Università di Sassari, I-07100 Sassari, Italy, 4Institute of Ion
Beam Physics and Materials Research, Forschungszentrum Dresden-Rossendorf, D-01314
Dresden, Germany, 5Institute of Materials Research, GKSS Research Centre Geesthacht
GmbH, D-21502 Geesthacht, Germany

The sorption properties of NaBH4/MH2 (M = Mg, Ti) systems prepared by high-energy ball milling havebeen thoroughly investigated. Concerning the system containing MgH2, the molar compositions 2:1 and
1:2 have been studied and show a multi-step pathway during desorption, where the formation of MgB2
confirms the destabilization of NaBH4 induced by the presence of MgH2. A noticeable kinetic enhancement
is achieved for the system rich in MgH2 (composition 1:2). Even though, full re-absorption is obtained forneither of the two compositions, fast kinetics is achieved. The unsuspected formation of the perovskite
type-hydrides NaMgH3 is detected and it is shown that this ternary phase contributes to reducing thegravimetric capacity of the systems. Conversely, in the system 2NaBH4/TiH2, there is no formation of theintermetallic TiB2.

Experimental
Three different mixtures were prepared,
namely 2NaBH4 + MgH2, NaBH4 + 2MgH2
and 2NaBH4 + TiH2. The samples werecharacterizedbyScanning
Electron
Microscopy, X-ray powder diffraction, Sievert
type apparatus, solid-state Nuclear Magnetic
Resonance and High Pressure Differential
Scanning Calorimeter (HP-DSC).

Results
Regarding the system based on MgH2, thatthe desorption kinetics can be improved bysimply operating on the stoichiometriccompound [Fig. 1]. In fact, while the system
NaBH4 + 2MgH2 desorbs in 3 hours, thecomposite 2NaBH4 + MgH2 desorbs in 20 h
indicating that the destabilization of NaBH4 ismainly correlatedwith the amount of MgH2. Full absorption is
not achieved for both compositions and theabsorbed hydrogen is directly linked to theamount of formed NaBH4 after the process.
Outstandingly, fast absorption are obtainedfor 2:1 and 1:2 composites. Moreover, theunsuspected formation of the perovskite
type-hydride NaMgH3 is detected in the final
products, which contributes to the decreaseof the sorption capacity of the whole system.
Remarkably, a novel route to produce thisternary hydride from Na/NaH and MgB2 isestablished. Concerning the 2NaBH4 + TiH2
system, the desorption is not fully reached
due to the stability of the TiH2 counterpart. In
contrast with the systems based on MgH2,
the formation of TiB2 is not detected.
500
0

450
-2

2 NaBH4 + MgH2

NaBH4 + 2MgH2

-4

400

350

-6

Temperature

In this work, a detailed study of the 2NaBH4 +MgH2 and NaBH4 + 2MgH2 composites isreported. It will be demonstrated thecomplete desorption for both the systems
and fast re-absorption kinetics. The formationof NaMgH3 is also observed. In a second partof this work the kinetic properties of thesystem 2NaBH4 + TiH2 are also discussed.

wt% H2Introduction

300

-8

-10

0

200

400

600

800

1000

250
1200

Time, min.

Fig. 1. Thermal programmed desorption (TPD)
profile acquired on the 2NaBH4 + MgH2 (blue line)
and NaBH4 + 2MgH2 (green line) systems.

Sebastiano Garroni, email: Sebastiano.garroni@campus.uab.cat, Tel. (+34) (666) 310427

19

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

ADDITIVES EFFECT ON SYNTHESIS AND DECOMPOSITION OF
MAGNESIUM BOROHYDRIDE.
R. Domènech-Ferrer, I. Lindeman, I. Llamas-Jansa, O. Gutfleisch.
IFW Leibnitz Institute, Dept. 21, IMW, Dresden, Germany.
The
synthesisofMg(BH4)2
has
been
performedbythemetathesis
reaction
2LiBH4+MgCl22LiCl+Mg(BH4)2 with and without 1% molar ratio of TiCl3, TiF3 and ScCl3. The synthesis ofmagnesium borohydride was compared by using these three additives as well as its decomposition steps.
The addition of these compounds has been found to reduce the reaction yield of Mg(BH4)2 in all cases
except for ScCl3. No significant improvement in the decomposition temperature was achieved in any case.
However, LiCl produced in the metathesis reaction has been found to destabilize the borohydride.

Introduction
Magnesium borohydride is a very promising
compound for on board hydrogen storage
due to its high gravimetric concentration(14.9%wt) and the low decomposition
enthalpy of 37kJ/mol H2 [1]. However, it
decomposes at too high temperature. Also,
the reversibility has been achieved only
under very high pressures (950 bar H2 at
400°C) [2].

case without any additive. There was no
significant improvement in the decomposition
temperature with any additive. However, thepresence of LiCl produced during milling
destabilizes Mg(BH4)2 by the formation of
Li2MgCl4 at about 150°C (Fig. 1)

Experimental
LiBH4 and MgCl2 with a molar ratio 2:1 havebeen milled for 12 hours in 10 bar of H2 withand without 1%mol of TiCl3, TiF3 and ScCl3.
Pressure and temperature were measured
during milling to follow in-situ the evolution of
the compounds inside the milling vial.
Raman, XRD, DSC and TG measurements
were performed to characterize the formation
anddecompositionofmagnesiumborohydride with and without additives.

Figure 1: TG measurement of Mg(BH4)2 + 2LiCl in
Ar atmosphere and its decomposition steps.

References
Results
Addition of TiF3 reduces the reaction yield ofmagnesium borohydride due to the formationof Li2MgCl4. TiCl3 destabilizes LiBH4 by theformation and decomposition of Ti(BH4)3
during milling [3]. Only sample with ScCl3
showed a reaction yield similar than in the[1] H. W. Li et al, Nanotechnology 20 (2009)
204013[2] G. Severa, Gordon’s Conference (2009).
[3] M. Au et al, J. Phys. Chem. C (2008), 112,
18661.

This work has been performed with the financial support of Funchy project.

20

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

MONDAYAFTERNOON
FuncHy21

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

TAILORING BOROHYDRIDES FOR REVERSIBLE HYDROGEN
STORAGE
Ulrike Bösenberg, Gagik Barkhordarian, Martin Dornheim, Rüdiger Bormann
Institute of Materials Research, GKSS Research Centre, Geesthacht, Germany
Due to the outstanding gravimetric hydrogen content, borohydrides have a high potential to be utilised asmaterials for hydrogen storage. However, reversible adsorption and desorption of hydrogen at reasonabletemperatures and hydrogen pressures could not be achieved for single-phase borohydrides so far. A
breakthrough was achieved by the development of the Reactive Hydride Composites (RHC), which containmetal borides. Thereby the sorption kinetics could be substantially improved and the reaction enthalpy
could be decreased to values of technological interest. The talk will summarise the recent comprehensive
understanding of the sorption kinetics and will propose critical issues for further research.

Introduction
The limited resources as well as the highemission of greenhouse gases and pollutants
during the combustion of fossil fuels areseriousconcerns
andrequirethedevelopment of alternative energy carriers,
such as hydrogen. One of the major
challenges for the implementation ofhydrogen technology is its safe and reliable
storage. Many metals react exothermicallywith hydrogen to form a hydride, the releaseof hydrogen requires a supply of heat andcan thus be controlled. However, at present,no single metal hydride fulfils all therequirements on storage capacity, sorption
temperature and reaction enthalpy. A
breakthrough was achieved by thedevelopment of the Reactive HydrideComposites (RHC) [1, 2, 3].

Results
With respect to gravimetric storage capacity,
the reversible system of 2LiBH4+MgH2 ↔
2LiH+MgB2+4H2 is most favourable, as it canstore up it 11.4 wt %. The reaction enthalpy
amounts to -46 kJ/mol H2, which leads to an
estimated equilibrium temperature at 1 barhydrogen of 170°C. However, kinetic
constraints limit the utilisation of thecomposite. Therefore, transition-metal based
additives were employed to enhance
nucleation, growth and transformation of the
MgB2 phase, which are the rate limiting
factors during desorption and absorption
process. The underlying mechanism has
been investigated in detail and is based on
the formation of nanoscale transition metal
borides. As a result, transition-based
additives improve the kinetics of the sorption
reactions significantly [4, 5, 6].

References[1] G. Barkhordarian et al.: GKSS patentapplication 2004, J. Alloys & Compounds 440(2007) L18-L21[2] J.J. Vajo et al.: patent application 2004, J.
Phys. Chem. B 109 (2005) 3719-3722[3] M. Dornheim et al., Scripta Materialia 56(2007) 841-846[4] U. Bösenberg et al., Acta Materialia, 55 (2007)
3951-3958[5] U. Bösenberg et al., Nanotechnology, 20(2009) 204003[6] U. Bösenberg et al., submitted to Acta
Materialia (2009)

Corresponding author: Rüdiger Bormann, email: ruediger.bormann@uni-bayreuth.de, Tel. (+49) (921)55520022

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

LIGHT-WEIGHT SODIUM ALANATE THIN FILMS GROWN BY
REACTIVE SPUTTERING
Matteo Filippi1, Jan H. Rector1, Robin Gremaud1, Michiel J. Van Setten2,
Bernard Dam3
1Department of Physics and Astronomy, Condensed Matter Physics, Vrije Universiteit, De Boelelaan
1081,1081 HV Amsterdam, The Netherlands2
2 Institut für Nanotechnologie, Forschungszentrum Karlsruhe P.O. box 3640 D-76021 Karlsruhe, Germany
3 Delft University of Technology, DelftChemTech, MECS, Julianaweg 136, 2628 BL Delft, The Netherlands
We report the preparation of sodium alanate (NaAlH4), a promising hydrogen storage material, in a thinfilm form using co-sputtering in a reactive atmosphere of atomic hydrogen. We study the phase formationand distribution, and the hydrogen desorption, with a combination of optical and infrared transmission
spectroscopy. We identify the formation of sodium alanate with metallic impurities. The as-deposited
NaAlH4 decomposes into NaH and Al upon high-temperature annealing. Moreover, we explore the effect ofmetallic titanium doping in the desorption properties of the alanate using different artificially obtained
heterostructures

Introduction
Thin films are a model system to explore newmetal hydride storage options, using
combinatorial
methodssuch
ashydrogenography. These methods allow afast and efficient exploration of thethermodynamic properties, having a speed ofanalysis that is out of reach for bulk chemical
methods. Here we report for the first time thesynthesis and characterization of lightweight
sodium alanate thin films.

decomposes into NaH and Al afterdesorption. The effect of metallic Ti doping is
also explored. After desorption we observe
for both the undoped and Ti-doped samples
a macroscopic Al segregation, which
probably hinders the reverse reaction undermoderate conditions. This result opens theroute to the analysis of the storage propertiesof the sodium alanate and other light-weightcomplex metal hydrides, such as LiAlH4, withcombinatorial techniques.

Experimental

References

We co-sputter Na-Al thin films in a hydrogen
reactive atmosphere. Atomic hydrogen isprovided by a hydrogen atomic source which
splits molecular hydrogen at a hot W
filament. We characterize the films with a
combination of optical transmission (in theUV-visible range) and infrared transmission
both in the as deposited state and after hightemperature annealing.

[1]R. Gremaud et al.; Advanced Materials 19(2007) 2813[2]M. Filippi et al.; Applied Physics Letters 95(2009) 121904

Results
We find optical signatures (in the IR and UV
regions) of the formation of NaAlH4, which
Corresponding author: Matteo Filippi, email: mfilippi@few.vu.nl, Tel. (+31) (20) 598 7912

23

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

ALANATES – SYNTHESIS, TRANSFORMATION MECHANISM
AND TECHNICAL STATE OF THE ART
Maximilian Fichtner, Christoph Frommen, Aline Léon, Wiebke Lohstroh
Alanates have been investigated for H storage applications with a focus on improving theirtransformation kinetics, and understanding the mechanism of the hydrogen absorption anddesorption. The phase transformations in the solid, the rate limiting steps of the transformation,
the evolution of different dopants during cycling and new ways to tune the thermodynamics will
be discussed in more detail. Moreover, technically relevant aspects such as safety properties
and coupling of alanate tanks with a high temperature PEM fuel cell will be presented.

24

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

BOROHYDRIDES
Ph. Mauron1, F. Buchter1, O. Friedrichs1, P. Martelli1, A. Remhof, A. Züttel1, K.
Chlopek2, E.G. Bardaji2, N. Hanada, W. Lohstroh2, M. Fichtner2, R. DomènechFerrer 3, I.L. Jansa3, O. Gutfleisch3
1

Empa Materials Science and Technology, Hydrogen & Energy, 8600 Dübendorf, Switzerland

2

Karlsruhe Institute of Technology (KIT), Inst. Nanotechnology, 76021 Karlsruhe, Germany

3

IFW Leibniz Institute for Solid State and Materials Research, Inst. for Metallic Materials, 01171
Dresden, Germany
The aim of the FuncHy Project from the Helmholtz-Initiative is to find a hydrogen storage
material for mobile applications with a gravimetric hydrogen storage density higher than 5wt%
operating at temperatures lower than 150°C with technically reasonable kinetics. Different
material classes were investigated, the one presented here are the borohydrides.
Different borohydrides were successfully synthesised with different new methods. With a wet
chemical method (Mg(BH4)2, Ca(BH4)2 [1]), directly from the elements (LiBH4 [2]), and byreactive ball milling (Mg(BH4)2 [3]).

Thermodynamic characterizations of the dehydrogenation reaction were made by pcT (LiBH4[4], NaBH4, 6LiBH4+ CeH2). The reversibility of LiBH4 [4] and Mg(BH4)2 [5] has been
investigated. The influence of different additives (metal chlorides) and nanoconfinement [6] on
the desorption properties of Mg(BH4)2 was investigated by DSC. It has been shown that thereaction of borohydrides with metals or metal hydrides is decreasing the thermodynamic stability
e.g. 2LiBH4 + Al [7] or 6LiBH4 + CeH2.
The crystal structure (β-, γ-phase of Ca(BH4)2 [8,9]) and dynamical properties (LiBH4) weresuccessfully determined by synchrotron and neutron powder diffraction.

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

Chlopek K, Frommen C, Leon A, et al., Synthesis and properties of magnesium tetrahydroborate, Mg(BH4)2, J Mat Chem 17(2007) 3496
Friedrichs O, Buchter F, Borgschulte A, et al., Direct synthesis of LiBH4 and LiBD4 from the elements, Acta Mater 56 (2008)
949
Llamas-Jansa I, Rongeat C, Doppiu S, et al., Characterisation of complex hydrides synthesised or modified by ball
milling, Int J Mat Res 99 (2008), 553
Mauron P, Buchter F, Friedrichs O, et al.O. Friedrichs, et al., Stability and reversibility of LiBH4, J Phys Chem B
112 (2008), 906
Hanada N, Frommen C, Lohstroh W et al., Thermal decomposition steps of Mg(BH4)2 under He flow and H2
pressure, J Mater Chem 18 (2008) 2611
Fichtner M, Zhao-Karger Z, Hu JJ, et al., The kinetic properties of Mg(BH4)2 infiltrated in activated carbon,
Nanotech 20 (2009) 204029
Jin SA, Shim JH, Cho YW, et al., Reversible hydrogen storage in LiBH4-Al-LiH composite powder, Scripta Mater
58 (2008) 963
Buchter F, Lodziana Z, Remhof A, et al., Structure of Ca(BD4)2 beta-phase from combined neutron andsynchrotron X-ray powder diffraction data and density functional calculations, J Phys Chem B 112 (2008) 8042
Buchter F, Lodziana Z, Remhof A, et al. Structure of the Orthorhombic gamma-Phase and Phase Transitions ofCa(BD4)2, J Phys Chem C 113 (2009) 17223

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4th Hydrogen & Energy Symposium

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Li-Mg-N-H hydrogen storage systems: composition variation,
Sorption properties and mechanistic study
Jianjiang Hu1, Wiebke Lohstroh1, Francesco Dolci1,2, Eveline Weidner2 andMaximilian Fichtner1
1

Institute for Nanotechnology, Karlsruhe Institute of Technology, Postfach 3640, D-76021
Karlsruhe, Germany

2

JRC Institute for Energy, Cleaner Energy Unit, Petten, the Netherlands

Li-Mg-N-H hydrogen storage materials offer attractive properties for solid state hydrogenstorage in mobile applications. The solid state reaction is reversible at moderate conditions (i.e.
at 200 °C and 100 bar H2) and the reported reaction enthalpy for the mixture Mg(NH2)2 + 2 LiH
amounts to 39 kJ / mol H2 and is thus in the desired range. Starting from the above system, thehydrogen content can be increased as more LiH is added to the system.
We will present a systematic study of the sorption properties of various Mg(NH2)2 + n LiH (n = 2,
3/8, 4) mixtures and the reversible hydrogen capacity, thermodynamic properties and thereaction mechanism will be presented. Remarkably, it has been shown that all mixtures exhibit
an intermediate hydrogenation step where a new ternary imide phase Li2Mg2(NH)3 is formed.
This intermediate phase and its implications for the actual usable hydrogen content will be
discussed. In addition, the effects of various additives, i.e. LiBH4, in enhancing hydrogen
desorption and absorption were investigated, which provides supportive information for thereaction mechanism.

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4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

REACTION PATHWAYS AND ROLE OF ADDITIVES IN REACTIVE
HYDRIDE COMPOSITES
Ulrike Bösenberg, Martin Dornheim, Rüdiger Bormann
Institute of Materials Research, GKSS Research Centre, D-21502 Geesthacht, Germany
In the frame of the Helmholtz initiative “Functional Materials for Mobile Hydrogen Storage” the reaction
pathways as well as the role of additives in Reactive Hydride Composites (RHC) such as LiBH4-MgH2,
Ca(BH4)2-MgH2 or NaBH4-MgH2 have been investigated in detail. For all systems the reaction pathway
during the desorption reaction shows a strong dependency on the applied temperature and pressure. The
role of transition-metal based additives and additives in general was exemplarily investigated for Zr-based
additives in the LiBH4-MgH2 system. From a comprehensive analysis of the chemical state, size as well as
location of the transition metal in combination with an analysis of the reaction kinetics a model is proposed,
which indicates nucleation and growth of MgB2 in a limiting role during the desorption reactions under the
given experimental conditions.

Introduction
The novel Reactive Hydride Composites(RHC) show extremely promising values regarding the reaction enthalpy and capacity byweight for future mobile applications. This isachieved by an exothermic reaction to form a
new compound during the endothermic desorption reaction. Thus, the overall reaction
enthalpy is lowered. One prominent example
for this material class is the system of LiBH4MgH2 reacting to LiH and MgB2 and hydrogen in the desorbed state. Other promisingsystems are Ca(BH4)2-MgH2 reacting to CaH2
and MgB2 during desorption or the system of
NaBH4-MgH2. In contrast to the hampered
absorption reactions of the pure borohydrides, the absorption reaction in the RHC
was observed to be much facilitated.

Results
The reaction mechanism and probable intermediate phases are proposed to depend
strongly on pressure and temperature during
the experiment [1].
Furthermore, for the system of LiBH4-MgH2
detailed investigations were performed toanalyze the function and mechanism of additives [2]. Therefore, information on state, sizeand location the transition metal is necessary
and X-ray absorption spectroscopy (XAS),
anomalous small angle scattering (ASAXS)

and transmission electron microscopy (TEM)
was performed exemplarily for Zr-based additives. Measurements of the as-milled aswell as cycled samples indicate a chemical
shift of the absorption edge of the compounds towards a lower oxidation state upon
cycling and partly during the ball-milling
process. The energy dependence of thesmall angle X-ray scattering near the Kabsorption edge is used to access directly
the resonant scattering contribution of theZirconium based additives. The scattering
curves indicate a weakly segregated networkof the transition metal additives in the grainboundaries of the particles. Upon cycling acoarsening of the crystallites as well as the
additives can be observed from fitting acorrelation length model to the scattering
curves. These observations were supported
recently by TEM investigations, showing thepresence of ZrB2 nanoparticles in the grainboundaries. In combination with analysis of
the reaction kinetics a model is proposed,
assigning nucleation and growth of MgB2 arate limiting role during the reactions.

References[1] Bösenberg et al; in preparation[2] Bösenberg et al; Nanotechnology 20 (2009)

Corresponding author: Ulrike Bösenberg, email: ulrike.boesenberg@gkss.de, Tel. (+49) (0)4152 87 2565

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4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

SYSTEM INTEGRATION: FROM MATERIALS RESEARCH TOTANK SYSTEM
J. M. Bellosta von Colbe, J. Jepsen, G. Lozano, R. Bormann, M. Dornheim
GKSS Research Centre Geesthacht GmbH, Institute of Materials Research, Dept. of Nanotechnology, D21502 Geesthacht, Germany
The overall sorption behaviour of light metal hydrides is found to be critically dependent on the amount ofsample and the design of the experimental vessel. As opposed to small sample batches, in large sample
batches of sodium alanate, the hydrogenation kinetics are almost entirely determined by heat transfer [1],despite the fact that its reaction enthalpy is significantly lower in comparison with other well known
hydrides like MgH2. Moreover, a study of the economics of hydrides shows distinct advantages incomparison with the more established storage technologies in a wide range of tank sizes [2].

Introduction
In the past most studies on light metal
hydrides for hydrogen storage have been
performed using small samples in the range
of a few mg to several grams only. Thus,
phenomena, factors and engineering aspects
which reveal their influence in larger samples
went unnoticed. Such are the thermal
conductivity and the cost.

Concept
The advantage of solid storage systems isthe fact that waste energy from the hydrogenconsumer can be used during discharging of
the tank and recovered during charging,redressing the energy investment of thecharge and leading to an overall increase in
the efficiency (Fig. 1). In order to achievethis, the size-dependent issues mentioned
need to be resolved.

Results
In order to efficiently store hydrogen, theoverall energy balance of the whole storage– consumer system has to be considered
andoptimized.
Therefore,
processes
characterized by unrecoverable energy
losses like compression and liquefaction
should be minimized, and maximum use ofwaste energy from the surroundings should
be made (Fig. 1). Thermal conduction, being
the key driver for good sorption kinetics ofmetal hydrides, plays a fundamental role.

