th

8 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory
and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materials
The 8th International Symposium “Hydrogen & Energy” serves as an information
platform of the fundamental science and the frontiers of research in Sciences
and Technology of Hydrogen & Energy (Hydrogen Production, Hydrogen Storage,
Hydrogen Applications, Theory and Modelling, Fuel Cells, Batteries, Synthetic
fuels).
The symposium consists of invited keynote lectures reviewing the key elementsof the hydrogen cycle, i.e. the hydrogen production, hydrogen storage andhydrogen combustion and fuel cells. Furthermore, contributions on theconversion of renewable energy in general and energy carriers beside andbeyond hydrogen are very welcome. The world leading experts present thecurrent research challenges and most important results in invited andcontributing talks. Early stage and experienced researchers present their newest
results and the open questions on posters as well as in a one slide presentation.
The conference will take place in the OYC hotel in Zhaoqing close to Guangzhou
in China. The OYC Hotel is set against a group of lakes surrounding thelimestone peaks in Zhaoqing, Guangdong Province, China. It enjoys a view blue
lakes and mountains which comprise a splendid panoramic landscape to thesouth of the Five Ridges.
The number of participants is limited to 120.

16. - 21. February 2014
OYC Hotel*******
Xinghu Dadao, Zhaoqing
526060 Guangdong, P. R. China
Tel.: +86 758 218 9887
URL: http://www.oychotel.com

8th Int. Symposium Hydrogen & Energy

PROCEEDINGS

Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

PROCEEDINGS

Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

PROCEEDINGS

Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

Welcome Address
It is our great pleasure to host such a distinguished group at the picturesque
Zhaoqing in China! On behalf of the steering committee of the syposium,
we would like to express the warmest welcome to each and every one ofyou!
In 2012, when Prof. Min Zhu attended the 6th Hydrogen and Energy
Symposium in Switzerland, it was in a beautiful snow mountain in Alps.
He proposed the idea of host this symposium in Southern China where thewinter is very warm, and more importantly, this will provide more chance
for Chinese scientists to communicate with European Scientists. Thissuggestion was strongly been supported by the other colleagues. Prof.
Züttel pay a special visit to Guangzhou to arrange the issue of thesymposium in Oct. 2013. Thanks to the effort of organizing committee andour colleagues and in particular the symposium is now ready to open.
This time we have about 70 participates to attend the symposium with oral
and poster presentation, about 20 from abroad and 50 from China. The
symposium will offer a great opportunity to discuss the latest scientificdevelopment in the areas of hydrogen production, storage, combustion, andfuel cells, just to name a few. In addition, you will also have plenty ofopportunities for networking and interaction during the many breaks andsocial events in our dense agenda.
Besides, as we are here embraced by all the beautiful lakes, woods andmountains, we also hope you will find time to enjoy the many beautiful
attractions in Zhaoqing and Guangzhou.
Finally, we would like to welcome all of you again, and wish you apleasant stay, and a productive conference. Thank you.
Professor Min Zhu
South China University of Technology
Guangzhou, P. R. China

PROCEEDINGS

Professor Andreas Zuttel
EMPA Materials Science and Technology
CH-8600 Dübendorf, Switzerland

8th Int. Symposium Hydrogen & Energy

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Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

CONTENTS
Timetable
Abstracts
MONDAY
morning

Chair: Min ZHU

09:00 - 09:40

Andreas ZÜTTEL,HYDROGEN'

WITH

03

09:40 - 10:05

Xuebin YU, 'The Application of Nanotechnology inHydrogen Storage'05

10:05 - 10:30

Yongjin ZOU, 'Catalytic Behaviour of Co-Zn-B/Graphene
Composite in Hydrogen Generation by Hydrolysis of
Alkaline Sodium Borohydride'07

10:30 - 10:55

Sheng GUO, 'Alkali and Alkaline-Earth Borohydrides for
Hydrogen Storage'