Heat transfer in large beds of hydrides canbe improved through several methods: Usinga high throughput of heating/cooling agent(which leads to high losses and has limits as
to its effectiveness); modifying the design ofthe bed to improve heat transfer (again, acompromise has to be struck to obtainreasonable capacities, as too small beds
decrease also this factor) and using highconductivity agents to improve the intrinsic
heat conductivity of the bed. This lastapproach, though implying slight losses incapacity, has shown to yield the best results.
Conventional
storage

HydrogenHydrogen

EnergySolidstorage
EnergyEnergyCharging
Storage

Storage

Consumer
Waste
heat

Consumer
Waste
heat

Discharging
EnergyEnergyFig. 1. Operation scheme of an integrated solid
storage system compared with the conventional
technology.

References[1] Lozano et al, Int. J. of Hyd. Ener. 34 (2009)
1896[2] Jepsen et al; in preparation

Corresponding author: Jose M. Bellosta von Colbe, email: jose.bellostavoncolbe@gkss.de, Tel. (+49)(4152) 87 2554

28

4th Hydrogen & Energy Symposium

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TUESDAY29

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

ON THE HYDROGEN-DEFECT INTERACTION
FRAMEWORK OF A DEFACTANT CONCEPT

IN

THE

Reiner Kirchheim
Institut für Materialphysik, Georg-August-Universität Göttingen, D-37077 Göttingen, Germany
For both hydrogen storage and hydrogen embrittlement the interaction of hydrogen with defects likeinterfaces, grain boundaries, dislocations and vacancies plays an important role. Models explaininghydrogen embrittlement as caused by enhanced local plasticity are discussed in the light of a novel
concept describing solute defect interaction in a thermodynamic framework.

Introduction
In textbooks on materials science thesolute/defect interaction is treated in terms ofa site energy spectrum, where hydrogenatoms find sites of different energy at a
defect. Fermi-Dirac Statistics is used todetermine the distribution of H-atoms among
these sites (a detailed analysis is provided inRef. [1]). An alternative approach is thedefactantconcept,
wherehydrogensegregating to the defect is lowering thedefect energy and, therefore, increases therate of defect generation.

Theoretical Background
Surfactants (SURFace ACTing AgeNTS).
molecules have a hydrophilic head group anda hydrophobic tail. They segregate to thewater surface and lower its energy  [2]Recently it has been proven that this can beapplied to other crystalline defects like
dislocations and vacancies as well [2] and a
new term “defactants (DEFect ACTing
AgeNTS)” was introduced [3], in order tocover the action of atoms segregating to
defects in solids and reducing their formationenergy like surfactants reduce surface
energies in liquids. By using the defectdensity , i.e. grain boundary area,

dislocation length, number of vacancies pervolume V a unified equation for the excess
solute can be defined as [3]:A 

1 n AV ,

V ,T ,  A , n B
where nA is the number of defactant atoms or
molecules.

Results
The novel defactant concept is useful for a
deeper insight into many phenomena likesuperabundantvacancies,hydrogenembrittlement, defect generation during ball
milling, enhanced mobility of dislocations,
thermal stability of nanocrystalline materials
etc. [2].

References[1] R. Kirchheim, in: H. Ehrenreich, F. Spaepen,(Eds.), Solid State Physics, Elsevier,
Amsterdam, 2004, Vol. 59, 203-305[2] R. Kirchheim, Acta Mater. 55 (2007) 51295138 and 5138-5148[3] R. Kirchheim, Int. J. of Materials Research 100(2009) 483

Corresponding author: Reiner Kirchheim, email: rkirch@ump.gwdg.de, Tel. (+49) (551) 39 5001

30

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

INDIRECT
NANOPLASMONICSENSINGAPPLIEDTO
HYDROGEN STORAGE IN NANOPARTICLES AND CATALYSIS
C. Langhammer, E. M. Larsson, V. P. Zhdanov, B. Kasemo and I. Zorić
Chalmers University of Technology, Department of Applied Physics, 412 96 Göteborg, Sweden

Introduction
The Localized Surface Plasmon Resonance(LSPR) is a collective excitation of the freeelectrons in a metal nanoparticle and is highly
sensitive to changes in the particle nanoenvironment. Nanoplasmonic sensing thus
offers a combination of ultrahigh sensitivity,
small sample volume and capability for realtime, remote readout as well as single-particle
measurement capability. Application of LSPRbased sensing in hydrogen storage in
nanoparticles and heterogeneous catalysis will
be discussed.

Experimental
The“indirect
nanoplasmonic
sensing”
technique employs arrays of Au nanodisks on
a substrate as plasmonically active sensor.
(Fig. 1a) The Au plasmon excitation causes apeak in the optical extinction vs. wavelength(λ) spectrum. The peak position, λmax, or width,
λfwhm, measured in the experiment, is sensitive
to surface changes. The Au LSPR sensor
nanodisks are protected by a thin SiO2 spacer
layer and decorated with smaller nanoparticles(1<D<20 nm), which are to be investigated. In
the presented work indirect sensing wasapplied to:i) study systematically the size-dependent
kinetics and thermodynamics of H2 ab/desorption in Pd clusters.
ii) take first steps towards single nanoparticle
hydrogen storage measurements.
iii) detect surface coverage changes on Pt
nanoparticles, with a sensitivity of less than 0.1
ML of oxygen during oxidation of H2 or CO.

concentration in the Pd clusters. This linear
scaling is verified by complimentary QCM
measurements. The obtained thermodynamic
data (Sieverts and Van’t Hoff analysis) andkinetics show strong particle size effects. The
scaling of the hydriding and dehydriding
satisfy power and power-exponential laws ingood agreement with diffusion-controlled
hydriding kinetics. The latter is explained by
the effect of surface tension on hydrogen
desorption from the nanoparticle surface. The
observed (almost) absent hysteresis for small
particles is explained by complementary
calculations showing that the contribution oflattice strain to the free energy of hydride
formation/decomposition
decreases
withdecreasing particle size.
Catalysis: Fig. 1c shows Δλmax and the sample
temperature shift, during the oxidation of H2(H2+½ O2 H2O) over Pt nanoparticles vs. therelative H2 concentration (α = H2/(H2+O2).
The most notable feature is the discontinuous
step up (down) in Δλmax at αcr = 0.5,
corresponding to the well known kinetic phasetransition in the H2+O2 reaction, where asudden transition occurs from an oxygen
covered surface at low α to a partiallyhydrogen covered surface at high α. This
result indicates the LSPR sensing mightprovide a valuable tool in the quest of bridging
the pressure and materials gaps in catalysis
research.

Results
Hydrogen Storage: The obtained p-Δλfwhm
isotherms agree very well with corresponding
literature data (Fig. 1b), implying linear scalingof the Au-sensor LSPR response to hydrogen

Fig. 1. a) Indirect sensing platform. b) p-Δλfwhm
hydrogen ab/desortion isotherms for Pd clusters(<D>=5nm). c) Kinetic phase transition duringoxidation of H2 on Pt clusters.

Corresponding author: Christoph Langhammer, email: clangham@chalmers.se, Tel. (+46) (0)31 772 3007
31

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

IMPROVING HYDROGEN STORAGE IN MAGNESIUM
Süleyman Er1, Gilles A. de Wijs2 and Geert Brocks1
1Computational Materials Science, Faculty of Science and Technology and MESA+ Institute for
Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands.
2

Electronic Structure of Materials, Institute for Molecules and Materials, Faculty of Science,
Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
Magnesium dihydride (MgH2) will become a very useful hydrogen storage material when(de)hydrogenation kinetics are improved and desorption temperature is markedly lowered. Recent
experimental and theoretical studies show that mixing MgH2 with lightweight transition metals (TM) (=Sc,Ti, V, Cr) noticeably improves the hydrogen kinetics. Here, using first-principles calculations, we show that
adding Al or Si to Ti-alloyed MgH2 destabilizes it significantly. As an alternative approach, we compare
thermodynamic properties of Mg-Ti-Al(Si) bulk systems to that of the nano-layered structures.

Introduction
We investigate hydrogen storage properties
of some of the most promising magnesium
based hydrides. In pure form, MgH2 stores
7.6 weight % hydrogen. However, forpractical reasons, hydrogen kinetics ofdesorption and absorption have to be
improved and desorption temperature (573K)
has to be pulled down considerably.

Computational Methods
Density Functional Theory (DFT) calculations
are performed at the level of the generalized
gradient approximation (GGA) using the
PW91 functional. We employ the projector
augmented wave (PAW) technique and aplane wave basis set, as implemented in the
Vienna Ab initio Simulation Package (VASP).
The accuracy of the results is warrantedusing a high kinetic energy cutoff (518 eV) forthe plane wave basis in combination withreasonably dense k-point meshes (at most-1with 0.02 Å spacing).

(de)hydrogenation kinetics of bulk MgH2 [1].
Within the set of tested lightweight TMs, themost promising alloying element is identified
as titanium. Here, for Mg-Ti hydrides, weestablish that the same phase transition
occurs both in the ordered structures, as wellas in the random alloy hydrides [2].
Ti alloying alone, however, is not sufficient todecrease the stability of the hydride phases
and eventually to reduce the hydrogen
desorption temperature. We find that Mg-Ti
hydrides are markedly destabilized by addingaluminium or silicon [3]. Contrarily, thestability of the initially immiscible Mg-Ti bulk
system, the case when all the hydrogens are
removed, is increased.
Finally, we show that controlling the structureof Mg-Ti-Al(Si) alloys (i.e., growing them inlayered forms) has a beneficial influence on
the thermodynamic properties [3]. In thisrespect, the Mg-Ti-Al(Si) system becomes astronger candidate for hydrogen storage.

Results

References

Recently, in connection with the experiments,
we found that TM alloying initiates a phasetransition
that
resultsinsignificant
enhancements
intheusuallyslow[1] S. Er et al., Phys. Rev. B 79, 024105 (2009).
[2] S. Er et al., J. Phys.: Condens. Matter (2009).
[3] S. Er et al., (in preparation)

Corresponding author: Süleyman Er, email: s.er@utwente.nl, Tel. (+31) (53) 489 3167

32

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

CATALYSIS/DESTABILIZATIONSTUDIESON
THE
MAGNESIUM/MAGNESIUM HYDRIDE SYSTEM: FROM LABSCALE TO THE REALIZATION OF A PORTABLE PROTOTYPE.
Chiara Milanesea, Andrea Girellaa, Giovanna Brunia, Vittorio Berbennia, Paolo
Matteazzic, Amedeo Mariniaab

CSGI - Physical Chemistry Dept., University of Pavia, Viale Taramelli 16, I - 27100 Pavia, Italy;
MBN Nanomaterialia SpA, Via G. Bortolan 42, I - 31050 Vascon di Carbonera (TV), Italy.

In the frame of the Italian joint project “Nanostore”, focused on Mg-based composites prepared by highenergy ball milling, many solutions have been explored in order to catalyze the sorption reactions of the
Mg - MgH2 system and to destabilize MgH2, lowering both its decomposition temperature and enthalpy.
The best promising systems, i.e. Mg – Ni – C – TiO2 and Mg – C – MO (MO = TiO2, Nb2O5) composites,
were optimized concerning stoichiometry, milling time and aggregation state (powders or pellets withdifferent density) for the use as H2 storage media (100 g H2) in a portable 1 kW PEM-FC prototype. The
first tests of the device will also be discussed.

Introduction
In this work the kinetic and thermodynamic
sorption performance of Mg – Ni – C – TiO2
and Mg – C – MO (MO = TiO2, Nb2O5)
composites optimized for the use as storage
materials in a portable prototype is shown.
The differences in the behaviour between
powders and pellets (prepared with different
densities by both conventional and nonconventional compaction methods) is
discussed.
Finally,the
set-upandperformance of the final version of the
prototype is presented.

Experimental
The composites were prepared on
industrial scale (100 g for each batch) by
high energy ball milling under 5 bar Ar fordifferent processing times (from 45 min to
240 min). Concerning lab scale analyses(500 mg samples), the activation was
performedbysubsequentcharging/discharging runs at 350 °C and35 bar/1 bar in a Sievert type apparatus.
Subsequently, the sorption properties ofthe fully activated mixtures were evaluated(280°C  T  350°C; 30 bar  P H2  1bar) by kinetic runs, TPD and PCI
analyses. The sorption enthalpies were
measured on fully activated samples (10mg) by high pressure calorimetry. The
chemical nature and the microstructure of
the phases formed after milling, charging
and discharging were evaluated byrefinement of the experimental X-ray
diffraction patterns. The performance ofthe best performing composites are underevaluation directly in the prototype tank(1500 g samples).

Results
Gravimetric capacities of 6.4% and 6.9%
were obtained for Mg – Ni – C – TiO2 and Mg– C – MO systems respectively at T = 350°C. At this same temperature, the lab scale
analyses showed that the composites charge
up to 90% of their filling up in 1.5 min
maximum. Moreover, more than 98% of thefull discharging, lasting 10 min, takes placewith a rate fully suitable to feed the 1 kW fuelcell. The first tests of the storage materials
directly in the prototype are very promising,with the storage performance being very
similar to that obtained on lab scale.

Corresponding author: Chiara Milanese, e-mail: chiara.milanese@unipv.it, Tel. (+39) 0382 987 670.

33

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

HYDROGEN STORAGE IN GLASS CAPILLARY ARRAYS
Kai Holtappels*, Martin Beckmann-Kluge*, Dan Eliezer***

BAM Federal Institute for Materials Research and Testing, Dept. II “Chemical Safety
Engineering”, Div. “Gases, Gas Plants”, 12200 Berlin, Germany** C.En Ltd., 3 Sonnhaldenstrasse, Postfach CH-8032, Zurich, Switzerland
A new light-weight storage system is being developed. Thereby gases are stored at high pressures inglass structures which are closed by an innovative technology. Basic material tests have been carried out
to determine storage capacities in dependence of main characteristics of the glasses and their structures.
Stresses in the structures were modelled by FEM software to find the best structures. First storage results
showed that gravimetric and volumetric storage capacities already surpassed the targets of the DoE 2010.

Introduction
Central to the realization of the profoundpotential of hydrogen technology is theresolution of obstacles inherent in thestorage of hydrogen. Conventional storage
methods pose weight, volume, safety, costand permeation obstacles and are unable tomeet future on-board application goals as
defined by the US Department of Energy(DOE). The success of the hydrogen
economy is entirely dependent on themeeting of these goals. A novel method ofhydrogen storage which utilizes an array ofthin sealed capillaries made of quartz orother glasses will be presented.

of hydrogen gas, under storage pressures of
up to 1200 bar. These findings have beenachieved in experiments conducted on
individual and multiple (array) capillaries, anddemonstrate the unique properties of glassmaterials. Thereby glasses which contains
approximately a third of the density of steel
whilst having three times the strength of steel
led finally to light-weight systems, becausesignificantly less material is necessary toreach the same pressure resistance.
Carrying out life cycle tests it turned out thatthe strength is also increased by adding
certain pressures to the structures ahead of
the storage.

Experimental
A special set-up was installed in safety
rooms in order to carry out various tests. It is
possible to realize hydrogen pressures ofmax. 1500 bar. On the one hand systematic
tests for the determination of basic material
properties like burst pressures, life cycles,
influences on the strength etc. have been
carried out. Applying special procedurehydrogen was also stored in the glass
structures.

Results

Fig. 1 Prototype for Hydrogen Storage

The C.En developed system ensures thesafe infusion, storage, and controlled release
Corresponding author: Kai Holtappels, email: kai.holtappels@bam.de , Tel. (+49) (30) 8104 3436

34

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

WEDNESDAY

35

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

LIGHT-WEIGHT METAL-BORON-NITROGEN
HIGH-CAPACITY HYDROGEN STORAGE

SYSTEMSFOR

Ewa Rönnebro
Pacific Northwest National Laboratory, 902 Battelle Blvd., Richland, WA 99354, USA
A promising high-capacity hydrogen storage material is ammonia borane, NH3BH3, releasing ca 12
wt% of hydrogen <150°C and regeneration is made feasible by a sequence of chemical reactions.
We have been exploring metal hydrides and borohydrides mixed with ammonia borane, to find ways toimprove sorption properties and to reduce impurity levels of borazine, diborane and ammonia. Composite
materials were prepared by ball milling and characterized with respect to phase composition, chemicalbonding and release rates.

Introduction
Hydrogen storage is a key technology indevelopmentofalternative
energyinfrastructures. The need for light-weight,
high-capacity materials has shifted our focus
from metal hydrides to metal borohydrides(i.e. Li, Ca, Mg). We have identified pathwaysfor direct hydrogenation of calcium andmagnesium borohydrides from their enddecomposition products at 700-900 bar H2pressures and 300-400°C according to:(1) 2CaH2 + CaB6 + 10H2 = 3Ca(BH4)2(2) MgB2 + 4H2 = Mg(BH4)2
opening the door to potential high-capacityhydrogen storage applications [1,2]. Althoughborohydride materials can store ca 11-19 wt%
hydrogen, the operation temperatures arehigh for practical applications and rehydrogenation kinetics is slow. Another highcapacity material is ammonia borane, NH3BH3,releasing ca 12 wt% of hydrogen <150°C.
Regeneration is made feasible by a sequenceof chemical reactions. Different approaches toimprove the performance have been reported
in the literature, such as composite systems,
scaffolding
andadditives[3,4,5].
By

combining metal hydrides and borohydrides
with ammonia borane, we are looking forways to improve sorption properties and to

reduce impurity levels of borazine, diborane
and ammonia.

Experimental
Composites of NH3BH3 and hydride materials
were prepared by ball milling andcharacterized by in situ and ex situ analysis

including XRD, Raman, NMR, DSC/TGA/MS
and kinetics studies.

Results
We have studied a series of composite
materials of NH3BH3 + hydrides with respect
to phase composition, chemical bonding,release rates and re-hydrogenation. We will
here report our experimental resultscomparing hydrogen sorption performancefor the different composites.

References[1] E. Rönnebro et al, JPCB, 111 (42) (2007) 12045[2] G. Severa et al, submitted (2009)[3] A. Gutowska et al, Angew. Chem. Int. Ed. 44 (2005)
3578[4] Z. Xiong et al, Nature Materials, Vol 7 (2008) 138[5] D.Heldebrant et al, Chem. Mater. 20 (2008) 5332

Corresponding author: Ewa Rönnebro, email: ewa.ronnebro@pnl.gov, Tel. (+1) (509) 375 6877

36

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

RECENT DEVELOPMENTS IN NITRIDIC HYDROGEN STORAGE
MATERIALS
Duncan H. Gregory.
WestCHEM, Department of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK.
Complex hydrides containing lithium and nitrogen offer new families of materials for high gravimetriccapacity hydrogen uptake. Such high capacity storage is often reversible with potentially rapid sorption
kinetics and good cycleability. Such nitrides, imides and amides also present vast opportunities for doping,catalysis and morphology/size control. This contirbution highlights how the materials chemistry of these
hydrides can be developed from conception and discovery through to modification and optimisation. We
also emphasise how an evolving understanding of storage and reaction mechanism can underpin
concepts of design from a materials chemistry perspective.

Introduction
This
work
describes
howvariouscomplementary synthesis strategies including
increasing compositional complexity andnanostructuring can afford new nitridic
materials for hydrogen storage. Further, wedemonstrate
how
inand
ex-situcharacterisation
techniquescanbeharnessed to understand the mechanisms
and processes of storage in these materials.

Results and Discussion
We present and discuss several different
case studies from our work at Glasgow toillustrate the approaches we are taking. First,
we consider the factors influencing theuptake of hydrogen in the archetypal nitridehydrogen system, Li-N-H. Studies comparing
the uptake of hydrogen by pure α-Li3N vs.
commercial sources of Li3N vs. β-Li3N
demonstrate certainly that sorption rate (andcapacity) is mediated by purity and particle
size and also possibly by crystal structure(polymorphism). The role of superionic Li+
conductivity may be instrumental in this andappears to have marked effects in theabsorption and desorption of hydrogen (andlithium) in cycling between lithium imide(Li2NH) and lithium amide (LiNH2) as
demonstrated by diffraction, solid state NMR
andMuSR
experiments.
We
also
demonstrate that when taken to the extreme– by chemically engineering nanostructures –tailoring particle size and morphology candramatically improve kinetics and reversible
capacity. We also consider how similar
approaches might be applied to more
complex nitrogen-containing systems andhere we show how with the most simple 1:1
combinations in the Li-Mg-N-H system, one
might both, for example, understand themechanisms of the dehydrogenation reaction
and also manipulate the rate and capacity ofhydrogen uptake. We report our results fromball-milling processing, powder X-ray andneutrondiffraction
andtemperature
programmed desorption experiments.
(a)

(b)

Fig. 1. (a) Li3N nanofibres; (b) Structure of
LiMgN.

References[1] D H Gregory; J. Mater. Chem. 18 (2008) 2321
[2] T. K. Mandal, D. H. Gregory; Annu. Rep. Prog.
Chem. Sect. A, 105 (2009) 21[3] D. H. Gregory, A. G. Gordon; International
patent (2004) WO2004057070

Corresponding author: Duncan H. Gregory, email: D.Gregory@chem.gla.ac.uk,
Tel. (+44) (0) 1413306438

37

4th Hydrogen & Energy Symposium

REACTION PATHWAYS
Mg(NH2)2 + LiH

Wildhaus, Switzerland 2010

IN

THE

REACTIVECOMPOSITE

Deniz Cakir1, Gilles A. de Wijs2 and Geert Brocks1
1Computational Materials Science, Faculty of Science and Technology and MESA+ Research Institute,
University of Twente, P.O. Box 217, 7500 AE Enschede, The Netherlands.
2

Electronic Structure of Materials, Institute for Molecules and Materials, Faculty of Science, Radboud
University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.

In 2002, Chen et al [1] reported reversiblehydrogen storage in a mixture of LiH + LiNH2
with a storage capacity of 6.5 wt %.
However, this system requires an operating
temperature in excess of 250 C to achieve ahydrogen pressure of 1 bar. Several efforts
including cation substitution have been
considered in order to improve the operating
conditions, which is necessary for onboard
applications. For instance, replacing LiH with
MgH2 markedly reduces the operating
temperature through the reaction MgH2 +2LiNH2 → Li2Mg(NH)2 + 2H2 ↔ Mg(NH2)2 +2LiH. Recent experimental results however
indicate that the latter is not a simple onestep reaction and full hydrogenation of
Li2Mg(NH)2 occurs in a two step sequence
via an intermediate Li2Mg2(NH)3 [2,3].
In this work we examine the stability andstructureofpossibleintermediates
Li1compounds,
namelyLi2-2xMgxNH,
LixMg(NH2)2-x(NH)x, and Li22xMgxNH2,
xMg(NH)2-x(NH2)x, by means of first-principles
DFT calculations. In order to get stability ofthese compounds, formation enthalpies arecalculated from total energy differences. We
include the vibrational zero point energies inorder to get accurate results. All intermediate
compounds are thermodynamically stablewith respect to the elements. Next we
consider possible reaction steps involving
these intermediate imides/amides. We findthat the intermediate amides Li1-2xMgxNH2 ormixed imide-amides LixMg(NH2)2-x(NH)x andLi2-xMg(NH)2-x(NH2)x, are energetically notfavorable. In contrast, the hydrogenation
reaction of Li2Mg(NH)2 via the intermediate
imides Li2-2xMgxNH is energetically favorable.
However, we do not find a clear preference
for one specific composition, as allcompounds Li2-2xMgxNH with ½ ≤ x ≤ ¾ leadto a similar reaction enthalpy. We predict that
all compounds within this composition range
are likely to occur as intermediates. The
experimentally proposed composition, x = ⅔,
lies within this range

References[1] P. Chen, Z. Xiong, J. Luo, and K. L. Tan,Nature 420, 302 (2002).
[2] J. Hu, Y. Liu, G. Wu, Z. Chiong, and P. Chen,
J. Phys. Chem. C 111, 18439 (2007).
[3] E. Weidner, F. Dolci, J. Hu, W. Lohstroh, T.
Hansen, D. J. Bull, and M. Fichtner, J. Phys.
Chem. C 113, 15772 (2009).

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4th Hydrogen & Energy Symposium

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CATALYTIC EFFECTS OF LiBH4 IN THE HYDROGEN SORPTIONREACTION OF 2LiH-Mg(NH2)2 SYSTEM
Jianjiang Hu1, Eveline Weidner2 and Maximilian Fichtner1
1

Institute for Nanotechnology, Karlsruhe Institute of Technology, Postfach 3640, D-76021
Karlsruhe, Germany

2

JRC Institute for Energy, Cleaner Energy Unit, Petten, the Netherlands

LiBH4 is an effective additive in enhancing hydrogen desorption and absorption for the 2LiH-Mg(NH2)2hydrogen storage system. We found in this study that the activation energy of the 2LiH-Mg(NH2)2 systemin the dehydrogenation was lowered by approximately 14% after doping with LiBH4. By following the phasedevelopment during H2 release from the LiBH4 doped system, we observed the formation anddisappearance of Li4(BH4)(NH2)3, a LiBH4 complex with LiNH2, as intermediate in the hydrogen sorption
process. Phenomenally, the driving force of the faster kinetics could be originated from LiBH4 which
captures and releases LiNH2, the intermediate in the pristine 2LiH-Mg(NH2)2 system, during the hydrogen
sorption process. In the presence of LiBH4 the crystallization of Mg(NH2)2 took place at much lower
temperatures, which might structurally favor the solid-solid hydrogen sorption reaction.

Introduction
In order to elucidate the catalytic mechanism,
both kinetic analysis and phase identification
were performed.

LiBH4, which could be of significance for theenhancement of hydrogen desorption.
-9.5

Experimental

Results
The activation energies were found to be
149.9 kJ/mol for the pristine sample and128.3 kJ/mol for the sample of 1Mg(NH2)22LiH-0.3LiBH4, i.e., ca. 14% reduction in theactivation energy by the addition of LiBH4.
XRD
results
revealthat
Mg(NH2)2
recrystallizes at a considerably low
temperature of 154°C in the presence of-10.5

Ea=128.3 kJ/mol

2ln( /Tmax )The activation energies for both pristine and
LiBH4 doped systems were measured. The
crystal structure of Li4(BH4)(NH2)3 wasdeterminedwithhighlycrystallized11
Li4( BD4)(NH2)3 by Neutron Diffraction andrefined via Rietveld method. X-ray powder
diffractometry and FTIR were used for thephase and composition identification in thehydrogen sorption process.

1-2 pure
1-2-0.3

-10.0

-11.0
-11.5
-12.0

pristine
Ea = 142.9 kJ/mol

-12.5
2.07

2.10

2.13

2.16

2.19

2.22

2.25

2.28

-1

1000/Tmax( K )Fig. 1. Kissinger Plot of pristine and LiBH4 doped
systems.

References[1] Hu, J. J.; Liu, Y.; Wu, G.; Xiong, Z.; Chua, Y.
S.; Chen, P. Chem. Mat. 2008, 20(13), 43984402[2] Meisner, G. P.; Scullin, M. L.; Balogh, M. P.;
Pinkerton, F. E.; Meyer, M. S. J. Phys. Chem.
B 2006, 110, 4186-4192

Corresponding author: Jianjiang Hu, email: jianjiang.hu@kit.edu , Tel. (+49) (7247) 82 8915

39

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

REACTION MECHANISMS OF FORMATION OF 2NaBH4+MgH2
BY HYDROGENATION OF 2NaH+MgB2
Claudio Pistidda1,2, Gagik Barkhordarian1, Christian Bonatto Minella1,
Sebastiano Garroni3 Torben Jensen4, Yngve Cerenius5, Martin Dornheim1,
Wiebke Lohstroh2, Maximiliam Fichtner2 , Rüdiger Bormann11Institute of Materials Research, GKSS Research Centre Geesthacht GmbH, Max-Planck-Straße 1, D2
21502 Geesthacht, Germany;
Institute of Nanotechnology, Forschungszentrum Karlsruhe GmbH,3
Postfach 3640, 76021 Karlsruhe, Germany; Departament de Física, Universitat Autònoma de Barcelona,
408193 Bellaterra, Spain; Interdisciplinary Nanoscience Centre (iNANO) and Department of Chemistry,
University of Aarhus, Langelandsgabe 140, DK-8000. Denmar; 5 MAX-lab, Lund University, S-22100 Lund,
SwedenThe formation mechanism of 2NaBH4+MgH2 by hydrogenation of 2NaH+MgB2 has been investigated indetail by in-situ methods. Depending on the applied hydrogen pressure several intermediate phases areobserved.

Introduction
With the aim of clarifying the reaction
mechanisms involved in the formation ofcomplex borohydrides, we investigated thehydrogenation reaction of 2NaH+MgB2.

Experimental
The NaH and the MgB2 were charged into ahardened steel vial and milled for 1 hour in a
Spex 8000 ball mill, with a ball to powder
ratio of 10:1. In situ XRD measurements
were performed at the MAX II Synchrotron, at
Beam line I711 in Lund.

reactions takes place. Besides the formationof NaBH4 , the formation of NaMgH3 as wellas the formation of an unknown phase isobserved under 50 bar H2 pressure andtemperatures up to 400°C. Moreover, someof the reaction products are in the liquidstate, as it is evidenced from the appearance/
disappearanceoftheamorphousbackground in the SR-PXD data and thesolidification peaks that appear in the DSC
measurements
duringcooling.
Hydrogenation at 5 bar H2 still yields theliquid state, however the formation of
NaMgH3 as well as of the unknown phase
could not be observed, consequently theformation of these two phases strongly
depends on the applied hydrogen pressure.

Results
The results presented indicate that during
heating in H2 atmosphere a series ofCorresponding author: Claudio.Pistidda, email: claudio.pistidda@gkss.de40

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

STUDY OF THE DECOMPOSITION OF Ca[BH4]2 PREPARED BY
REACTIVE BALL MILLING
Carine Rongeat1, Shunsuke Kato2, Andreas Borgschulte2, Andreas Züttel2,
Ludwig Schultz1 and Oliver Gutfleisch1
1

IFW Dresden, Institute for Metallic Materials, D-01069 Dresden, Germany
Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
2

Ca[BH4]2 is one of the more interesting material for solid state hydrogen storage due to its high hydrogencontent and suitable thermodynamic properties for mobile application. This compound can be synthesised
by reactive ball milling of a mixture of CaH2 and CaB6 under high hydrogen pressure. This techniqueenables to add directly a dopant to the mixture during the synthesis process to improve it. The effect ofdifferent dopant on the decomposition is discussed in details.

Introduction
The synthesis of Ca[BH4]2 from thedecomposition products CaB6 and CaH2
necessitates drastic conditions at 440°C and
700 bar [1]. Reactive ball milling is used as
an alternative technique near room
temperature. The decomposition of thismaterial is analysed here by a combination ofdifferent characterisation techniques.

Despite this low yield, it is possible to identify
Ca[BH4]2 by IR spectroscopy [2]. The
decomposition of the Ca[BH4]2 phase formed
during milling follows a multi-step process(Figure 1) which differs if it performed in
vacuum or H2 atmosphere. It is suggested
that different intermediate phases are formed
depending on the atmosphere.

Experimental
The starting mixtures CaH2 + CaB6 with TiCl3
or TiF3 as additives were ball milled under
140 bar H2 to mechano-synthesised Ca[BH4]2
through reaction (1).
(1) 2CaH 2  CaB6  10 H 2  3Ca[ BH 4 ]2Infrared (IR) spectroscopy was used for thecharacterisation of the as-milled compounds.
The decomposition was studied by thermal
desorption spectroscopy (TDS) in highvacuum and differential scanning calorimetry(DSC) under H2 atmosphere with maximum
500°C.

Results
After 24 h milling of CaH2 and CaB6 under
140 bar H2, we can observe a H2 pressure
decrease in the vial related to H2 absorption
from the mixture. The quantity of H2
absorbed represents 19% of the total amount
expected for the complete reaction (1).

Fig. 1. TDS spectra of H2 (top) and B2H6 (bottom)
releases for the decomposition of pure Ca[BH4]2(a) and of milled sample with TiCl3 (b) or TiF3 (c).

References[1] Ronnebro et al; J. Phys. Chem. B Lett. 111(2007) 12045[2] Rongeat et al; submitted

Corresponding author: Carine Rongeat, email: c.rongeat@ifw-dresden.de, Tel. (+49) (351) 4659 669

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4th Hydrogen & Energy Symposium

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THURSDAYMORNING

42

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

FROM MICROSPOTS TO HYDROGENVIBRATIONAL SPECTROSCOPYSTORAGE

BY

Andreas Borgschulte,1 Robin Gremaud,1 Motoaki Matsuo,2 Shin-Ichi Orimo,2Andreas Züttel1
1Empa, Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2

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

Raman spectroscopy on diffusion multiples (gradient samples) made of different hydrides and/or
compounds is utilized as a high-through put method searching for new complex hydride phases. With
studying the kinetics of formation of the various phases, the diffusion coefficients of the exchanged species
can be determined. Particularly, the measurement of ion diffusivity in Li-based complex hydrides will help
the search and development of fast lithium-ion conductors.

Introduction
In this work we give an overview how we use
the investigation of vibrations in solids togain valuable information on the functioningof hydrogen storage in complex hydrides andillustrateits
prospectforfurther
investigations. Particularly, we demonstrate
the applicability of a novel high-throughput
method using spatially resolved Raman
spectroscopy.

corresponding pseudo-binary phase diagram
is obtained. In addition, the kinetics ofinterdiffusion can be investigated.

Setup
For gradient samples, powder will be pressed
into pellets. Pieces of these pellets madefrom different materials will then be sintered
together at elevated temperatures. The thus
prepared sample will be investigated byspatially resolved Raman spectroscopy(“hydrogenography”).

Applications
Fig. 1. Hydrogenography by Raman
By interdiffusion of different hydrides,
samples with locally different compositions
are obtained. Spatially resolved Raman
spectroscopy allows the determination of
possibly formed new phases in one single
sample, and with further characterization theTracer-Diffusion of hydrogen incomplex hydrides, e.g. in LiBH4 [1]Pseudo binary phase diagrams ofcomplex hydrides, e.g. LiNH2-LiBH4etc. [2]Exchange of halide anions incomplex hydrides, e.g. LiBH4-LiI,
LiBH4-LiBF4. [2]References[1] R. Gremaud et al. Phys. Rev. B 80, 100301(R)(2009).
[2] M. Matsuo,et al. J. Am. Chem. Soc., 2009,131 (45), pp 16389–16391.

Corresponding author: A. Borgschulte, email: andreas.borgschulte@empa.ch, Tel. (+41) (44) 823 4639

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HYDROGEN DESORPTION MECHANISUMS AT THE SURFACES
OF AlH3 AND LiBH4
Shunsuke Kato1, Michael Bielmann1, Kazutaka Ikeda2, Valentina ZakaznovaHerzog1, Arndt Remhof1, Shin-ichi Orimo2, Andreas Borgschulte1, Andreas
Züttel1
1

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Laboratory for
Hydrogen & Energy, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland.
2
Tohoku University, Institute for Materials Research, Katahira 2-1-1, Sendai, 980-8577, Japan.
The surface processes of AlH3 and LiBH4 were investigated with repect to the surface oxidation andhydrogen desorption mechanims at the hydrides surfaces. The surface changes were systematicallyinvestigated by means of X-ray Photoelectron Spectroscopy, Thermal Desorption Spectroscopy and Mass
Spectrometry. The surface condtion, i.e., surface oxide layer, singnificaly affects thier hydronge desorption
kinetics.

Introduction
Under
practical
conditions,surfacecontamination of hydrogen storage material
by impurity gasses has to be taken into
account since the surface conditions are
crucial for the hydrogen sorption kinetics [1,2]. This study focuses on two different
families of hydrides, namely, covalent-likeand complex hydrides, AlH3 and LiBH4
respectively. The hydrogen desorption
mechanisms at the hydrides surfaces were
investigated.

Results
A closed surface oxide layer prevents
thermodynamically unstable AlH3 from thedecomposition (as depicted in Fig. 1). The
surface oxidation of LiBH4 reduces thediborane desorption and results in theenhanced desorption of hydrogen moleculesfrom the surface oxide layer.

Experimental
Surface changes of AlH3 during thehydrogen desorption. The surface changes
were investigated by means of in situ X-ray
Photoelectron Spectroscopy (XPS) combinedwith Thermal Desorption Spectroscopy (TDS)
and Mass Spectrometry (MS).
Surface oxidation study of LiBH4 and thehydrogen desorption kinetics. The cleansurface was prepared, and subsequently
modified by exposing to O2 with the amountof 3 L up to 107 L at 313 K (1 L = 10-6 Torrs).
The induced surface changes were analyzed
by XPS. The hydrogen desorption processes
were studied by TDS and MS.

Fig. 1. Mechanism of hydrogen desorption fromthe surface of AlH3 (schematic). (a) inhibition ofhydrogen desorption by surface oxide layers, e.g.
Al2O3 (b) breaking of surface oxide layers (c)recombination of hydrogen and growth of metallic
Al phase [1].

References[1] S. Kato, M. Bielmann, K. Ikeda, S. Orimo, A.
Borgschulte, A. Züttel, Appl. Phys. Lett. inpress.
[2] A. Borgschlute, M. Bielmann, A. Züttel,
G.Barkhordarian, M. Dornheim, R. Bormann,
Appl.
Surf.
Sci.
254
(2008)
2377.

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

44

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

TOWARDS SOLAR FUELS BY NOVELPHOTOELECTROCATALYTIC APPROACH
Gabriele Centi and Siglinda Perathoner
Univ.of Messina and INSTM/CASPE (Lab. of Catalysis for Sustainable Production and Energy),
Dip. di Chimica Industriale ed Ing. dei Materiali, Salita Sperone 31, 98166 Messina (Italy).
Solar fuels, in particular those obtained by converting CO2 to liquid fuels using water and solar energy, will
be an important aspect of the future scenario for sustainable energy. After introducing possibilities andperspectives in solar fuels, the lecture will discuss more specifically the photoelectrochemical/catalytic(PEC) approach to solar fuels. It will be presented the concept of PEC reactor, which differentiates fromthe conventional ones. The same apparatus can be used also for a separate H2 and O2 production fromwater by photoelectrolysis (photosplitting) and for the H2 production by photoreforming. From CO2 it ispossible to produce isopropanol using carbon nanotube based electrode.

Introduction
Producing solar fuels is a hot topic with large
scientific and industrial interest, as well as
great attention from the public [1]. There aremany options, but the winning solution is still
unclear. After introducing possibilities andperspectives in this field, and limits andconstrains as well, the lecture will discuss
more specifically an approach to solar fuels(photoelectrochemical/catalytic - PEC conversion of CO2) which is considered thepreferable, although highly challenging.
The PEC solar cell differentiates from theconventional photoelectrochemical apparatus
in terms of electrodes and operations insolventless conditions [2]. The same cell canbe used also for the photoproduction of H2
from
water
and/orwaste
organics(photoreformingofbioethanol
wastesolutions).
Isopropanol can be synthesized from CO2
using carbon nanotube based electrode.

PEC solar cell
For a practical use of PEC solar cells, thedesign should be quite different from thatused typically in literature. The anode andcathode in the PEC device should be in theform of a thin film separated from a protonconducting membrane (Nafion®, for example)
and deposited over a porous conductive

substrate which allows the efficientcollection/transport of the electrons over theentire film as well the diffusion of protons
to/from the membrane. It is also necessary toallow an efficient transport of the gas.
The PEC reactor shows analogies to PEM
fuel cells. One side of the cell is composedby a nanostructured TiO2-based thin film
where photo-electrolysis of water using solar
light occurs. Protons diffuse through amembrane on the other side of the PEC
device and react with CO2 in the presence ofelectrons(generatedinwater
photodissociation; anode and cathode sides
are connected by a wire) and a special
electrocatalyst, based on the concept ofnanoconfinement.
The lecture will discuss aspects related to the
preparation of the nanostructured titania thinfilm (photoanode) and its performances in thephotoproduction of H2 (from water andalcohols), and of the preparation andperformances of the carbon nanotube based
electrode (cathode) for the reduction of CO2
to liquid hydrocarbons and alcohols.

References[1] Centi, G. et al; Solar production of fuels fromwater and CO2. In Carbon-Neutral Fuels andEnergy Carriers. Taylor & Francis (2009).
[2] Centi, G. et al.; Green Chem., 9 (2007) 671.

Corresponding author: Gabriele Centi, email: centi@unime.it, Tel. (+39) (090) 6765609

45

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CARBON DIOXIDE AS HYDROGEN VECTOR IN H2 STORAGE
AND DELIVERY
Gábor Laurenczy
École PolytechniqueCH-1015, Switzerland

FédéraledeLausanne(EPFL),

SB

ISIC

LCOM,

Lausanne

The homogeneous catalytic decomposition of formic acid in aqueous solution provides an efficient in situ
method for hydrogen production that operates over a wide range of pressures, under mild conditions, andat a controllable rate. A continuous high pressure hydrogen generator has been built, the catalyst
remained active after a large number of times stopping and re-starting the process. In the HCOOH – CO2
cycle the greenhouse carbon dioxide gas is used as hydrogen vector.

Introduction
Hydrogen is the carrier of energy – thesource of energy of the future. H2 is aversatile fuel for classical engines, gas
turbines and fuel cells; having two problems:
storage and delivery [1].

hydrogen storage and delivery, making thesesystems suitable for practical applications [5].

Experimental
The homogeneous catalytic decomposition of
formic acid in aqueous solution have been
carried out using hydrophilic rutheniumbased catalysts, generated from the highly
water soluble ligand meta-trisulfonatedtriphenylphosphine (TPPTS) and RuCl3.

Results and conclusions
Formic acid (HCOOH) has the advantage
over other organic molecules to decompose
only into gaseous products (H2 and CO2), ina very selective homogeneous catalytic
reaction, operating in environmentally friendly
solvent, in water: a new catalytic system has
been developed that efficiently andselectively generates high pressure hydrogenfrom formic acid [2-4]. Carbon dioxide can berecycled,
reducedinto
formicacid
electrochemically or by direct hydrogenation.
These recent results concerning thehomogeneous
catalytic
formicacid
decomposition
reactions
have
been
considered as a breakthrough in theFig. 1. The “green” carbon dioxide – formic acidcycle.

Acknowledgment. Swiss National Science
Foundation(FNS),
Swiss
Innovation
Promotion Agency (CTI) and EPFL are
thanked for financial support.

References[1] L. Schlapbach, A. Züttel, Nature, 414, 353(2001).
[2] C. Fellay, P. J. Dyson, G. Laurenczy,International patent application (2006).
[3] C. Fellay, P. J. Dyson, G. Laurenczy, Angew.
Chem. Int. Ed., 47, 3966 (2008).
[4] C. Fellay, N. Yan, P. J. Dyson, G. Laurenczy,
Chem. Eur. J., 15, 3752 (2009).
[5] F. Joó, ChemSusChem,1 805 (2008).

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

46

4th Hydrogen & Energy Symposium

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NEW CATALYSTS AND PROCESSES FOR AMINE BORANES AS
CHEMICAL HYDROGEN STORAGE MATERIALSHeinz Berke*, Yanfeng Jiang, Chunfang Jiang, Xinghua Yang, Olivier Blacque,Thomas Fox
University of Zurich, Institute of Inorganic Chemistry, Winterthurerstr. 190, CH-8057 Zürich,
Switzerland
A new rhenium based catalyst for the dehydrogenation of ammonia borane and amine boranes ispresented leading to borazine or cycloborazanes, respectively. Furthermore a new prototypical reaction ofammonia borane with imines was studied bearing great potential for improvement of the dehydrogenation
selectivities concerning the boron/nitrogen products.

Introduction
Various Amine boranes possess hightheoretical hydrogen storage capacities.
Their practical application is however often
hampered by irreversibility of hydrogen
release (“fuelling”) or up-take (“refuelling”) or
by low selectivities for these processes
leading to a plethora of complex compounds.
These deficiencies are thought to beresolvable by the involvement of catalysts orby development of new “fuelling” or“refuelling” processes. Catalytic approaches
have been pursued in particular for thedehydrogenationofammoniaborane(H3B-NH3), however, mainly noble metal
catalysts were found to be active enough toestablish reasonable reaction rates andtemperatures
andalso
acceptable[1]
selectivities .

Experimental and Results
Our group has studied a rhenium based
dehydrogenation catalysis of ammonia
borane and methyl amine boranes and foundrelatively selective processes operating at[2]60-80°C .
NH3•BH3
Me2NH•BH3

cat.

- H2
cat.
- H2

1/n [H2N-BH2]n

cat.

- H2

1/2 [Me2N-BH2]2
cat. =

1/3 [HN=BH]3
R3P

Br

H

Re
NO

PR3

Quite remarkable is the high selectivity forthe formation of borazine and cycloborazanes, respectively. Mechanistic studies
revealed involvement of rhenium monophosphine complexes. The reaction was
found to be half order in the imine and firstorder in ammonia borane. Furthermore, we
explored the possibility to apply a “metalfree”
transferhydrogenation
betweenammonia borane and imines producing
amines and [BH2=NH2] as a primaryintermediate[2].
R

H
C

N

R' + H3B NH3H2B NH2

Slow

Fast
HN
1/3 HB

H
B
N
H

NH
BH

+

R

H2
C

N
H

or Polyborazylene

R'

+

R

H2
C

N
H

R'

Detailed deuterium isotope studies revealed
kinetic isotope effects, from which aconcerted mechanism in the form of a double
H transfer was concluded. Further studies
will be devoted to the use of imines withdiminished hydrogenation enthalpies toestablish reversibility of the process.

References[1] Hamilton et al; Chem. Soc.Rev. 38 (2009) 279;
Stephens et al; Dalton Trans. 25 (2007) 2613
[2] Berke, Chem. Com. (2007) 3571-3573;
Berke et al; Organometallics 28 (2009) 5493
[3] Berke et al; Angew. Chem. Int.,(2009) subm.

Corresponding author: Heinz Berke, email: hberke@aci.uzh.ch, Tel. (+41) (44) 635 4680

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KEMERIT – CARBON MATERIAL FOR ENERGY APPLICATION
Alexey Kozlov1, Chingiz Barnakov1, Zinfer Ismagilov2
Institute of Coal and Coal Chemistry SB RAS, Pr. Sovetskiy 18, Kemerovo, 650099, Russia
Boreskov Institute of Catalysis SB RAS, Pr. Ak. Lavrentieva, 5, Novosibirsk, 630090, Russia
The samples of amorphous carbon material (ACM) were prepared from different precursors by thermocatalytic synthesis (heat treatment of precursor and reactant mixture in inert atmosphere at temperature of
600-800C). The surface area of the samples was varying from 1000 to 3000 sq.m./g, micropore volume ofthe samples was varying from 0.5 to 1.6 cub.cm/g. It was established that the best hydrogen storage
capacity of the samples is 5.5 wt % at 4 MPa and 77 K and the best methane storage capacity of thesamples is 25 wt % at 4 MPa and 273 K. Application of ACM sample as support for proton exchange
membrane fuel cell cathode catalysts exhibits better performance compared with commercial Vulcan XC72R.

Introduction
The purposes of this paper are summarizing
our results connected with synthesis andproperties of ACM and discussion new dataobtained for the last time.

Experimental
Coal, coal coke, petroleum coke, phenol,
alizarin, 8-quinolinol, nitroaniline, 1,2,3benzotriazol and other organic compounds
were used as precursors of ACM samples.
Detailed description of the synthesis waspresented in patent [1].

Results
The adsorption of CH4 and H2 was studied witha high-pressure volumetric device designed
for the purpose. The data for the several
ACM samples are collected in Table 1. It isrevealed that H2 storage by adsorption on the
ACM samples as well as on AX-21 isconsiderable only at temperature of 77 K andvalue of CH4 adsorption is up to 25 wt.% attemperature of 273 K and pressure of 4 MPa.
In paper [2] ACM sample was used forsynthesis of platinum cathode catalysts for
proton exchange membrane fuel cells.
Investigations were conducted on ACM
sample prepared from petroleum coke.
Platinum particles were deposited on thesample with using of special method.

Commercial Vulcan XC-72R support wasused as comparing sample. The membraneelectrode assembly testing showed that thePt cathode catalysts on ACM exhibit better
performance in comparison with a catalyst on
conventional carbon black support Pt/Vulcan
XC-72R.
Table 1. Textural and adsorption characteristics of
ACM samples
Precursor

ABET/A,
2
m /g

АХ-21
2800/2680
Coal “D mark” 3100/2960
Petroleum coke 3200/3050
Phenol2240/1871
8-quinolinol
2550/2235
m- nitroaniline 2970/2780

VS/V,
3
sm /g

H2 ,
wt.%

CH4,
wt.%

1.60/1.20
1.55/1.08
1.62/1.12
1.53/0.98
1.59/1.21
1.86/1.57

5.1
3.5
4.5
5.0
5.2
5.5

17.2
12.8
15.8
17.0
18.0
25.5

ABET – BET surface area, A – micropore surface area,
VS – total pore volume, V – micropore pore volume, H2 –H2 adsorption at 77 K and 4 MPa, CH4 – CH4 adsorption
at 273 K and 4 MPa.

This work was carried out at financial supportof the RFBR (project no. 07-03-96042) and
the Russian Science Support Foundation.

References[1] Barnakov Ch.N. et al. Patent RU2206394[2] Z.R. Ismagilov, et al. Catalysis Today, 102–103 (2005) 58.

Corresponding author: Alexey Kozlov, email: kemerit@rambler.ru, Tel. (+7) (3842) 368188

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A MULTIDISCIPLINARY, BIOLOGICAL APPROACH USINGSOLAR ENERGY TO CAPTURE CO2 WHILE PRODUCING H2
AND HIGH VALUE PRODUCTS

Jiri Muller
Institutt for Energiteknikk, Kjeller, Norway

Many areas of algae technology have been developed over the last decades, and there is anestablished market for products derived from algae, dominated by health food and aquaculture.
In addition, the interest for active biomolecules from algae is increasing rapidly. The need forCO2 management, in particular capture and storage is currently an important technological,
economical and global political issue and will continue to be so until alternative energy sourcesand energy carriers diminish the need for fossil fuels. This presentation summarizes in an
integrated manner different technologies for use of algae, demonstrating the possibility of
combining different areas of algae technology to capture CO2 and using the obtained algal
biomass for various industrial applications thus bringing added value to the capturing andstorage processes. Furthermore, we emphasize the use of algae in a novel biological process
which produces H2 directly from solar energy in contrast to the conventional CO2 neutral
biological methods. This biological process is a part of the proposed integrated CO2
management scheme.

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4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

FROM HYDRIDES TO SYNTHETIC FUELS
Andreas Züttel, Shunsuke Kato, Oliver Friedrichs, Andreas Borgschulte
Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen& Energy, CH-8600 Dübendorf, Switzerland
The natural energy cycle is based on the photosynthesis of the plants. The solar light as the energy input
allows the dissociation of water into hydrogen and oxygen (light cycle). The hydrogen is the used to reduce
the absorbed CO2 to carbohydrates (dark cycle). Finally, the carbohydrates are converted in a very slow
anaerobic process into hydrocarbons, i.e. the fossil fuels. Electricity produced by photovoltaics can beused in an electrolyzer for the production of hydrogen. The CO2 from the atmosphere is the reduced withthe hydrogen be the inverse watergas shift reaction and the Fischer-Tropsch synthesis to hydrocarbons.

Energy density
The hydrogen density of hydride materials is,based on to today’s knowledge, limited at
150 kg H2/m3 and 20 mass%. This corresponds to an energy density of 5800 kWh/m3
and 7.8 kWh/kg, which is about 60% of theenergy density of petrol. This value is basedon the materials only and drops to <10% for
the comparison of storage systems.

Furthermore, syngas CO + H2 then reacts tosynthetic hydrocarbons by the FischerTropsch synthesis:
n CO + (2n+1) H2  CnH2n+2 + n H2O
at 1 bar and 160 - 200°C. The enthalpy of thereaction is for octane H(n=8) = -1685 kJ/mol
Oktan. The upper heating value of octane isHC = -5430 kJ/mol.

Liquid hydrides
Some complex hydrides are liquid at room
temperature e.g. Al[BH4]3. Furthermore, theless stable hydrides also exhibit fasthydrogen desorption rates. Therefore, liquidcomplex hydrides may have advantages forthe application as compared to the salt likesolids, e.g. the handling, the mass transport,
the thermal conductivity. Several liquid
hydrides are identified and there properties
analyzed.
Fig. 1. Synthetic fuel cycle.

Synthetic fuels
Hydrogen reacts with carbondiaxid tocarbonmonoxid in the reversed watergasshift reaction:

The cycle conserves thermodynamically 60%of the electrical energy in the form ofhydrocarbons.

CO2 + H2  CO + H2O

ReferencesH = -2.8 kJ/mol[1] A. Züttel, Philosophical Magazin (2009), in
press
Corresponding author: Andreas Züttel, email: mailto:andreas.zuettel@empa.ch, Tel. (+41) (44) 823 4038

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THURSDAYAFTERNOON51

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INVESTIGATION OF HYDROGEN STORAGE ALLOYS AND
THEIR APPLICATION TO ON-BOARD STORAGE TANK
Etsuo Akiba, Kohta Asano, Shigeru Tsunokake*, Tatsuya Fuura*, Yoshiki
Sakaguchi** Masanori Monde**
AIST, Tsukuba Central 5, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565 Japan. *Japan Metals &Chemicals Co., Ltd., 232 Oguni Oguni-machi, Nishiokitama-gun, Yamagata 999-1351, Japan.
**SAMTEC Co. Ltd., 1000-18, Enmeicho, Kashiwabara, Osaka, 582-0027, Japan. *** Saga
University, 1 Honjo, Saga, 840-8502, Japan.
Under a national project since 2005, we have developed a hybrid tank system for on boardhydrogen storage as well as Ti based BCC alloys for hybrid tank system. Fabrication
technologies of the hybrid tank have been developed. Ti-Mn-V alloys developed contained 2.8
mass % of hydrogen. Modelling of the tank has also investigated for improvement of tankdesign.

Introduction
Major on board hydrogen storage methods
are compressed gas, liquid hydrogen andhydrogen storage materials. However, atpresent any of single methods meet therequirements from vehicular application.
The hybrid tank system is combination ofhydrogen storage materials and compressedgas. Takeichi et al. [1] have proposed theconcept of the system and demonstrations
using real size tanks have been carried out
by Toyota Motor Co [2].
Development of the tank system has been
conducted under the Japanese national
project and materials for the hybrid tank arealso investigated.
In the hybrid tank,hydrogen pressure reaches to 35 MPa insome cases but there is little work in thispressure region so far.
In this paper, recent progress in fabrication of
the hybrid tank and in material investigation
is introduced.

Experimental
The Ti-V-Mn alloys with BCC structure wereprepared using arc melting method. The
alloys produced are used for hydrogenation
as is. X-ray diffraction and the Rietveld
analysis using RIETAN software were carriedout.

Results
It was found that the relation of chemicalcomposition of alloys and lattice parameter.
Lattice parameter linearly related to hydrogenequilibrium pressure.
It means that weestablished the design concept of Ti-V-Mn
alloys. According to the concept, hydrogencapacity of 2.8 mass % has been realized.
For hybrid tank development, we have firstly
established the original design of the tankbased on modelling and developed
manufacturing method. Figure 1 shows theconcept of hybrid tank developed.

Fig. 1. Concept of hybrid tank.

References[1] N. Takeichi et al; Int J. Hydrogen Energy. 28(2003) 1121
[2] D. Mori et al; Proceedings of MH2008 (2008)

Corresponding author: Etsuo Akiba, email: e.akiba@aist.go.jp, Tel. (+81) (298) 61 4541

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4th Hydrogen & Energy Symposium

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A METAL HYDRIDE AS A MEANS OF ENERGY STORAGE IN A
CANAL BOAT
Alex Bevan, David Book, Andeas Züttel* and Rex Harris
School of Metallurgy and Materials, University of Birmingham, UK.
*Empa Materials Science and Technology, Switzerland.

This paper describes the application of a large- scale (~240 kg) metal hydride store as a meansof energy storage on board a converted canal boat. The standard diesel engine was replaced
by a 10kW NdFeB permanent magnet electric motor together with a lead-acid battery stack
and a 1kW PEM fuel cell supplied by pure hydrogen from metal hydride powder contained
within stainless steel tubes.This store provided substantial additional electric energy storage
and was the most expensive element in the conversion process. Thus the performance of thisstore was of particular significance and is the main subject of this paper.

Introduction
Hydrogen has considerable potential as aneffective means of storing electricity which, intransportation, can be converted into traction bymeans of a PEM fuel cell and an electric motor. If
the hydrogen is generated and distributed bymeans of low (or zero) carbon technologies, thenthis provides an effective means of reducing thecarbon footprint of long-range transportation. Oneof the major challenges to the introduction of thistechnology is the mobile storage of the hydrogenwith sufficient gravimetric and volumetric density.
Consequently there is considerable effort on thedevelopment of light-weight, solid-state hydrogen
stores but, for road transport, the favoured choiceat this juncture is high pressure (~700bar)
hydrogen storage in light-weight composite tanks.
In the case of water-based transportation
however, the storage requirements are much
more relaxed and conventional metal hydrides canbe employed as a practical means of solid statehydrogen storage. This option has been exploredin the current project and this paper describes thepreliminary findings on a converted electric canalboat.

Experimental
A standard British Waterways (BW) maintenancecanal boat was kindly provided by BW and thiswas converted to the current vessel (the Ross
Barlow*) over a period of around 2 years. The
diesel engine (~15kw) was removed and thespace converted to accommodate a 10kW NdFeB

based motor and a lead-acid battery stack. The
conventional tiller was also supplemented with
NdFeB actuated power steering. This provided thepossibility of remote operation of the vessel. At theother end of the boat the space was adapted toaccommodate the stainless steel hydrogenstorage system, hydrogen delivery and flow
measurement facilities and the 1kW PEM fuel cell
(Reli-On). These units were accommodated in awell ventilated space with an explosion hatch at
the front of the boat together with hydrogendetectors. The storage unit could be charged fromexternal hydrogen cylinders on the bank of thecanal and the water temperature was regulated bya heat exchanger via the canal. Laboratory
equipment was also constructed to cycle
automatically the hydrogen storage material sothat accelerated ageing trials could be carried out.

Results
The Ross Barlow has been subject to extensive
trials and, overall, the experience has been very
encouraging
and largely
trouble-free.
Thehydrogen store has performed extremely well andthere has been no observable decrease in thestorage capacity or in the kinetics of hydrogen
absorption or desorption. It was also decided tosubject the storage alloy (based on the Lavescompound TiMn2 with ~1.9wt% H2) to someaccelerated ageing trials in the laboratory. The
results of these investigations are reported in thispaper

*Named after a post graduate student who died in 2005.
Corresponding author: Rex Harris, email: I.R.Harris@bham.ac.uk . Tel + 44 (0)121 414 5165

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HYDROGEN CYCLE FOR A SELF-SUFFICIENT ACCOMODATIONUNIT (SELF)
U. Vogt1, M. Bielmann1, V.Zakaznova-Herzog1, M. Zimmermann2, S. Machini2,
B. Olsson2, A. Züttel1
1

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec. Hydrogen &Energy, CH-8600 Dübendorf, Switzerland
2
Empa Materials Science and Technology, Dept. Civil and Mechanical Engineering, Sec. BuildingTechnologies, CH-8600 Dübendorf, Switzerland
The aim of the project SELF is to build up a self sufficient accommodation unit for independent living,working or research on nearly any place in Europe. For that reason, it has to be assured that the unit canbe transported by helicopter or track to the places of use. Outside the civilisation SELF will attain energy
and water from the environment, storage it and thus represent an energy-independent living and modern
prospective building concept with a stand-alone power system (SAPS).

Energy concept
Electricity will be gained by PV, stored in Liion batteries and used for daily purposes,
light and controlsystem of the unit. As thedimension of the PV facilities will be
designed for sufficient power supply in
wintertime, it will produce excess electricity
during summertime which cannot be stored
in batteries. Surplus energy will betransformed into hydrogen by an electrolyser
and stored in metal hydrides. The hydrogen
will be used for cooking and heating during
wintertime. For this purpose, a new type ofcatalytic porous burner will be developed,
which can convert the energy, stored ashydrogen, very efficient in heat without any
pollutions like CO2 or NOx. The only reactant
will be water which is even beneficial for theroom climate. The water electrolysis andhydrogen storage is superior compared tolong term electricity storage regarding
storage density, storage volume and storage
weight.

H2 electrolysis and storage
Hydrogen synthesis by electrolysis fromwater and electrical energy will produce only
H2 and O2 without any exhaust gases. The
H2 production will be carried out from excessenergy during summertime by a commercial
electrolyser with a production rate of 1l/min.
The total hydrogen production is calculated

to be 3.8 to 4.5 kg during 100 days ofoperation.
For hydrogen storage, metal hydrides will be
used supported in metal tanks. The total
weight for H2 storage is limited to 320 kg.

Concept of H2 synthesis and storage

Catalytical H2 burner
A self-igniting catalytic H2 diffusion burner
based on porous ceramics will be developed
for cooking and heating. This ensures a very
high safety aspect and can be used safe also
in closed rooms, as no waste gases will be
released.
Reference
U.P. Grossmann, J. Lehmann, F. Menzl, A nonstationary hydrogen cooker with portable hydride
storage and catalytic hydrogen burner, Int. Journalof Hydrogen Energy 25 (2000) 87-90

Corresponding author: Ulrich Vogt, email Ulrich.Vogt@empa.ch54

4th Hydrogen & Energy Symposium

SYNTHESISAND
NANOCOMPOSITES

Wildhaus, Switzerland 2010

PROPERTIESOF

LiBH4-Mg(BH4)2

Elisa Gil Bardají, Maximilian Fichtner
Karlsruhe Institute of Technology (KIT), Institute of Nanotechnology, P.O. Box 3640, D-76021
Karlsruhe, Germany
Mixed-metal borohydride LiMg(BH4)x has been synthesized either by ball milling or by the reaction of thesingle borohydrides in an organic solvent. The resulting LiBH4-Mg(BH4)2 nanocomposite has been
investigated by X-Ray Powder Diffraction (XRD), High Pressure Differential Scanning Calorimetry (HPDSC) and Thermogravimetric Analysis (TGA). The thermal properties of the material remarkably differ fromthe properties of the starting materials.

Recently, it has been proposed that mixedmetal borohydrides based on alkali andselected transition metals could haveacceptable thermodynamics for reversiblehydrogen storage and still maintain a highhydrogen capacity.1 Additionally, first reports2
on bialkali borohydrides, such as LiK(BH4)23
and NaK(BH4)2, have been published. In the4case of LiBH4-Ca(BH4)2 nanocomposite
even a partial reversibility has been
confirmed for the first time in the case of amixed borohydride composite. This work
deals with the LiBH4-Mg(BH4)2 system.

Experimental
A 1:1 mixture of LiBH4 and Mg(BH4)2 was ballmilled in Fritsch P6 planetary mill.
Subsequently, diethylether was added to the
product and the suspension was stirred
overnight, under reflux. Following extractionof the solvent led to the formation of a white
powder, which was dried under vacuum.
Both as-milled as well as as-synthesizedmaterials were investigated by x-ray powder
diffraction and thermal analysis.

Results
The thermal decomposition properties of theresulting material are remarkably different
from those of each single borohydride. For
instance, the differential scanning calorimetry(DSC) profile of the as-milled material [LiBH4Mg(BH4)2] is showed in Figure 1. Three
endothermic peaks appear below 200°C
followed by a broad exothermic contribution
and finally two additional endothermic
events. Remarkably, the melting point peakof LiBH4 at ca. 280°C can not be detected.
6

exo.

5

Intensity(mW/mg)

Introduction

4
3
2
1
0
-1
50

100

150

200

250

300

350

400

450

500

Temperature(°C)

Fig. 1. DSC profile of as-milled LiBH4Mg(BH4)2 nanocomposite under 5 bar H2 at aheating rate of 5 K/min..

References[1] Li et al., J. Alloys Compd.,315, 2007, 446.
[2] Nickels et al; , Angew. Chem. Int. Ed., 47,2008, 2817 / Xia et al., J. Phys.: Condens.
Matter.,20,2008,445210.
[3] Seballos et al., J. Alloys Compd., 476, 2009,446.
[4] Lee et al., J. Phys. Chem. C ,113, 2009, 15080

Corresponding author: Elisa Gil Bardají, email: elisa.gil@kit.edu, Tel. (+49) 7247-82-8909

55

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PELLETS OF MgH2-BASED COMPOSITES AS PRACTICAL
MATERIAL FOR SOLID STATE HYDROGEN STORAGE
Giovanni Principi1, Ashish Khandelwal1, Filippo Agresti1, Giovanni Capurso1,
Amedeo Maddalena1, Sergio Lo Russo2
1

Università di Padova, Dipartimento di Ingegneria Meccanica,Settore Materiali, via Marzolo 9,35131, Padova, Italy.
2
Università di Padova, Dipartimento di Fisica and CNISM, via Marzolo 8, 35131, Padova, Italy
Hydrogen absorption/desorption (a/d) properties and mechanical stability of pellets made of compressedball-milled MgH2 powders mixed with catalysts (Nb2O5 and graphite) and a binding agent (aluminium
powder) have been investigated. The best cycling behaviour and mechanical strength stability have been
observed for pellets of catalyzed MgH2 powders added with 5 wt% aluminium annealed in vacuum at 450°C before starting the a/d cycles. This mechanical stability to cycles has been attributed to the formation ofa solid solution of aluminium in magnesium.

Introduction
During scaling up studies of MgH2 based
powders in a specially designed reactor it
was observed that the hydrogen storage
capacity as well as the a/d kinetics
decreased with the ongoing cycles due to aclose compaction of the powder particles
inside the reaction chamber associated withlocal overheating [1]. These observations
motivated us to study MgH2 based powders
moderately pressed in the form of pellets withthe addition of some binding agent in order toretain stable mechanical consistency andstructure with persistent free paths forhydrogen diffusion.

Results
It is found that a pre-heating treatment of thepellet to the temperature sufficient to form
intermetallic phases and/or solid Mg-Al
solutions (450 °C) increases the resulting
performance of the material, as concerns
both functional and mechanical stability. A
good mechanical stability has been observedin the case of pellets with 5 wt% Al. Thesepellets show a constant 5.3 wt% hydrogencapacity up to 50 cycles and constantkinetics after 10 cycles.

Experimental
MgH2 powder was ball milled with Nb2O5 (5wt %) and graphite (1 wt%) in a SPEX 8000
shaker mill for 20 hours using steel balls withball to powder ratio of 10:1. The pellets ofmilled powder with and without aluminum
powder were prepared by pressing thepowders in Ar atmosphere with a uniaxialpressure of 180 MPa by means of an Instron1121 tester. Structural characterization was
done by X-ray diffraction. Kinetic andthermodynamic tests were performed using a
Sievert’s type gas reaction controller. The
tests for compressive strength resistance ofthe pellets were performed using the same
Instron 1121.

Fig. 1. Pictures of the pellets after different cycles
The enhanced stability of the pellets in this casehas been attributed to the presence of the Al in
solid solution with Mg.
[1] Verga et al; Int. J. Hydrogen Energy
34(2009)4602.

Corresponding author: Giovanni Principi, email: giovanni.principi@unipd.it, Tel. (+39) 049 827 5513

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FRIDAY

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EXPERIMENTAL RESULTS AND SIMULATIONS OF A LABSCALE HYDROGEN STORAGE TANK BASED ON NaAlH4.
Inga Utza, Farida Joppicha, Antje Wörnera, Maximilian Fichtnerb, Oleg Zabaraba

DLR Deutsches Zentrum für Luft- und Raumfahrt, ITT, Pfaffenwaldring 38-40, 70569 Stuttgart,
Germany.
bInstitute for Nanotechnology, Forschungszentrum Karlsruhe (KIT), Herrmann-von-Helmholtz
Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
Experimental results of absorption and desorption reactions of cerium-doped NaAlH4 in an air-heated tankare presented. With a hydrogenation pressure of 100 bars a maximum capacity of 3.5 wt% is reached after
4 h during absorption experiments. For desorption, after 5 h reaction a capacity of 3.5 wt% is reached at apressure of 4 bars and 150°C. Additionally, the kinetics of the material and the tank geometry have beenmodelled and the influence of cooling heat transfer and inlet hydrogen temperature are analyzed.

Introduction
In this work absorption and desorption
reactions of 300 g cerium-doped sodium
alanate provided by KIT have been tested ina lab-scale test-setup. The material has beenchosen as it proves high hydrogen capacitiy
and good cycling stability [1]. The hydrating
and dehydrating reaction of doped sodium
alanate proceed in two steps with a required
temperature for absorption of ~80 and fordesorption of ~150°C.
st
1 step: 3 NaAlH4 ↔ Na3AlH6 + 2 Al + 3 H2
2nd step: Na3AlH6 ↔ 3 NaH + Al + 3/2 H2.
The tank model used in this work is based ona model for LaNi5 [2] and has been extended
to these two-step kinetics of sodium alanate.

Experimental

In the newly-built experimental setup, thetank is heated with air from a blower andfor absorption, the H2 is pre-heated by athermostatic bath. The flow rate fordesorption and absorption reactions canbe either flow or pressure controlled.

Results
The experimental charge- discharge cyclesof the air-heated tank (diameter: 43 mm)show good reproducibility. For the absorption
reaction ~2 wt% H2 have been stored in 30
min and a total capacity of 3.5 wt% has beenreached in 4 h. Desorption results show acapacity of 3.5 wt% in 5 h. Simulations showfor low inlet and air temperatures high rates
in the beginning of an absorption, as thereaction heat is removed quickly. However,as the kinetics of the material are rather slow,
in the end of the reaction the absorption heatis marginal, the tank gets cool and thereaction slows down. Thus, by increasing the
air temperature during the reaction one canachieve fast absorption times.

References
Fig. 1. Experimental test-setup, reactor on the left.

[1] Bogdanović et al; J. Alloys Compd. 471(2009)383[2] Coutourier et al; Proceedings of the ASME
ES2008-54031

Corresponding author: Inga Utz, email: inga.utz@dlr.de, Tel. (+49) (711) 6862 492

58

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Wildhaus, Switzerland 2010

CORRELATION BETWEEN MORPHOLOGY, WATER UPTAKE,
AND PROTON CONDUCTIVITY IN RADIATION GRAFTEDPROTON EXCHANGE MEMBRANES
S. Balog1, U. Gasser1,2, K. Mortensen3, L. Gubler4, H. Ben youcef4, and G. G.
Scherer4
1

Laboratory for Neutron Scattering, ETH Zurich & Paul Scherrer Institut, Switzerland
Adolphe Merkle Institute, University of Fribourg, Switzerland
Department of Natural Sciences, University of Copenhagen, Denmark
4Electrochemistry Laboratory, Paul Scherrer Institut, Switzerland
2
3

An SANS investigation of hydrated proton exchange membranes is presented. To understandthe relationship between morphology, water uptake, and proton conductivity, we applied thetechnique of contrast variation.

Experimental

3

le
ve
l in
cr

ea
se
s

10

2

lin
k

10

a

os
s

b

cr

-1

Our membranes were synthesized byradiation-induced grafting of poly(ethylenealt-tetrafluoroethylene) (ETFE) with styrene
inthepresenceofcrosslinker(divinylbenzene, DVB), and by sulfonatingthepolystyrene.
Crosslinking
highlyinfluences the fuel cell relevant properties.
We report on the domain structure, focusing
on the impact of crosslinking on therelationship between the domain structure,
water uptake, and proton conductivity.

(Fig. 1.), indicating a percolated network offinely dispersed aqueous pores in thehydrophilic domains.

 [mS cm ]Introduction

e dc
f

1

10

1

10

2

10

volume fraction of water [%]SANS contrast variation method was used.
The ion exchange capacity, proton
conductivity, water uptake, and hydration
number were characterized using ourstandard procedures.

Fig. 1. Proton conductivity versus volume
fraction of water in the hydrated
membranes. The crosslink level is a.) 0%,b.) 5%, c.) 8%, d.) 10%, e.) 15%, f.) 20%.

Results

References

The membranes are separated into twophases. The amorphous phase hosts thewater and swells upon hydration, swelling
being inversely proportional to the degreeof crosslinking. Hydration and proton
conductivity exhibit linear dependence on
swelling. Proton conductivity and volumetricfraction of water are related by a power law[1] S. A. Guersel et al. Radiation grafted
membranes. Fuel Cells I, vol. 215 of Advancesin Polymer Science, pages 157-217.
[2] L. Gubler et al. Radiation-grafted proton
conducting membranes. Handbook of Fuel Cells:
AdvancesinElectrocatalysis,
Materials,
Diagnostics and Durability, vol. 5 & 6Corresponding author: Sandor Balog, email: sandor.balog@psi.ch, Tel. (+41) (56) 310 5586

59

4th Hydrogen & Energy Symposium

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HYDROGEN PRODUCTION BY ALKALINE ELECTROLYSIS:SURFACE AND ELECTROCHEMICAL INVESTIGATIONS OF
MATERIALS FOR DIAPHRAGMS
V. Zakaznova-Herzog1, N. Xanthopoulos2, J. Stojadinovic1, B. Fumey1, M.
Gorbar1, D. Wiedenmann1,3, B. Grobéty3, U. Vogt1, A. Züttel1
1

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

2

Laboratoire Analyse des Surfaces, EPFL-SB-CIME, CH-1015 Lausanne, Switzerland

3

University of Fribourg, Dept. of Geosciences, Chemin du Musée 6, Pérolles, CH-1700 Fribourg

Production of hydrogen using high pressure alkaline electrolysis is well established and allows obtaining
high purity pressurised hydrogen and oxygen gases. The electrolyser’s efficiency depends significantly on
the ion-conductivity of diaphragms/membranes separating oxygen and hydrogen. Currently useddiaphragms are made of asbestos, which are not only prohibited by recent health regulations, but also
require high energy consumption. Therefore, we are looking for a new material to substitute asbestos
which has an equal or even better performance. High gas purity, i.e., low gas penetration, is achieved
through the small size of pores which is smaller than the hydrogen and oxygen bubbles. High ionic
conductivity in asbestos is mainly achieved through its excellent wettability, the effects related to the
fibrous structure and the specific porosity. The aforementioned properties most probably with the interplayof surface processes influence the ion conductivity. We report our first results of X-ray photoelectron
spectroscopic study of pristine and reacted asbestos diaphragms and olivine mineral (Mg2SiO4) in 25%
KOH at ambient conditions. The data combined with impedance measurements and tests in theelectrolysis cell will allow the evaluation of new possibilities materials for new diaphragms.

Idea
Chrysotile mineral is known for its high ion
conductance and gas tightness combinedwith high resistance to bases and acids,
good flexibility and robustness. Qualitatively
it can be explained by the special chemicalcomposition (Mg silicate and OH group) but
also the crystal structure (giving the presence
fibres and pores). Some of silicate minerals
of serpentine group have also the fibrous
structure of asbestos, but contain otheradditional to Mg cations (like Al, Na, Fe etc)
and can not be directly used as a substituting
material. Other available Mg-silicate minerals
don’t have a fibrous crystal structure. Recent
XPS study of leaching of Mg silicate mineralsrevealed the presence monolayer OH
coverage on surface [1]. These surface
complexes appear to be stable in the highvacuum XPS. Considering this new
information, we can purposely create highsurface area mineral membranes that have
OH group presented on the surface
comparable to asbestos surface.

Results
In the present study, we collected XPS
spectra of pristine and used asbestos
diaphragm and from the olivine freshly
fractured and exposed to 30% KOH solution.
at ambient conditions. The survey XPS
spectra reveal strong changes in surface
composition due to the reaction with KOH.
The changes in oxygen chemical state on thesurface can be detected from high resolution
O 1s spectra and show an additional
contribution (up to 10%). The position andthe line width of the additional oxygen
contribution species are similar to theobserved previously OH- species.

References[1] Zakaznova-Herzog V.P., H.W. Nesbitt, G.M.
Bancroft and J.S. Tse. (2008) Geochim.
Cosmochim. Acta 72, 69-86

Corresponding author: V. Zakaznova-Herzog, email: valentina.herzog@empa.ch, Tel. (+41) (44) 823 4352

60

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

FIRST-PRINCIPLES INVESTIGATIONS OF HYDROGENATIONPROCESS OF GRAPHENE: IN CONTEXT OF HYDROGEN
STORAGE
Jieun Cho, Seok Ho Lim, Noejung Park
Department of Applied Physics, Dankook University, Yongin-si, 448-701, Korea
We use density-functional theory methods to investigate the energetics related to hydrogenation ofgraphene fragments. This work is motivated by recent experimental assertions that hydrogen spills overfrom metal catalyst to bridged carbon surfaces and a substantial amount of storage can be attained inroom temperature. Concerned with doubt regarding those suggestions, we try to answer threequestionable points: the thermodynamic stability of chemisorbed hydrogen atoms on graphene, the2feasibility of hydrogen diffusion through the sp -bonded carbon surface, and the effect of metal particles
regarding whether the presence of metal particles can stabilize the hydrogen chemisorptions and lower the
diffusion barrier. Unlike previous models, our results suggest that the pure carbon surface can not be an
appropriate receptor for room temperature hydrogen storage, even though the spill-over to an unexploredsurface might deserve further investigation in pursuit of room temperature hydrogen storage.

Introduction
Hydrogen has been considered an ideal fuelfor renewable energy because it is abundanton Earth, and its oxidation product, which is
nothing but water, is environment-friendly
and completely harmless. However, how tostore enough amount of hydrogen remains a
big challenge and needs a breakthrough.
During recent years, a new class of sorbent
materials has been explored using theapproach of the so-called hydrogen spillover.
The spillover phenomenon can be defined as
dissociative chemisorptions of hydrogenmolecules on metal catalyst and subsequentmigration or surface diffusion of the atomic
hydrogen onto the support surfaces. Some
research group claimed that a few weightpercents of hydrogen can be reversibly
stored into carbon material near room
temperature
throughthespilloverphenomena. In the present work, weinvestigate the feasibility of hydrogen
spillover onto the carbon-based receptor.

Experimental
To obtain the geometries and energetics ofadsorption and desorption reactions ofmolecular hydrogen, density functional theory(DFT) calculations were performed with thegeneralized gradient-corrected approximation(BLYP). Local minimum structures andminimum energy reaction paths were
determined. All calculations reported wereobtained with the Vienna Ab initio Simulation
Package (VASP) and NWchem package.

Results
In consistence with previous works, we foundthat hydrogen chemisorptions onto carbon
surfacecansatisfy
thermodynamic
requirement for room temperature hydrogenstorage if an appropriately-sized predefined
sp3 region is provided. However, the barrier
for migration of chemisorbed hydrogen was
found to be too high. The barrier calculatedwith DFT/GGA/BLYP method is found to bearound 0.8 eV. This indicates that the sp2
carbon surface can be a proper receptor forroom temperature hydrogen storage. We
suggest that surfaces with lower diffusion
barriers should be provided in order for the
spillover to be used in hydrogen storage nearroom temperature.

Corresponding author: Noejung Park, email: noejung@dku.edu, Tel. (+81) (031) 8005 3208

61

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OPTIMIZATION OF METAL DISPERSION AND HYDROGENADSORPTION IN DOPED GRAPHITIC MATERIALS FOR
HYDROGEN STORAGE
Gyu-Bong Kim1, Noejung Park2, and Seung-Hoon Jhi1
12Department of Physics, POSTECH, Pohang 790-784, Republic of Korea, Dept. Applied
Physics, Dankook University, Yongin 448-701, Republic of Korea

The non-covalent hydrogen binding on metal atoms dispersed on carbon clusters and graphene is studied
with the use of the pseudopotential density-functional method. Substitutional doping in graphenes is
explored to control the ionic state of the metal atoms that plays a crucial role for dispersion and hydrogen
adsorption. It is found that the presence of acceptor-like states in the absorbents is essential for enhancing
the metal adsorption strength and for increasing the number of hydrogen molecules attached to the metal
atoms. This finding enables the optimization of hydrogen adsorption and metal dispersion in graphitic
materials, which is useful for developing solid hydrogen storage and efficient catalysts.

Introduction
The interaction of hydrogen molecules withmetal atoms is a key physicochemical
process involved in fuel cell catalysts andhydrogenstorage.
Transition
metal
complexes have been studied extensively inthis respect as they were shown to be very
promising in terms of hydrogen binding
strength and storage capacity at ambientconditions. Here we study the dispersion of
metal atoms in doped graphenes and thehydrogen adsorption on these metals withthe use of ab initio methods.

adsorption thereon. The H2 adsorption insuch complexes exhibits a crossover
between Kubas and multipole Coulombinteractions depending on the ionic state ofmetals and the number of adsorbed H2. Our
study suggests that material characteristics
such as doping conditions can be optimized
utilizing such an understanding of theadsorption mechanism in metal-dispersedmaterials.

Computational
The DFT calculations are performed using
the spin-polarized pseudopotential totalenergy method as implemented in the VASP
package. To investigate the accuracy of thedensity-functional calculations, part ofcalculations are repeated using the MP2 ingraphene clusters with various basis sets as
implemented in NWCHEM packages.

Results
Boron-doped graphenes were found to beeffective for dispersion of both alkaline-earth
and transition metals and hydrogen

Fig. 1. Consecutive H2 binding energies to Mgand Ca-C32−xBx complexes.

References[1] Kim et. al.; Phys. Rev. B 79 (2009) 155437[2] Kim et. al.; Phys. Rev. B 78 (2008) 085408

Corresponding author: Seung-Hoon Jhi, email: jhish@postech.ac.kr, Tel. (+82) (54) 279 2094

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A BRIEF REVIEW OF CYCLAM AND RELATED COMPLEXES OF
NICKEL: HYDROGEN REDUCTION AND CARBON FIXATION
Andrew Churchard and Wojciech Grochala
ICM and Faculty of Chemistry, The University of Warsaw, Poland

The macrocyclic, tetraamine ligand, 1,4,8,11tetraazacyclotetradecane, commonly referred to as
cyclam, has shown itself to be a remarkably usefulligand. Beley et al1 were the first to show the
surprisingly high efficiency of a reduced form ofNi(cyclam)2+ in catalysis of the electroreduction of
CO2 in water.
2
In 2006, Grochala noted the similarities
between CO2 and H2 in Mulliken electronegativity andPearson hardness, postulating that Ni(cyclam)
complexes may be useful for reducing H2, and thus
as catalysts in complex hydride hydrogen stores.
In this contribution we will review selected
literature, focusing mainly on nickel cyclam
complexes, covering the concepts of hydrogen
reduction and carbon dioxide fixation. We will also
report on on our own work including the synthesis
and characterisation of two Ni(cyclam)(BH4)2
isomers, see figure.

References[1]Beley et al; J. Chem. Soc., Chem Comm. 2 (1984) 1315
[2]Grochala, W; Phys Chem. Chem. Phys. 8 (2006) 1340

Corresponding author: Wojciech Grochala, email: wg22@cornell.edu, Tel. (+48) 22 554 0828

63

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Al IN ZIF-8: ENCAPSULATING MAGIC
Ewa Banacha, Hans Stila, Huub Kooijmana and Hans Geerlingsa, baShell Global Solutions International BV, Innovation & Research, 1030 BN Amsterdam, theNetherlandsbDelftChemTech, Materials for Energy Conversion and Storage, Delft University of Technology,
2600 GA Delft, the Netherlands
Synthesis and characterization of a Al/ZIF-8 composites by applying the organometallic precursors isdemonstrated. Since the crystal structure of ZIF-8 should be preserved as its cavities will serve as a matrix
for aluminum nanoparticles , ( so called “magic clusters”) main focus is to find a suitable precursor. We
have been able to identify amine-alane adduct: dimethylethylamine alane as the one which does not affectthe structure of ZIF-8. Synthesized product is further analyzed by employing various analytical techniques.

Introduction
Zeolitic imidazolate frameworks (ZIFs) are a
new class of nanoporous materials which
consist of
tetrahedral transition metalclusters (Co, In, Zn, etc.) linked by simple
imidazolate ligands. Those materials exhibit
a tunable pore size, possess exceptional
chemical stability and the rich structural
diversity of zeolites. ZIF-8 is a prototypical
ZIF compound (Zn(MeIM)2, MeIM=2methylimidazolate) with sodalite type ofstructure.
In this project we focus on the Al/ZIF-8
system that has been prepared employing
precursor chemistry originating from themetal organic chemical vapour depositionof metal thin films (MOCVD) to load
nanoporous crystalline powder of ZIF-8 withaluminumnanoparticles
toyield
nanocomposites which could be used forreversible storage of hydrogen.

Experimental
Aluminum loaded ZIF-8 species weresynthesized by a gas-phase loading andsolution infiltration method using two typesoforganometallic
compounds(triethylaluminum and dimethylethylamine
alane).
In order to correlate the data sets fromdifferent microscopy methods with theelectrochemical
performance,
newconcepts for multi-scale characterisation
have to be established.

Results
Utilizing various analytical techniques(PXRD, ICP, TEM, solid state NMR)
characterization and comparison of the
products were conducted to reveal the most
optimal way of preparation and the mostsuitable organometallic precursor.

References[1] K.S. Park, et al, PNAS, 103, 2006, 27[2] D.M. Frigo, et al, Chem. Mater., 6, 1994,
190[3] H. Wu, et al, J. Am. Chem. Soc., 129,
2007, 5314
[4] B. Kiran et al., Phys. Rev. Lett. 98, 2007,
256802[5] D.M. Cox et al., J.Phys.Chem. , 1988,
92, 421-429

Corresponding author : Ewa Banach, email: ewa.banach@shell.com,

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POSTERSSESSION 1
MONDAY

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4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

IMPACT OF MULTI-SCALE PORE STRUCTURE ON IONCONDUCTIVITY OF ASBESTOS GAS SEPARATION
DIAPHRAGMS FOR ALKALINE WATER ELECTROLYSIS
D. Wiedenmann1,2, L. Holzer2, M. Gorbar1,2, U. Vogt2, V. Zakaznova-Herzog2, A.
Züttel2, B. Grobéty1
1

University of Fribourg, Department of Geosciences, Pérolles, 1700 Fribourg, Switzerland
Empa, Swiss Federal Laboratories for Materials Testing and Research, 8600 Dübendorf,
Switzerland
2

High-pressure alkaline electrolysis is a very efficient method to produce hydrogen on anindustrial scale. To ensure high gas purity, anode and cathode of the electrolysis cell are
separated by a porous and ion conductive diaphragm, which prevents intermixing of producedhydrogen and oxygen. In the case of zero-gap geometry, a flexible asbestos tissue is used, as it
easily can be installed between the electrodes without being damaged. In order to keep the cell
resistance low, the ionic conductivity of the porous diaphragm is crucial. Thereby, theconductivity is related to the pore structure. The aim of this study is to characterize the multiscale pore structure by means of tomography and to establish a link to the electrochemical cell
performance.

Introduction

Results

Due to recent health regulations, asbestos
based gas separation diaphragms are
ptohibited in new electrolysers. For thedevelopment of alternative material concepts
a thorough understanding of the link between
microstructure and cell performance isfundamental.

As shown in figure 1, the asbestos
diaphragm can be considered as a 3-phasematerial consisting of macro-pores, densesolid material and a nano-porous phase with
reduced permeability. Whereas the solid
phase can be distinguished from thepermeable material with micro-CT on a lager
scale, the details between macro-pores andthe nano-porous phase require highresolution FIB-tomography. New concepts for
multi-scale analyses and their correlation
with electrochemical measurements arepresented in this paper. Effects of pore
structure (connectivity, percolation, tortuosityand constrictivity) will be discussed.

Experimental
In this study the multi-scale pore structure ischaracterized by X-ray microtomography(resolutions 1µm/2.5µm) and low voltage
FIB-nanotomography (resolution 15 nm).
Basedonmodernimage
analysestechniques, the 3D pore structure is
described quantitatively.
The influence of the permeability regarding
the electrochemical performance can becharacterized by impedance spectroscopy.
In order to correlate the data sets fromdifferent microscopy methods with theelectrochemical performance, new concepts
for multi-scale characterisation have to beestablished.

Fig. 1: 2d-images from tomography stacks bymicro-CT(left)andFIB(right).
Corresponding author: Daniel Wiedenmann: daniel.wiedenmann@empa.ch, Tel. (+41) (44) 823 4860

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STRUCTURAL AND THERMODYNAMICAL PROPERTIES OF
DOUBLE-ANION COMPLEX HYDRIDE, Mg(BH4)(NH2)
Kazutoshi Miwa,1 Tatsuo Noritake,1 Masakazu Aoki,1 Mitsuru Matsumoto,1
Shin-ichi Towata,1 Hai-Wen Li,2 and Shin-ichi Orimo2
1

Toyota Central R&D Labs., Inc., Nagakute, Aichi 480-1192, Japan
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba, Sendai 980-8577,
Japan
2

The double-anion complex hydride, Mg(BH4)(NH2), has been synthesized by heating the mixture ofMg(BH4)2 and Mg(NH2)2 with the molar ratio of 1:1 up to 180°C. The x-ray diffraction (XRD) analysis
reveals that the structure of Mg(BH4)(NH2) is tetragonal with the lattice constants of a = 5.771 Ǻ and c =20.553 Ǻ. Using these experimental information, we have constructed model structures and performed thefirst-principles calculations for them. The symmetry is expected to be I41 (No. 80): The calculated lattice
constants agree well with the experimental ones and the structure fairly reproduces the measured XRD
pattern. Unfortunately, the hydrogen desorption reaction of Mg(BH4)(NH2) is predicted to be exothermic. In
a practical point of view, it is necessary to stabilize the material for reversible hydrogen storage
applications.

Introduction
The
double-anion
complexhydride,Mg(BH4)(NH2), has been synthesized. The
starting material for sample preparation is a
pre-milled mixture of Mg(BH4)2 and Mg(NH2)2
in a 1:1 molar ratio. The crystalline
Mg(BH4)(NH2) can be obtained with heat
treatment at 155-180°C. The x-ray diffraction(XRD) analysis indicates that the structure is
tetragonal with the lattice constants of a =5.771 Ǻ and c = 20.553 Ǻ. However, thedetailed crystal structure is still uncertain. In
this study, the first-principles calculations are
performed to predict the structural andthermodynamical
properties
ofMg(BH4)(NH2).

MethodOur calculation is based on density functional
theory within the ultrasoft pseudopotential
method. Assuming the symmetry of crystal,
the arrangement of cations and anions isdetermined roughly, and then the detailed
structural parameters are optimized by the
first-principles calculations.

Results
The model structure with space group I41(No. 80) gives a satisfactory result. The
calculated lattice constants are a = 5.778 Ǻand c = 20.726 Ǻ which agree well with theexperimental ones. This structure also
reproduces the measured XRD pattern.
The enthalpy change for the following mixing
reaction is obtained to be H = -10 kJ/mol,
1/2Mg(BH4)2 + 1/2Mg(NH2) → Mg(BH4)(NH2).
This supports the formation of the doubleanion system. The hydrogen release ofMg(BH4)(NH2) proceeds along the following
reaction,
Mg(BH4)(NH2) → MgH2 + BN + 2H2.
This reaction is predicted to be exothermicwith H = -7 kJ/mol H2, indicating that thereaction is not reversible. In a practical pointof view, it is necessary to improve thereaction thermodynamics.

Corresponding author: Kazutoshi Miwa, email: miwa@cmp.tytlabs.co.jp

67

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A COMPARATIVE STUDY OF POROUS HYDROGEN STORAGE
MATERIALS
Allan Walton, Steve Tedds, David Book, School of Metallurgy and Materials, University ofBirmingham, Birmingham, UK
The hydrogen sorption behaviour of a range of porous materials have been assessed using agravimetric balance over a wide range of temperatures (77-293 K). The porous materials
assessed include: zeolites; porous carbons; metal organic frameworks (MOFs); and Polymers ofIntrinsic Microporosity (PIMs). The structural characteristics of these materials have been
investigated using both volumetric and gravimetric techniques to assess the pore structure,density and surface area. PCT curves were used to calculate the heats of adsorption vshydrogen uptake, and to monitor the temperature dependence of hydrogen capacity.

Porous materials have demonstrated high H2
capacities (up to 7.5 excess wt% at 77 K at
70bar) [1]. The maximum hydrogen uptake
has been shown to be linearly related to
specific surface area (SSA). However, atlower pressures, the temperature dependenthydrogen capacities have been shown to berelated to the strength of the adsorbate –absorbent interactions, i.e. the isosteric heatof adsorption. In this work, these heats havebeen calculated for a range of materials using
multiple pressure composition isotherms
measured over a wide range of temperatures.
The heats of adsorption are related to thepore size for each type of material.

the Toth and Langmuir-Freundlich fits inconjunction with the Clausius-Clapeyron
equation as well using a Virial method. At
50% fractional coverage the heats ofadsorption for most of the materials wasaround 4 kJ mol-1H2. However, at lower
fractional coverages the heats of adsorption
differed significantly, with the activated carbon
giving the highest values.
Wt% H2 vs Temperature at 0.1 MPa

2.5

IRMOF-1
Cu-BTC
Zeolite NaX
Activated carbon

2
wt% Hydrogen

Introduction

1.5
1
0.5
0
77

Experimental
Variable temperature hydrogen isotherms
were recorded on a Pressure Controlled
Gravimetric Balance (Hiden IGA 001) up to
1.6 MPa. A pumped liquid nitrogen cryostat
was used to control temperatures from 87-300
K, stable to ±0.1 K. Wt% H2 values were
calculated as: the mass of H2 / dry mass ofthe sample.
Results
All of the materials exhibited a Type 1
adsorption isotherm. Although IRMOF-1
exhibited the highest uptake at 1.6 MPa (3.8
wt% at 87 K), at 0.1 MPa all of the otherporous materials exhibited higher capacities.
The heats of adsorption for all materials were
calculated versus fractional coverage using

87

97

107
Temp (K)

117

127

137

Conclusion
The heats of adsorption for each material did
appear to correlate with pore size. Generally,
the materials with a small pore size
demonstrated a steeper hydrogen uptake at
low pressure. However at 0.1 MPa the wt% H2
did not directly correlate with the heat ofadsorption, which would indicate that surface
area is likely to have an increased influence inthis pressure range. A comparison is madebetween the surface area, pore size and heatof adsorption with reference to the ‘usable’hydrogen storage capacity (in a vehicular
store) at different temperatures.
[1] M.K. Thomas; Dalton Trans., 2009,p1487 1505

Corresponding author: Allan Walton, email: a.walton@bham.ac.uk, Tel. (+44) 121 414 3960

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ANALYSIS OF THERMAL DECOMPOSITION OF T-BUTYLAMINEBORANE
Jordan Feigerle, Norm Smyrl, Jonathan Morrell, Ashley C. Stowe
B&W Y-12 National Security Complex, 301 Bear Creek Road, MS 8097, Oak Ridge, TN 37831
USA
Amine boranes are a class of hydrogen storage materials which release significant yields of hydrogen gas
upon heating to temperatures relevant for automotive applications. The thermodynamic stability of thisclass of amine boranes is correlated with the extensive di-hydrogen bonding between hydrides bound toboron and amine protons. Further, the hydrogen evolution follows a bimolecular pathway via the dihydrogen bonding network. The thermal decomposition of t-butylamine borane (tBuAB), (CH3)3CH2NBH3,
has been studied in order to understand the reaction pathway of hydrogen sorption and the impact of the t1
1113butyl substitution dehydrogenation thermodynamics. H, B, and C solid state nuclear magnetic
resonance (NMR) spectroscopy has revealed that heating initiates two separate reaction pathways:
isomerization and hydrocarbon abstraction resulting in varying yields of isobutane and hydrogen. It is also
possible that tBuAB dissociates about the N-B bond giving rise to borane stretching modes in the gas
FTIR. Trapped t-butylamine (tBuA) which slowly diffuses from the tBuAB solid in 13C NMR studies
appears to be present; however, this spectral region is convoluted by other decomposition products. 11B
NMR indicates that the major reaction pathway results in hydrogen evolution with isobutane formation
being present in smaller yields. The t-butyl substitution lowers the thermodynamic stability—compared to
NH3BH3—but results in impure hydrogen gas stream and lowered capacity due to isobutene evolution.

Introduction
Amine boranes release significant yields ofhydrogen gas with heating; however, there
are still significant challenges in rehydriding
the spent fuel. The boron nitride oligomericproducts are thermodynamically stable withrespect to the hydrided fuel such thatdigestion and chemical processing is being
considered.
Investigation of substituted
amine boranes can potential reveal subtly inthe decomposition pathways that may help
control the eventual decomposition products
allowing
for
lessenergyintensive
rehydrogenation. Further, it was shown that
CBN species were less thermodynamicallystable than BN analogues [1].

Results
1

13

11

H, C, and B solid state MAS NMR
studies of t-butylamine borane (tBuAB)oheated isothermally to 80-95 C over 10 hr
evolved hydrogen and isobutane through acomplex reaction pathway. A minor amountof dissociation was also observed in evolved
gas FTIR studies. Trapped t-butylamine gas
was observed in the 13C solid state NMR
spectrum. This was due to slow diffusion
through the decomposing tBuAB lattice.
Evolution of hydrogen gas dominates thedecomposition. As the reaction proceeds,
both [BNH]x—from initial isobutane release—and [CBNH]x oligomers are observed.
Although the hydrogen yield is reduced by
isobutane evolution, the [CBNH]x products
are more thermoneutral and thus more easily
regenerated.
Perhaps the addition of substituted amine
boranes as a mixture with ammonia borane
will yield a material with sufficient H2 yields
which results in a more thermoneutral[CBNH]x product.

References[1] D. J. Grant, M. H. Matus, K. D. Anderson, D.
M. Camaioni, S. R. Neufeldt, C. F. Lane, D. A.
Dixon, J. Phys. Chem. A 2009, 113, 6121–6132.

Corresponding author: Ashley Stowe, email: stoweac@y12.doe.gov, Tel. (+1) (865) 241 0675

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DESTABILIZATION REACTION OF LiBH4 + MH COMPOSITESENHANCED BY HYDROGEN BACK PRESSRURE
Jae-Hyeok Shim,1 Jae-Hag Lim,1 Sami-ullah Rather,1 Young-Su Lee,1
Daniel Reed,2 Yoonyoung Kim,1 David Book,2 Young Whan Cho1
1

Advanced Functional Materials Research Center, Korea Institute of Science and Technology,
Seoul 136-791, Republic of Korea
2

School of Metallurgy and Materials, University of Birmingham, Birmingham B15 2TT, U.K.

Hydrogen back pressure remarkably promotes the formation of metal boride during the dehydrogenation of
4LiBH4 + YH3, 6LiBH4 + CeH2 and 6LiBH4 + CaH2 composites, which seems to be a general phenomenon
in LiBH4-based reactive hydride composites that enables mutual destabilization between LiBH4 and metal
hydride. The formation of metal boride plays a crucial role in the reversible hydrogen storage properties ofthese composites. The dependence of the dehydrogenation behavior on hydrogen back pressure might beassociated with the microstructural evolution of the dehydrogenation products formed by a solid-liquid
reaction.

Introduction
In this study, we investigate the effect ofhydrogenbackpressureonthedehydrogenation path of 4LiBH4 + YH3,
6LiBH4 + CeH2 and 6LiBH4 + CaH2
composites. Also, the reversibility of thedehydrogenation
andrehydrogenation
reactions of these composites is investigated.

Experimental
6LiBH4 + CaH2, 4LiBH4 + YH3, 6LiBH4 +CeH2 composites were prepared by ball
milling. The dehydrogenation was conducted
at 350 oC for 24 hours at two different initialpressures, vacuum and 3 bar of hydrogen.
The rehydrogenation was done for 24 hours
at 90 bar of hydrogen. XRD analysis was
carriedoutontheball-milled,dehydrogenatedandrehydrogenatedsamples.
Raman
spectroscopy
wasperformed on the dehydrogenated samples
at room temperature.

composite starting from vacuum presents
fast kinetics up to about 1 hour, thedehydrogenation rate becomes slow after
about 1 hour. The amount of hydrogen
released after 24 hours is less than 2 wt%.
On the other hand, this composite releases
about 7.2 wt% hydrogen after 24 hours,
when the dehydrogenation starts with a 3 barhydrogen back pressure. The 6LiBH4 + CeH2
composite exhibits dehydrogenation behavior
similar to that of the 4LiBH4 + YH3 composite,
in terms of the effect of the initial pressure
conditions. This positive effect of hydrogenback pressure during dehydrogenation is
unexpected, considering that hydrogen backpressure would retard the decomposition of
metal hydrides in a thermodynamic sense.

Results
The dehydrogenation profiles of the 4LiBH4 +YH3 and 6LiBH4 + CeH2 composites at 350o
C are shown in Fig. 1. Althoughdehydrogenation of the 4LiBH4 + YH3

Fig. 1. Dehydrogenation profiles of the 4LiBH4 +YH3 composite under (a) static vacuum and (b)hydrogen back pressure and those of the 6LiBH4+ CeH2 composite under (c) static vacuum and (d)hydrogen back pressure.

Corresponding author: Jae-Hyeok Shim, email: jhshim@kist.re.kr, Tel. +82-2-958-6760

704th Hydrogen & Energy Symposium

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EFFECT OF NANOSTRUCTURING ON THE HYDROGEN
STORAGE PROPERTIES OF LaNi5 SYSTEMS
Benedetto Schiavo1,2, Boby Joseph3, Giacomo D’Alì Staiti1,2, Naurang L. Saini3
1

Dip. di Fisica e Tecnologie Relative (DIFTER), Università di Palermo, Italy
Istituto Tecnologie Avanzate, SS 113, Base di ASI ‘‘L. Broglio” ,Trapani, Italy
3
Dip. di Fisica, Università di Roma “La Sapienza”, P.le Aldo Moro 2, Rome, 00185 Italy
2

Pressure–composition isotherms of LaNi5 alloys were studied as function of ball-milling time. Results
indicate a strong hindrance to the hydrogenation of the long-time ball-milled samples. Local structural
studies reveal that the nanostructured powders are characterised by reduced unit cell volume andenhanced atomic disorder. Results of the x-ray diffraction and differential scanning calorimetry are inagreement with the results of the local structure studies.

Introduction
Nanostructuring using ball-milling is found tobe very effective in improving the hydrogen
sorption kinetics of materials like Mg [1].
However,ball-milling
inducednanostructuring is found to have an adverse
effect on the hydrogen sorption properties of
the conventional hydrogen storage material,
LaNi5 [2]. We have studied the above systemusing a number of experimental techniques a brief summary of the results are presented.

Experimental
Ball-milling of the LaNi5 powders, withvarying milling times, were performed using a
Fritsch miller. Some of the milled samples
were annealed under high vacuum.
Hydrogen sorption properties of thesesamples were studied by measuring thepressure-composition isotherms (PCIs) at
35°C using an automated Sievert’s
equipment. Local structure of these samples
were studied using the Ni K-edge extended
x-ray absorption fine structure (EXAFS).
Differential scanning calorimetry (DSC) andx-ray diffraction (XRD) were also utilised forthe characterization of the samples.

Results
With increase in milling time, PCIs showed
an increased in the plateau-pressure and areduction in the hydrogen capacity atpressures below 20 bar [2]. DSC

measurements indicated an increase in thedefect density with milling time. Observed
enhancement in H2 intake in the initial part of
the PCIs can be explained considering themilling induced particle size reduction andincrease in surface defects. XRD results
reveal that the long-time milled samples haveidentical crystal phase as that of the unmilled, but with slightly reduced lattice
parameters and drastically reduced average
crystallite sizes [3]. EXAFS results revealed a
reduction in the near-neighbour (NN)distances in the long time ball-milled
samples. In addition, a large increase in theatomic disorder was evident (as seen from
the
large
mean
squarerelativedisplacements (MSRDs) of the NN distances)[4]. Interestingly, in the long-time ball-milled
samples, annealing is found to be have little
effects in bringing back the atomic order [4].
Decrease in the NN distances and thecorresponding increase in the MSRDs may
be causing a higher energy barrier for thehydride phase formation in the long time
milled powders.

References[1] A. Zaluska et al., J. Alloys Compd 288 (1999) 217[2] B. Joseph, B. Schiavo, J. Alloys Compd 480 (2009)912[3] B. Joseph, B. Schiavo et al., Proc. of HYSDAYS2009, Torino, Italy[4] B. Joseph, A. Iadecola, B. Schiavo et al., J. Solid
State Chem. (submitted)

Corresponding author: B. Schiavo, email: benedetto.schiavo@difter.unipa.it, Tel. (+39) 0923 550130

71

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POROSITY GRADED ZrO2 DIAPHRAGMS FOR ALKALINEELECTROLYSIS
M. Gorbar 1,2, D. Wiedenmann 1,2, V.P. Zakaznova-Herzog 1, U.F. Vogt 1, B.
Grobety 2, A. Züttel 1
1

Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
2
University of Fribourg, Dept. of Geosciences, Chemin du Musée 6, Pérolles, CH-1700,
Fribourg, Switzerland
The investigation and characterization of metal oxide based ceramic materials is essential for the quest tofind materials to replace the chrysotile asbestos diaphragm used in today’s alkaline electrolyses. As asuitable material with high chemical stability to KOH 3-mol%-Y2O3-doped tetragonal-ZrO2 powder waschosen. Initial tests were performed using a lab electrolyser cell with Ni wire mesh electrodes of 34 mm
diameter. Test focus was the ion conductivity, gas purity as well as chemical and mechanical stability.

Introduction
There is an increasing interest in hydrogenas an energy carrier. A well-establishedmethod of producing high purity hydrogenfrom water is the alkaline electrolysis. Suchzero-gap electrolysers operate at 85°C, 32
bars and use a 25 wt% KOH solution. In
these electrolysers the asbestos diaphragm
prevents the mixing of hydrogen andoxygen, while warranting sufficient ion
conductivity. Although long-term studies
have shown that chrysotile asbestos isstable in KOH at temperature below 100°C,
higher temperatures will cause thediaphragm to dissolve. Due to these limiting
factors and the ban on use of asbestos inmany countries a replacement for asbestos
is crucial for the continuation of thistechnology.

Experimental part
To produce replacement diaphragms
graded porous substrates of ZrO2 havebeen prepared. Mixtures of 3-mol% Y2O3doped tetragonal ZrO2 powder (TZ-3Y) andcarbon as pore formers were uniaxialy
pressed at 50 kN to a cylindrical preform (d= 50 mm, 2.5 mm thickness) andsubsequently sintered at 1200°C for 1 hour.
Careful attention was given to keep thepore size of the TZ-3Y diaphragms samples
below the diameter of the hydrogen bubbles
evolving during electrolysis [1]. The
Diaphragms were tested using the labelectrolytic cell setup with a current density
2of 200 mA/cm and ambient conditions.
This work provides the basis for thedevelopment of new diaphragms withimproved mechanical stability, better cell
performance and better electric power
efficiency.

Results
By using different amounts of carbon as apore former (10, 20 and 30 vol%,respectively) the effect on the open porosity
was examinant. Carbon powder and fibres
where used, allowing for spherical andfibrillose pore structure after carbon burnout. This method for making ceramic bodies
having a graded porosity improved ion
conductivity and so reduced the cell voltage
drop. A slight decline in the hydrogen purity
was noted. All results were recorded andcompared to initial tests done using
chrysotile-asbestos as a diaphragm.
[1] E. Barendrecht et al., The Effect of Gas Bubble
Evolution on the Energy Efficiency in Water
Electrolysis. Annual Report 1983, Technische
Hogeschool Eindhoven.

Corresponding author: Michal Gorbar, email: michal.gorbar@empa.ch , Tel. (+41) (44) 823 4301

76

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POSTERSSESSION 2
TUESDAY73

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

HYDROGEN-POWERED APU FOR MOBILE RAIL CATERINGSERVICE: THE IHPOS-E PROJECT
M. Bielmann1, M. Hachen2, A. Züttel1
1

EMPA Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
2
Berne University of Applied Sciences, Department Energysystems, 2501 Biel/Bienne

Energy concept
Hydrogen as a high density energy carrier isdeveloping in niche markets as a viableeconomical alternative to other sources ofoff-grid energy supply. In these markets, they
directly compete with batteries as abenchmark solution. While hydrogen canhardly compete in applications where low
energy capacity is needed, in domains withhigh energy capacity the technology starts tobe competitive.

unit is based on a metal-hydride hydrogenstorage offering low pressure hydrogenstorage with safety benefits compared topressurized hydrogen.

The main advantages of hydrogen as sourceof energy in an APU system are:

Scalable energy content

No output dependence on "state ofcharge"Higher volumetric energy storage
density

These advantages are explored the project
IPHOS.

Application
Elvetino is the catering company of the Swiss
Railway. As a speciality, they provide quality
espresso coffee in a mobile sales unit directlyat the seat of the passengers. Currently, theunits are powered by Li-Ion Batteries. Whileon low-traffic connections this solution is
viable, on high-volume connections thesolution proved not sufficient and not flexible
to the needs of the company. The company
CEKA, specialized in just-in-time productionof electrical tools decided to solve theproblem by a fuel cell unit offering the same
service but a flexible energy content with norestrictions regarding charging times. The

Outlook
The current solution is based on an aircooled fuel cell. The implementation of awater-cooled fuel cell can offer significant
energy and space savings through water
preheating and more efficient waste-heatmanagement. It reduces the complexity of
the integration of metal hydride energy
storage as a source of hydrogen, where highkinetics are demanded and hard to satisfy
because of limited heat transfer to the tank.
Water heating can be implemented bycatalytical combustion of hydrogen, reducing
the necessary electrical output of the fuel cellfurther. While synergies for other APUapplications must be sacrificed for energy
efficiency, such a solution can potentially be
far superior to a battery based solution in thisparticular application.

Corresponding author: Michael Bielmann, email: michael.bielmann@empa.ch74

4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

STUDY OF HYDROGEN CONTENT AND DEPTH PROFILE IN
MAGNESIUM AND MAGNESIUM ALLUMINIUM FILMS BY ERDA
Pragya Jaina, Ankur Jaina, Devendra Vyasa, S.A.Khanb, I.P.Jaina*
ab

Centre for Non-Conventional Energy Resources, University of Rajasthan, Jaipur-302055, India
Inter University Accelerator Centre, Aruna Asif Ali Marg, New Delhi 110 067, India

Pd/Mg/Pd and Pd/Al/Mg/Pd multilayered films were deposited on Si/glass substrate using vapour
deposition technique. Pd was deposited on both sides to ensure a fast dissociation rate and good transport
properties of hydrogen and to avoid oxidation of Mg from both surface and substrate side. The particle size
and roughness is estimated in nano-meter range by AFM studies. The nano structured films have beenohydrogenated at 230 C and 5 bar H2 pressure for 2hrs. The morphological and structural changes havebeen investigated by AFM and GIXRD. Hydrogen content and depth profile is measurement by Elastic
Recoil Detection Analysis using 100MeV Ag ion beam.

Experimental
Mg (150nm) and Mg (100nm)/Al (50nm) films
were prepared and capped by 20nm Pd fromboth sides on Si/ glass substrate using vapor-6
deposition technique at 10 torr vacuum. The
phase identification and modifications due tohydrogen have been made by GIXRD and
AFM
techniques.
Hydrogencontent
measurements were done by ERDA using
100 MeV Ag ion beam irradiation.

1200

1000

2500
2000

1000

600

400

Pd[200]1500

800

Pd/Mg/Pd-H
Pd/Al/Mg/Pd-H

PdH0.7[200]Y Axis Title

3000

MgH2[110]3500

AlH3[100]

Pd[111]

4000

Pd[111]

Pd/Mg/Pd
Pd/Al/Mg/Pd

Mg[002]4500

Al[111]Thin film technique provides powerful way toinvestigate the interaction between nanoscaled Mg and H because the composition,interface and crystallinity of thin film can beeasily controlled on nano scale [1]. Thus,
various attempts have been undertaken to
study the hydrogen storage properties of Mg
thin films [2]. The present work reports
hydrogen content and depth profiling of Pd
capped Mg and Mg/Al thin films.

crystal found in AFM images confirm the
XRD findings.

Intensity

Introduction

200

500
0

0
25

Fig.1

30

35

2

40

45

50

20

25

30

35

40

45

50

X Axis Title

GIXRD of pristine and hydrogenatedPd/Mg/Pd and Pd/Al/Mg/Pd thin films.

On hydrogenation of Mg thin film, MgH2 [110]peak appears indicating the formation ofmagnesium hydride. Although small amountof Palladium hydride phase with orientation[200] is visible, but still considerable amountof Pd was found to be unreacted as like asother studies done on similar systems [3]. In
case of Mg-Al system a peak of AlH3 [100] is
observed along with MgH2 peak.

Results

References

XRD patterns of as-prepared Pd/Mg/Pd and
Pd/Al/Mg/Pd films indicate Mg [002], Pd [111]and Pd [200] as the preferential growthorientation in both samples with anadditional peak of Al [111] in Mg-Al system.
Randomly oriented hexagonal platelets of Mg[1] R. Domenech-Ferrer, M. Gurusamy Sridharan,
G. Garcia, F. Pi, J. Rodriguez-Viejo, J. Power
Sources 169 (2007) 117–122.
[2] J. Paillier, S. Bouhtiyya, G.G. Ross, L. Roue,Thin Solid Films 500 (2006) 117–123.
[3] Sanjiv Kumar, G.L.N. Reddy, V.S.Raju, J.
Alloys Compd. 476 (2009) 500-506

Corresponding author: I.P.Jain*, email: ipjain46@gmail.com, Tel. (+91) (141) 2711049

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NMR STUDIES ON Li2(BH4)(NH2) AND Li4(BH4)(NH2)3
Pascal Martelliº¹, Arndt Remhofº, Matthias Ernst², Motoaki Matsuo³, Shin-ichi
Orimo³, Andreas Züttelº¹º EMPA Materials Science and Technology, Dept. Energy, Environment & Mobility, Abt. 138 “Hydrogen &Energy”, Überlandstrasse 129, 8600 Dübendorf, Switzerland¹University of Fribourg, Physics departement, Ch. du Musée 3, 1700 Fribourg, Switzerland²ETH Zürich, Physical Chemistry, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland³Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan--

Complex hydrides with (BH4) and (NH2) anions are recently discussed as a new lithium fast-ion conductors with
-3
-1
[1]
[2]
7
conductivites in the order of 10 S cm at room temperature which is comparable with Nafion . We used Li nuclear
magnetic resonance (NMR) spectroscopy to measure the Li mobility within LiBH4, Li2(BH4)(NH2) and Li4(BH4)(NH2)3. In
pure LiBH4 the phase transition is accompanied by a sudden sharpening of the signal. We attribute this effect to a
motional narrowing due to the increased Li mobility within the high temperature phase. Similar Li mobilities are observedin Li2(BH4)(NH2) and Li4(BH4)(NH2)3 even at room temperature.

Introduction
Research on lithium ion conductors is
significantly important because they may
potentially be applied to solid electrolytes toimprove safety and energy-density related
issues of conventional lithium-ion batteries. [1]Experimental
The NMR measurements, were carried out at
ETH Zürich, using a Bruker Cryomagnet BZH
400/89 with an applied magnetic field of 9.4
T, and a frequency of 155.5 MHz. LiBH4 wasprovided by Sigma Aldrich, Li2(BH4)(NH2)and Li4(BH4)(NH2)3 were prepared at Tohoku
University.

is
The
phase
transitionin
LiBH4
accompanied by a sudden sharpening of thesignal. Thereby the FWHM decreases from
12.7 Hz at RT to 0.6 Hz at 150°C by morethan one order of magnitude. We attribute
this effect to the increased diffusivity of Li
through the lattice. This effect, known as“motional narrowing”, can be observed forLi2(BH4)(NH2) and Li4(BH4)(NH2)3. at much
lower temperatures as displayed in fig.2.

Results

7

Fig. 2: Li (I=3/2) NMR spectra of Li2(BH4)(NH2)and Li4(BH4)(NH2)3 measured at selected
temperature below their thermal decomposition.
Fig. 1: 7Li (I=3/2) NMR spectra of LiBH4 at low
and high temperature phase.
7

Figures 1 and 2 show the respective Li andLi2(BH4)(NH2), Li4(BH4)(NH2)3 NMR spectra.

References[1] Matsuo, M., Remhof, A., Martelli, P., Zuettel,
A., JACS 131, 16389 (2009).
[2] J. Electrochem. Soc., 149, (12), 1556 (2002)

Corresponding author: Pascal Martelli, email: pascal.martelli@empa.ch, Tel. (+41) (44) 823 4746

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THERMODYNAMIC PROPERTIES OF LH3/AlF3 AND MgH2/MgF2
SYSTEMS AS HYDROGEN STORAGE MATERIALS: A
COMPUTATIONAL APPROACH
Marta Corno, Piero Ugliengo, Marcello Baricco
Dipartimento di Chimica IFM, NIS Centre of Excellence and INSTM, University of Torino, Via P.
Giuria 7/9, 10125, Torino, Italy.
Thermodynamic properties of aluminium and magnesium hydrides and fluorides, both pure and mixed,
have been computed by ab initio calculations. The DFT method with the pure GGA Hamiltonian PBE has
been applied and the reference code used is CRYSTAL06 with localised Gaussian basis set. An importantstage of the study has been the calibration of computational parameters, specifically for Hamiltonian andbasis set. Solid solutions have been modelled and characterised by means of structural, electronic,
vibrational and thermodynamic properties.

Introduction
In this work ab initio calculations on AlH3/AlF3
and MgH2/MgF2 are presented. In particular,
the full characterisation of computed
structural, electronic, vibrational and thermodynamic properties has been carried out bothon pure compounds and on solid solutions.
Several significant reactions have been
simulated, such as formation, fluorination anddehydrogenation.

Experimental
The Density Functional Theory has beenchosen, considering different Hamiltonians,from pure GGA (PBE) to hybrid (B3LYP),
within the periodic CRYSTAL06 code. [1]The calibration of the computational strategy
has regarded also the optimization of thebasis set, ranging from polarized double- toquadruple-zeta cases.

Results
We optimised the computational strategy forthe simulation of hydrides and fluorides oflight-metals, showing how different choices ofcomputational parameters could affect thecharacterised properties.
++→
Fig. 1 Fluorination reaction of aluminium hydride.

Different configurations for solid solutions
have been studied, using a newly
implemented algorithm in the CRYSTAL
code, which allows the classification bysymmetry for each H/F ratio. The computed
thermodynamic values have shown a fairagreement both with experimental andthermodynamical calculations.
These data are relevant to improve ourunderstanding of solid solutions for which
only scarce experimental data are available.
This work is part of the European FP7
Project FLYHY “Fluorine Substituted HighCapacity Hydrides for Hydrogen Storage at
low Working Temperatures”. [2]References[1] www.crystal.unito.it[2] www.flyhy.eu

Corresponding author: Marta Corno, email: marta.corno@unito.it, Tel. (+39) (011) 670 4597

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R&D STATUS ON HYDROGEN PRODUCTION, STORAGE, ANDUTILIZATION TECHNOLOGIES IN KOREA
Moon-Sun Chung, Jong-Won Kim
Hydrogen Energy R&D Centre, Korea Institute of Energy Research, Daejeon, Republic of Korea
In October 2003, Korean government launched Hydrogen Energy R&D Center (HERC) as a member ofthe 21st Century Frontier R&D programs supported by the MEST. The HERC has conducted research on
the key technologies for the production, storage, and utilization of hydrogen energy for expediting
realization of hydrogen economy based on renewable energy sources. The main purposes of this article
are to overview the current status of research programs conducted by Hydrogen Energy R&D Center
based on the present topics and to introduce achievements in each research program as well as the future
works in Korea.

R&D Issues on Hydrogen Energy
Production of hydrogen from biomass may
be achieved by biological fermentation or
photosynthesis process [1, 2]. In addition,
photochemical hydrogen production as well
as low or high temperature water electrolysis
is one of the final goals to achieve though it
is not show any marked economy of scale atthe present [3].
There are three main hydrogen storage
methods
including high compression,
chemical hydride and hydrogen storage
materials. We have already demonstrated
the highly pressurized hydrogen system on
fuel cell vehicles with Hyundai motor
company. The nano-structured hydrogenstorage materials have some advantages
such as high volumetric storage capacity,
little energy loss, and highest safety [4, 5].
However, they still have low specific storage
capacity and poor cyclic properties. We also
try to develop a hydrogen storage systemusing chemical hydride like NaBH4.
Finally, hydrogen can be used as a fuel in theconventional internal combustion engines aswell as in the fuel cells. Further, if there is notransformation of linear momentum forreciprocal motion into angular momentum forcircular motion than mechanical loss can be
reduced. Additionally, the manufacturing costof internal combustion engine is relatively low
in comparison with that of fuel cells. For
these reasons, a linear piston engine withgeneration system using hydrogen is apromising technology to obtain electricity
from hydrogen combustion directly [6].

Roadmap for Hydrogen Energy R&D in Korea.

References[1] M.-S. Chung et al; 2007 Asian Bio-Hydrogen
Symposium (2007)[2] M.-S. Kim, et al; Int. J. Hydrogen Energy, 31(2006) 812-816[3] J.-O. Baeg,et al; Advanced Fuctional Materials,
16 (2006) 1349-1354[4] Y.-W. Cho, et al; Catalysis Today, 120 (2007)
292-297[5] J.-H. Kim, et al; Angew. Chem. Int. Ed. 46(2007) 8230-8233[6] D.-H. Cho, “Mover stabilization device of linear
motor and generator”, Korea Patent 20038698

Corresponding author: Dr. Moon-Sun Chung, email: moonschung@kier.re.kr, Tel. (+82) (42) 860 3591

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IMPROVEMENT OF DECOMPOSITION PROPERTIES OF LiBH4
DISPERSED ON MODIFIED MULTI-WALLED CARBON
NANOTUBES
Filippo Agresti1, Ashish Khandelwal1, Giovanni Capurso1, Sergio Lo Russo2,
Amedeo Maddalena1, Giovanni Principi1
1

Università di Padova, Dipartimento di Ingegneria Meccanica,Settore Materiali, via Marzolo 9,35131, Padova, Italy.
2
Università di Padova, Dipartimento di Fisica and CNISM, via Marzolo 8, 35131, Padova, Italy
The decomposition properties of LiBH4 dispersed on multi-walled carbon nano-tubes (MWCNT) have beenstudied. Commercial MWCNT were ball milled for different times in order to increase the specific surface
area (SSA). Thermal programmed desorption measurements (TPD) have been performed on samples withdifferent SSA of MWCNT and different LiBH4 to MWCNT ratio. Pressure composition isotherms (PCI) havebeen obtained at different temperatures in order to estimate the ΔH and ΔS of decomposition. It has been
observed that the dispersion of LiBH4 on MWCNT leads to lower decomposition temperature compared topure LiBH4. Moreover, the decomposition temperature further decreases with increasing MWCNT surface
area. An interpretation of the kinetic effect is given in the work.

Experimental
Commercial MWCNT have been modified
by high energy ball milling in order toincrease the SSA. Samples have been
milled using a SPEX 8000M shaker millwith a ball to powder ratio of 10:1. LiBH4
has been deposited on the MWCNT bysolvent infiltration technique using methyl
tert-butyl ether (MTBE). Samples withdifferent LiBH4:MWCNT mass ratios andsamples with fixed composition but using
MWCNT with different SSA have been
prepared.

8
desorbed H2 (wt%)

LiBH4 is one of the most studied complex
hydride for hydrogen storage, due to its
high theoretical gravimetric hydrogencapacity (18.4 wt%). The research isaddressed to reduce the decomposition
temperature (>400 °C) and to improvereversibility. In this work it is shown that
LiBH4 deposited on MWCNT modified byball milling exhibits lower decomposition
temperature compared to the pure material.

°C. The decomposition temperature of
LiBH4 further decreases with increasing the
SSA of MWCNT and the effect is proposed
to be due to heterogeneous nucleation of
decomposition products or intermediatephases on the carbon surface from liquid
LiBH4.

rate (wt% H2 / min)Introduction

120

180

240

300

360

6
4
2

0.20

480

8
6
4
2

2.5 °C / m in

0

0.25

420

2

As Received CNT (200 m /g)
2
BM 15 m in CNT (230 m /g)
2
BM 90 m in CNT (260 m /g)
2
BM 600 m in CNT (410 m /g)
pure LiBH 400.25

LiBH 4: MW CNT (1:1.8)

0.20

0.15

0.15

0.10

0.10

0.05

0.05

0.00

0.00
120

180

240

300
T (°C)

360

420

480

Fig. 1. Dehydrogenation profiles of samples preparedusing supports with different SSA compared with pure
LiBH4.

Finally, the dispersion of LiBH4 on the highsurface area of MWCNT does not seem tolead to thermodynamic destabilization withrespect to pure material due to size effectResults
LiBH4 dispersed on MWCNT shows
decreased decomposition temperature withrespect to pure material by more than 60
Corresponding author: Filippo Agresti, email: filippo.agresti@unipd.it , Tel. (+39) 049 827 5828

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HYDROGEN EVOLUTION FROM DECOMPOSITION OF
BOROHYDRIDES: THE “BORON EFFECT”
F. Pendolino a, S. Garroni b, C. Milanese c, A. Girella c, A. Borgschulte a, D. Baro b,
A. Marini c and A. Züttel aabcEmpa, Abt. 138 “Hydrogen & Energy”, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland
Department de Fisica, Universitat Autonoma de Barcelona, E-08193 Bellaterra, Spain
CSGI Dep. Physical Chemistry, University of Pavia, Viale Taramelli 16, I-27100 Pavia, Italy

The boron effect was investigated for the thermal decomposition of light metal borohydrides M(BH4)n (M =Li, Na, K, Ca). The addition of boron enhanced the dehydrogenation process via the formation of new
intermediate. A partial decomposition of material was needed in order to form this intermediate. The
decomposition temperature of lithium borohydride and calcium borohydride was lowered of 150 °C and 20°C respectively.

Introduction

Results

Hydrogen as a future energy carrier requires
a technology to efficiently store it in a solidmaterial which can release and rechargehydrogen as fast as possible at minimum
energy loss [1]. The purpose of this work is
to investigate of the “boron effect” on thedehydrogenation of alkali and alkaline earthmetalborohydrides under hydrogenpressure in non-isothermal conditions (nonequilibrium).

The addition of boron affected thedehydrogenatio
n, changing thereaction
path
via
a
new
intermediate.
The formationofanewintermediate
occurred afterpartialdecompositionof the material.
Positively, the Figure 2: DSC traces forboron
effect Ca(BH4)2 and Ca(BH4)2 +B
decreased the under 1bar H2 at 11 ºC/min
for LiBH4
Td
of 150 °C and 20 °C
and Ca(BH4)2
respectively (Fig. 1, 2). On the other hand,the boron presence inhibited the thermal
decomposition of NaBH4. The nature of new
intermediate is the key to describe themechanism of reaction, that is currently
under investigation.

Experimental
The boron mixtures M(BH4)n+B wereprepared by mixing various molar ratios,
X=moles M(BH4)n / moles amorphous B, in amortar. The thermal decompositions werestudied by means of differential scanningcalorimetry (DSC), mass spectrometry andvolumetricanalysisinthemixturetemperature range 25-600ºC.

References
Figure 1: DSC traces for LiBH4 and LiBH4+B under
1bar H2 at 11 ºC/min.

[1] L. Schlapbach & A. Züttel Nature, p. 353, v.414(2001)[2] F. Pendolino et al. Phys. Chem. C, p.17231,
v. 113 (2009)

Corresponding author: Flavio Pendolino, email: flavio.pendolino@empa.ch Tel. (+41) (44) 823 4776

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4th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010LITHIUM FAST-ION CONDUCTION IN LiBH4
Motoaki Matsuo and Shin-ichi Orimo
Institute for Materials Research, Tohoku University, 980-8577 Sendai, Japan−3[1]

We have recently reported that LiBH4 exhibits lithium fast-ion conduction (more than 1×10 S/cm), which[2]
was observed during attempts to clarify the microwave absorbing mechanism. The lithium ion
conductivity of LiBH4 jumps by three orders of magnitude due to its structural transition from orthorhombic
to hexagonal (fast-ion conduction) phases at approximately 390 K. The fast-ion conduction phase can bestabilized by addition of lithium halides, resulting in the enhancement of the ion conductivity at room
temperature(RT).[3-5]Introduction
The lithium fast-ion conduction in LiBH4
could potentially aid the development of
new solid electrolytes for lithium-ion
secondary batteries. Therefore, research
directions on LiBH4 are to stabilize the fastion conduction phase to least possible
temperatures, and also to enhance theconductivity. In this work, we describe theeffects of lithium halide (LiCl and LiI)
addition to LiBH4 on the stability and thelithium ion conductivity.

conduction phase was stabilized at RT,
resulting in the high ion conductivity of-5
2×10 S/cm. These properties were foundto be attributed to the dissolution of LiCland LiI into LiBH4. Furthermore, justrecently, complex hydrides with (BH4)– andanions,Li2(BH4)(NH2)and(NH2)–
Li4(BH4)(NH2)3, were found to exhibit lithium−4[6]
fast-ion conductivity of 2×10 S/cm at RT.

Experimental
Approximately 500 mg mixtures of LiBH4
and LiCl or LiI were mechanically milled for
5 h under Ar. The lithium ion conductivity
was determined by ac complex impedance
method between 303 and 433 K. The
samples were examined by ex- and in-situ
powder X-ray diffraction measurements(XRD). Thermal analysis was carried out bydifferential scanning calorimetry (DSC).

Results
As shown in Figure 1, the LiCl addition
lowered the transition temperature of LiBH4
by 30 K (380 → 350 K), indicating thestabilization of the lithium fast-ion
conduction phase at lower temperature.
Additionally, the ion conductivity in theorthorhombic phase was increased by one
order of magnitude. In the case of LiI
addition, on the other hand, the fast-ion

Fig. 1. Temperature dependences of the lithium
ion conductivity of LiBH4 (black), LiBH4+0.33LiCl(blue) and LiBH4+0.33LiI (red).

References[1] Matsuo et al; Appl. Phys. Lett. 91 (2007) 224103[2] Matsuo et al; Appl. Phys. Lett. 90 (2007) 232907[3] Matsuo et al; Appl. Phys. Lett. 94 (2009) 084103[4] Oguchi et al; Appl. Phys. Lett. 94 (2009) 141912[5] Maekawa et al; J. Am. Chem. Soc. 131 (2009) 894[6] Matsuo et al; J. Am. Chem. Soc. in press

Corresponding author: Shin-ichi Orimo, email: orimo@imr.tohoku.ac.jp, Tel. (+88) (22) 215 2093

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

SCIENCE OF HYDROGEN & ENERGY AWARD 2007

Prof. Dr. Ronald Griessen

Ronald Pierre Griessen, was born March 7, 1945 in
Switzerland. He received 1964 his Baccalauréat, from
Gymnase français in Bienne, Switzerland. From1964 – 1969 he studied Physics and Mathematics at the Swiss
Federal Institute of Technology (ETH) in Zürich and finishedwith a Diploma-thesis on: "Magnetostriction of type-II
superconductors". From 1969 – 1973 he was PhD student in
the Low Temperature Physics Group of Prof.dr J.L. Olsen at
the ETH. PhD-thesis on: "Oscillatory Magnetostriction and thestress dependence of the Fermi Surface of Al, In, Zn and Mg".
From 1974 – 1976 he was Research Associate at the
McLennan Physical Laboratory of the University of Toronto,
Canada where he worked on the electronic structure of spindensity-wave systems and quantum oscillations.In 1976 he
was visiting scientist at the ETH, Zürich and from 1976 – 1980
senior lecturer at the Vrije Universiteit in Amsterdam. Since
1980 he is Full Professor in charge of the Department ofCondensed Matter Physics.

Ronald Griessen has investigated the thermodynamics of palladium films and the isotope
effect on the electronic structure of hydrides. Furthermore, the effect of anharmonicity and
Debye-Waller factor on superconductivity of PdHx and PdDx have been studied by Ronald
before he developed a semi-empirical model for the heat of solution of hydrogen in transition
metals. He also studied the trapping energy for hydrogen on lattice defects as well as the heatof solution of disordered transition metals. The volume expansion upon hydrogen absorption,
the Gorsky-effect, the diffusion, electromigration and the hydrogen diffusion in magnetig fields
are just a few other subjects treated and described by Ronald Griessen. Then Ronald decided
to test the world of high pressure hydrogen and described the properties of hydrides formed atvery high pressure as well as the properties of hydrogen gas in a wide temperature andpressure range. During the intense investigation of superconductors and metal hydrides underhigh hydrogen pressure in a diamond anvil cell, Ronald has discovered the switchable opticalproperties of yttrium and lanthanum hydride films. This has then stimulated Ronald toinvestigate thin films with optical methods and to develop new methods for the combinatorial
search of new hydride phases as well as for the determination of the thermodynamic
parameters e.g. stability and kinetics of the hydrides. Furthermore, new applications for
hydrides as hydrogen detectors and optical filters have been developed in his group.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2008

Prof. Dr. Louis SchlapbachLouis Schlapbach, born March 4, 1944 in Belp Switzerland. He
graduated from the Swiss Federal Institute of Technology Zurich(ETHZ) in Experimental Physics and got his PhD in Solid State
Physics – Magnetism also at ETHZ. As a postdoc at a CNRS
laboratory in Paris, he studied hydrogen storage in intermetallic
compounds. Back at ETHZ, he developed the surface science
aspects of the hydrogen interaction with metals and alloys.
From 1988 till 2001, Louis Schlapbach was Full Professor for
Physics at the University of Fribourg. As such he built up a
research team of 20-25 people working on the topic „New
Materials and their Surfaces“ resulting in about 40 PhD, 200
scientific papers and some patents. A strong collaboration withindustry was established. In spring 2001, he has been
appointed CEO of Empa, the materials science and technology
institution of the ETH domain with 750 coworkers in Dübendorf,
St. Gallen and Thun.

Louis Schlapbach started his scientific work in 1970, 38 years ago, with the investigation of theHall effect, electrical transport and magnetic susceptibility of liquid rear earth elements like
Cerium. 30 years ago in 1970 he was coauthor with Busch and Waldirich on a paper about thehydrides of La-Ni compounds. LaNi5 was subsequently investigated in view of the structure,surface segregations, hydrogen occupation of interstitial sites and as electrode material.LaNi5 isstill the base material for most of the electrochemical applications of metal hydrides today. The
work on LaNi5 was complemented by the research on FeTi. Louis Schlapbach realized theimportance of the surface composition for the hydrogen sorption process and he was able todescribe the role of the surface-active species. Furthermore, he investigated the changes of thesurface composition of LaNi5 and FeTi in oxidizing atmospheres and he found the formation of
metallic clusters as superparamagnetic particles acting as the active sites in hydrogendissociation and recombination. The investigation of the surface of metal hydrides was further
intensified by means of X-ray photoelectron spectroscopy. Louis Schlapbach was the firstscientist correctly describing the activation process of a metal hydride and, furthermore, tomodel the chemical composition and states of the elements in a surface profile. He also
succeeded to analyze the electronic structure of raere earth elements and their hydrides bymeans of photoemission spectroscopy. In 1990 Louis Schlapbach edited the two books"Hydrogen in Intermetallic Compounds I & II" of the Springer Sereies. The books became a very
important reference for all the researchers active in the field of hydrides.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Dr. Gary Sandrock

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

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

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SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Prof. Dr. Jens Norskov

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

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

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Prof. Dr. Rüdiger Bormann

Rüdiger Bormann was born September, 14 1952 in Germany.
He received 1977 his diploma in physics (Metalphysics), fromthe University Göttingen and 1979 his Dr. rer. nat. from the
University Göttingen. From 1981 to 1982 he was visiting
scientist in the Dept. of Applied Physics at Stanford University,
U.S.A. From 1982 to 1988 he was Assistant Professor(Hochschulassistent) at the University Göttingen where hereceived the Habilitation University Göttingen, venia legendi in1988. From 1989 to 1997 he was Professor of Metalphysics(GKSS Research Centre, Geesthacht and Hamburg Universityof Technology) and from 1996 to 2009 he was director of theInstitute for Materials Research, GKSS Research Centre,
Geesthacht and since 2009 he is Professor of Applied Materials
Physics and President of the University of Bayreuth

Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses,
metastable crystalline and amorphous alloys as well as the thermodynamics and kinetics of theamorphous phase formation by mechanical alloying. This was the basis for the investigation of
Mg and Mg-Ni hydrides and the thermodynamics of nanoscale magnesim hydride. The
discovery catalytic effect of metal oxides on the hydrogen sorption kinetics of magnesium was agreat step forward in the development of hydrogen storage materials. Furthermore, very
important was also the interpretation of the role of the grain boundaries for the diffusion ofhydrogen in the passivating hydride phase formation. Recently the discovery of the so called
reactive hydride composites by the combination of two hydrides has opened a new field ofmaterials design for hydrogen storage. Therefore, we award Prof. Rüdiger Bormann with the
Science of Hydrogen & Energy prize 2010.

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

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

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Prof. Dr. Reiner Kirchheim

Reiner Kirchheim was born May 24, 1943 in Halle/Saale,
Germany. He studied Physics at the University of Stuttgart from
1966-1971 and received the diploma for the work
“Electrochemical studies of oxygen solid solutions in highmelting
metals”
atthe
Max-Planck-Institut
fürMetallforschung/University of Stuttgart. He received his Ph.D.
for the thesis entitled “Thermo- and electrotransport of oxygenand nitrogen in Va metals“ from the University of Stuttgart, MaxPlanck-Institut für Metallforschung in 1973. In 1988 he received
the Habilitation “Measurements and modelling of hydrogensolubility and diffusivity in disordered metal lattices“ from the
University of Stuttgart, Faculty of Chemistry Metallurgy.
Since 1993 he is Full Professor (Gustav Tamman Chair)
University of Göttingen Göttingen Germany and Director GeorgAugust-Universitaet Goettingen, Institut für Materialphysik
Göttingen Germany.

Prof. Reiner Kirchheim has investigated 30 years ago oxygen in metals, especially diffusion,
thermotransport and thermopower of oxygen in transition metals and alloys. In 1980 he started
to study diffusion of hydrogen in dillute alloys of copper and niobium in palladium. He developed
an electrochemical method for the measurement of the hydrogen diffusion in palladium andpalladium alloys and performed fundamental studies on the diffusion mechanism of interstitial
species. The interaction of hydrogen with dislocations in palladion and the interpretation with amodel based on the Fermi-Dirac distribution are of great importance for the understanding of
the interstitial site occupation of hydrogen inalloys and amorphous metals.
For the enormous contributions on the hydrogen dynamics and thermodynamics in metals aswell as the hydrogen interaction with dislocations, grain bounderies and interfaces we award
Prof. Reiner Kirchheim with the Science of Hydrogen & Energy prize 2010.

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PARTICIPANTS

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Akiba Etsuo, Prof. Dr.

AIST
ETRI
Tsukuba Central 5, 1-1-1, Higashi
JP-305-8565 Tsukuba

email: e.akiba@aist.go.jp
Tel: +81-298-61-4541
Fax: +81-298-61-4541

Balog Sandor, Dr.

ETH Zürich & Paul Scherrer Institut
Laboratory for Neutron Scattering
Villigen PSI
CH-CH-5232 Villigen

email: sandor.balog@psi.ch
Tel: (41) 56 310 5586
Fax: : (41) 56 310 2939

Banach Ewa, Ms.

Shell Global Solutions
Innovation & Research
Grasweg 31
NL-1031 HW Amsterdam

email: ewa.banach@shell.com

Beckmann-Kluge Martin, Mr.

BAM Federal Institute forMaterials Research and Testing
Chemische Sicherheitstechnik
Unter den Eichen 87
DE-12205 Berlin

email:
martin.beckmann-kluge@bam.deBellosta von Colbe Jose, Dr.

GKSS REsearch Centre Geesthacht GmbH
Instute of Materials Research
Max Planck St.
DE-21502 Geesthacht

email:
jose.bellostavoncolbe@gkss.de

Berke Heinz, Prof. Dr.

University of Zurich
Institute of Inorganic Chemistry
Winterthurerstrasse 190
CH-8057 Zurichemail: hberke@aci.unizh.ch
Tel: 0041635 4681
Fax: 00416356803

Bielmann Michael, Dr.

EMPA
Hydrogen and EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: michael.bielmann@empa.ch
Tel: (+41) (44) 823 4342
Fax: (+41) (44) 823 4022

Boesenberg Ulrike, Dr.

GKSS Research Centre Geesthacht
Institute for Materials Research
Max-Planck-Str. 1
DE-21502 Geesthacht

email: ulrike.boesenberg@gkss.de
Tel: 0049 4152 87 2565
Fax: 0049 4152 87 2625

Borgschulte Andreas, Dr.

Empa
Mobility, Environment, and Energy
Ueberlandstrasse 129
CH-8600 Dübendorf

email:
andreas.borgschulte@empa.ch
Tel: (+41) (44) 823 4639
Fax: (+41) (44) 823 4022

Bormann Rüdiger, Prof. Dr.

University Bayreuth

email:
ruediger.bormann@uni-bayreuth.deTel: +491716150053

Universitätsstrasse 30
DE-95440 Bayreuth
Boulouchos Konstantinos, Prof. ETH Zürich
Dr.
Institute of Energy Technology
Sonneggstrasse 3
CH-8092 Zürich

email: boulouchos@lav.mavt.ethz.ch
Tel: 044 632 56 48
Fax: 044 632 11 02

Buchter Florian, Dr.

ABB Schweiz AG, Corporate Research
Segelhofstrasse 1
CH-5405 Baden 5 Dättwil

email: florian.buchter@ch.abb.com
Tel: +585867088

Cakir Deniz, Dr.

University of Twente
Faculty of Science-Computational
Science
HOGEKAMP 10162
NL-7500 AE Enschede

PROCEEDINGS

email: D.Cakir@tnw.utwente.nl
Materials Tel: +31 53 489 3155
Fax: +31-53-4892910

904th Hydrogen & Energy Symposium

Wildhaus, Switzerland 2010

Capurso Giovanni, Dr.

University of Padova
Mechanical Engineering - Materials Section
Via Marzolo, 9I-35131 Padova (Italy)

Email: giovanni.capurso@gmail.com

Centi Gabriele, Prof

Univ. Messina
Dept Ind Chem and Eng Materials
Salita Sperone 31
IT-98166 Messina

email: centi@unime.it
Tel: +390906765609
Fax: +39090391518

Cho Young Whan, Dr.

KIST
email: oze@kist.re.kr
Advanced Functional Materials Research Centre
PO Box 131, Cheongryang
KR-130-650 Seoul

Chung Moon-Sun, Dr.

Korea Institute of Energy Research
Hydrogen Energy R&D Centre
71-2 Jang-dong, Yuseong-gu
KR-305-343 Daejoen

email: moonschung@kier.re.kr
Tel: +82-42-860-3591
Fax: +82-42-860-3598

Churchard Andrew, Mr.

ICM, University of Warsaw
Chemistry
Zwirki i Wigury 93
PL-02-089 Warsaw

email: achurch@icm.edu.pl

Corno Marta, Dr.

Università degli Studi di Torino
Dipartimento di Chimica I.F.M
via P. Giuria, 7
IT-10125 Torino

email: marta.corno@unito.it
Tel: 00390116704597

Dam Bernard, Prof. Dr.

Delft University of Technology
Applied Science
Julianalaan 139
NL-2628 BL Delftemail: b.dam@tudelft.nl

Domènech-Ferrer Roger, Mr.

IFW
21Helmholtzstraße
DE-D-01069 dresden

email:
r.domenech.ferrer@ifw-dresden.de

Dornheim Martin, Dr.

GKSS Research Centre Geesthacht
Nanotechnology
Max-Planck-Straße 1
DE-21502 Geesthacht

email: Martin.Dornheim@GKSS.de
Tel: 0049 41502 87 2604
Fax: 0049 41502 87 2636

Er Süleyman, Dr.

University of Twente
Hogekamp Building. Room: 10164
NL-7500AE Enschede

email: s.er@utwente.nl
Tel: (+31)(53) 489 3167
Fax: (+31)(53) 489 2910

Fichtner Maximilian, Dr.

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

email: m.fichtner@kit.edu
Tel: +49 7247 825340

Filippi Matteo, Dr.

Vrije University
Physics and Astronomy
De Boelelaan
NL-1081 HV Amsterdam

email: mfilippi@few.vu.nl
Tel: +31 20 598 7912
Fax: +31 20 598 7991

Friedrichs Oliver, Dr.

Empa
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Duebendorf

email: oliver.friedrichs@empa.ch
Tel: (+41) (44) 823 4153
Fax: (+41) (44) 823 4022

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Garroni Sebastiano, Mr.

Universitat Autonoma de Barcelona
Physics Department
Edifici Cc(C3/210)
ES-088193 Bellaterra

email:
sebastiano.garroni@campus.uab.cat
Tel: +34935811657

Gianola Corinne, Ms.

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: corinne.gianola@empa.ch
Tel: +41448234692
Fax: +41448234022

Gil Bardají Elisa, Dr.

Karlsruhe Institute of Technology
Institut of Nanotechnology
Hermann-von-Helmholtz Platz 1
DE-D-76344 Eggenstein-Leopoldshafen

email: elisa.gil@kit.edu
Tel: ++49 (0)7247 82 8909
Fax: ++49 (0)7247 82 6368

Gorbar Michal, Mr.

Empa
Hydrogen & Energy, Abt. 138
Überlandstrasse 129
CH-CH-8600 Dübendorf

email: michal.gorbar@empa.ch
Tel: (+41) (44) 823 4301
Fax: (+41) (44) 823 4022

Gregory Duncan, Prof. Dr.

University of Glasgow
Chemistry
University Avenue
GB-G12 8QQ Glasgow

email: D.Gregory@chem.gla.ac.uk
Tel: 00441413306438
Fax: 00441413304888

Gremaud Robin, Dr.

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: robin.gremaud@empa.ch
Tel: (+41) (44) 823 4933
Fax: (+41) (44) 823 4022

Gutfleisch Oliver, Dr.

IFW Dresden
IMW
Helmholtzstr. 20
DE-01069 Dresden

email: o.gutfleisch@ifw-dresden.de
Tel: +49 351 4659 664
Fax: +49 351 4659 541

Haggi Ahmed Abdirizak, Ms.

Educational Institue
BiaoChimic
Wayaki way
KE-00100-7556 Nairobi

email: jimale_org@yahoo.com
Tel: 0041
Fax: 0041

Han Sang-Sup, Dr.

Korea Institute of Energy Research
Greenhouse Gas Research Centre
102 Gajeong-ro, Yuseong-gu
KR-305-343 Daejon Metropolitan City

email: sshan@kier.re.kr
Tel: +82-42-860-3378
Fax: +82-42-860-3134

Harris Rex, Prof. Dr.

Metallurgy and Materials
The University of Birmingham
Edgbaston
Birmingham B15 2TT
UKBAM Federal Institute forMaterials Research and Testing
Chemical Safety Engineering
Unter den Eichen 87
DE-12205 Berlin

email: I.R.Harris@bham.ac.uk
Tel: (+44) (0) 121 414 5165
Fax: (+44) (0) 121 414 5247

Holtappels Kai, Dr.

email: kai.holtappels@bam.de

Hu Jianjiang, Dr.

Karlsruhe Institute of Technology (KIT)
Institute for Nanotechnology
Hermann-von-Helmholtz Platz 1
DE-76344 Eggenstein-Leopoldshafen

email: jianjiang.hu@kit.edu
Tel: 0049 7247 828915
Fax: 0049 7247 82 6368

Jhi Seung-Hoon, Prof. Dr.

Pohang University of Science and Technology
Physics
Hyojadong San 31
KR-790-784 Pohangemail: jhish@postech.ac.kr
Tel: +82-54-279-2094
Fax: +82-54-279-3099

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Kato Shunsuke, Mr.

Empa
Dept. Environment, Energy and MobilityÜberlandstrasse 129
CH-8600 Dübendorf

email: shunsuke.kato@empa.ch
Tel: +41 (44) 823 4327
Fax: +41 (44) 823 4022

Kiichi Kojima, Mr.

Toyota motor Co,
Fuel Cell System Engineering Div
Toyotacho1-1
JP-471-0826 Toyota

email:
amanohiromi@nano.tec.toyota.co.jp
Tel: 81+565-72-9200
Fax: 81+565-23-0355

Kim Jaheon, Prof. Dr.

Soongsil University
Chemistry
511 Sangod-Dong Dongjak-Gu
KR-156-743 Seoul

email: jaheon2@gmail.com
Tel: +82-2-820-0459
Fax: +82-2-824-4383

Kim Ji Woo, Mr.

Seoul National University
Materials Science and Engineering
Gwanak
KR-151-742 Seoul

email: novel04@snu.ac.kr
Tel: +82 2 880 8306
Fax: +82 2 872 8307

Kirchheim Reiner, Prof. Dr.

Friedrich-Hund-Platz 1
DE-D-37077 Goettingenemail: rkirch@ump.gwdg.deKozlov Alexey, Dr.

Institute of Coal and Coal Chemistry
SB RAS
Sovetskiy Avenue, 18
RU-650099 Kemerovo

email: kemerit@rambler.ru
Tel: 73842368188

Langhammer Christoph, Dr.

Chalmers University of Technology
Applied Physics
Fysikgränd 3
SE-41296 Göteborg

email: clangham@chalmers.se

Laurenczy Gabor, Dr.

EPFL
ISIC LCOM
BCH
CH-1015 Lausanneemail: Gabor.Laurenczy@epfl.ch
Tel: 0041216939858
Fax: 0041216939780

Lee Nam-Hee, Dr.

Sejong University
Faculty of Nanotechnology andAdvanced Materials
98Gunja-dong, Gwangjin-gu
KR-143-747 Seoul

email: namhee74@chol.com

Lindemann Inge, Ms.

IFW
Helmholtzstraße 20
DE-D-01171 Dresden

email: I.Lindemann@ifw-dresden.de
Tel: +49 (0)351-4659-669

Martelli Pascal, Mr.

EMPA
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Duebendorf

email: pascal.martelli@empa.ch
Tel: (+41) (44) 823 4746
Fax: (+41) (44) 823 4022

Matsuo Motoaki, Dr.

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

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

Mauron Philippe, Dr.

EMPA
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Dübendorf

email: philippe.mauron@empa.ch
Tel: (+41) (44) 823 4099
Fax: (+41) (44) 823 4022

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Milanese Chiara, Dr.

University of Pavia
Department of Physical Chemistry
Viale Taramelli, 16
IT-27100 Pavia

email: chiara.milanese@unipv.it
Tel: +39-0382-987670
Fax: +39-0382-987670

Miwa Kazutoshi, Dr.

Toyota Central R&D Labs., Inc.
Computational Physics Lab.
Nagakute
JP-480-1192 Aichi

email: miwa@cmp.tytlabs.co.jp
Tel: +81-561-71-7462
Fax: +81-561-63-5258

Muller Jiri, Dr.

Institute for Energy Technology - IFE
Box 40NO-NO-2027 Kjeller

email: jiri@ife.noTel: 0047 63 80 61 85

Orimo Shin-ichi, Prof. Dr.

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

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

Park Noejung, Prof. Dr.

Dankook University
Applied Physics
126, Jukjeon-dong, Suji-gu
KR-448-701 Yongin-city

email: noejung@dku.edu
Tel: +82-10-7674-3211
Fax: +82-31-8005-3208

Pendolino Flavio, Mr.

EMPA
Hydrogen & Energy
Uberlanstrasse 129
CH-8600 Dubendorf

email: flavio.pendolino@empa.ch
Tel: (+41) (44) 823 4776
Fax: (+41) (44) 823 4022

Pistidda Claudio, Mr.

GKSS
Max-Planck-Straße 1
DE-21502 Geesthacht

email: claudio.pistidda@gkss.deRamirez-Cuesta Anibal Dr.

STFC
ISIS
GB-OX11 0QX Chilton

email:
timmy.ramirez-cuesta@stfc.ac.uk
Tel.: (044) 7787105335

Remhof Arndt, Dr.

Empa
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Duebendorf

email: arndt.remhof@empa.ch
Tel: (+41) (44) 823 4369
Fax: (+41) (44) 823 4022

Rongeat Carine, Ms.

IFW Dresden
Institute for Metallic Materials
Helmholtzstrasse 20
DE-01069 Dresden

email: c.rongeat@ifw-dresden.de
Tel: +49 (0)351-4659-669

Ronnebro Ewa, Dr.

Pacific Northwest National Laboratory
509 Battelle Boulevard
US-99354 Richlandemail: ewa.ronnebro@pnl.gov
Tel:
Fax:

Schaer Roland, Mr.

Hilti AG
Advanced mechatronics
Technisches Zentrum
FL-9494 Schaan

email: roland.schaer@hilti.com
Tel: 00423 234 2321

Schiavo Benedetto, Mr.

Università degli Studi di Palermo
Department of Physics andrelated Technologies
Viale delle Scienze, bdg n.18
IT-90100 Palermo

email:
benedetto.schiavo@difter.unipa.it
Tel: 0923550130

PROCEEDINGS

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Shim Jae-Hyeok, Dr.

Korea Institute of Science and Technology
email: jhshim@kist.re.kr
Advanced Functional Materials Research Center Tel: +82-2-958-6760
39-1 Hawolgok-dong, Seongbuk-gu
Fax: +82-2-958-5379
KR-136-791 Seoul

Stojadinovic Jelena , Dr.

Empa Duebendorf
Hydrogen and Energy
Ueberlandstrasse 129
CH-8600 Duebendorf

email: valentina.herzog@empa.ch
Tel: 448234352

Stowe Ashley, Dr.

B&W Y-12 national Security Complex
Technology Development
301 Bear Creek Road MS8097
US-37831 Oak Ridge

email: stoweac@y12.doe.gov
Tel: 18652410675

Suh Jin-Yoo, Dr.

Korea Institute of Science and Technology
Materials Science and Technology
Research Division39-1 Hawolgok-dong, Seongbuk-gu
KR-136-791 Seoul

email: jinyoo@kist.re.kr
Fax: +82-2-958-5379

Taube Klaus, Dr.

GKSS-Forschungszentrum Geesthacht GmbH
Nanotechnology
Max-Planck-Strasse 1
DE-D-21502 Geesthacht

email: klaus.taube@gkss.de
Tel: +49 4152 872541
Fax: +49 4152 872625

Utz Inga, Ms

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

email: inga.utz@dlr.de
Tel: 0049 (0)711 6862 492

Vogt Ulrich, Dr.

EMPA
Senior Scientist
Ueberlandstr. 129
CH-8600 Duebendorf

email: ulrich.vogt@empa.ch
Tel: 001 44 823 4160
Fax: 001 44 823 4022

Walton Allan, Dr.

University of Birmingham
Metallurgy and Materials
Pritchats Road
GB-B152TT Birmingham

email: a.walton@bham.ac.uk
Tel: 44 121 414 3960

Wiedenmann Daniel, Mr.

Empa
Abt. 138Überlandstrasse 129
ch-8600 Dübendorf

email: daniel.wiedenmann@empa.ch
Tel: (+41) (44) 823 4862
Fax: (+41) (44) 823 4022

Zakaznova-Herzog Valentina,
Dr.

Empa Duebendorf
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Duebendorf

email: valentina.herzog@empa.ch
Tel: +44 823 43 52
Fax: +44 823 40 22

Züttel Andreas, Prof. Dr.

EMPA Materials Science & Technology
Energy, Environment and Mobility
Sec. Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: andreas.zuettel@empa.ch
Tel: (+41) (44) 823 4692
Fax: (+41) (44) 823 4022

PROCEEDINGS

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Information

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Map from Zürich (upper left corner) to Wildhaus (lower right corner)

Map of the region Wildhaus

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Map of Wildhaus

EMERGENCY TELEPHONE NUMBERS
POLICE

117

FIRE FIGHTERS

118

AMBULANCE144

RESCUE HELICOPTER

1414

Corinne Gianola

076 398 9985

Andreas Züttel

079 215 4601

Hotel Hirschen Wildhaus, Reception

071 998 5454

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Wildhaus Region

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