09'CLOSING

THE

CYCLE

Chair: Andreas ZÜTTEL
11:20 - 11:45

Yongfeng LIU, 'Hydrogen Storage Properties andMechanisms of alkali-meal-added Li-Mg-N-H system'

11

11:45 - 12:10

Huaiyu SHAO, 'Geometrical effect study in Mg-based
BCC structure materials for hydrogen storage'

13

12:10 - 12:50

Young Whan CHO, 'Control of Thermodynamic andKinetic Properties of Metal Hydride Composite Confinedin Mesopore Cages'

15

MONDAYafternoon

Chair: Young Whan CHO

14:00 - 14:40

Micheal Hirscher, 'Nanoporous Framework
Hydorgen Storage and H2/D2 Isotope Separation'

for

17

14:40 - 15:05

Yigang YAN, 'New Methods to Apply Nanostructures on
Mg(BH4)2'

19

15:05 - 15:30

Jianmei Huang, 'Increased air stability and decreased
dehydrogenation temperature of LiBH4 via modification
within poly(methylmethacrylate) '21

15:30 - 15:55

Ulrich VOGT, 'Development and characterization of gas
separation membranes for alkaline water electrolysis'

23

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8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

Chair: Micheal Hirscher
16:20 - 16:45

Nicholas STADIE, 'The Mystery of Diborane Evolution
During The Decomposition of Γ-Phase Magnesium
Borohydride'25

16:45 - 17:10

Weitong CAI, 'Towards Easy and Fully Reversible
Dehydrogenation of LiBH4 by Catalyzing of Hierarchic
Nanostructured CoB'

27

17:10 -17:35

Fangming XIAO, 'THE STUDY OF THE INTEGRATEDHYDROGEN STORAGE SYSTEM OF METAL HYDRIDEFOR THE APPLICATION OF FUEL CELL'29

17:35 - 18:15

Tejs VEGGE, 'Computational Design of Nanoparticle
Catalysts for Sustainable Production of Synthetic Fuels'

31

TUESDAY
morning

Chair: Tejs VEGGE

09:00 - 09:40

Ping CHEN, 'Amidoboranes-Formation and Application'

33

09:40 - 10:05

Arndt REMHOF, 'Borohydrides: New Insights from NMR'35

10:05 - 10:30

Teng HE, 'Transition Metal Catalyzed Dehydrogenationof B-N-H Based Materials in Solid State'37

10:30 - 10:55

Cunke HUANG, 'CeTi2Al20: a Catalyst-Reactant Integral
Agent to NaAlH4 Synthesis'

39

Chair: Ping CHEN
11:20 - 11:45

Haiyan LENG, 'Effect of Microwave Irradiation on The
Hydrogen Desorption Properties of MgH2/LiBH4
Composite'41

11:45 - 12:10

Hailiang CHU, 'Calcium Borohydride Modified by N-HGroup for Hydrogen Storage'43

12:10 - 12:50

Hannes JÓNSSON, 'Nanoparticle Catalysis of Hydrogen
Evolution'

45

TUESDAY
afternoon

Chair: Hannes JÓNSSON

14:00 - 14:40

Xingguo LI, 'Title Synthesis and Properties
Nanostructured Hydrogen Storage Materials'of47

14:40 - 15:05

Elsa CALLINI,'Spontaneous Dehydrogenation Reactions
Investigated by In-situ Spectroscopy'

49

15:05 - 15:30

Chaoling WU, 'Rapid Solidification to Affect
Properties of V-Based Hydrogen Storage Alloys'

51

PROCEEDINGSon

8th Int. Symposium Hydrogen & Energy

15:30 - 15:55

Zhaoqing, P.R. China 2014

Moreno DE RESPINIS, 'Oxynitrogenography:
Search for Oxynitrides for Solar Water Splitting'

The

53

16:20 - 16:45

Yunfeng ZHU, 'Recent Study on Hydrogen Storage
Properties of Mg-Based Materials Prepared by
HCS+MM'55

16:45 - 17:10

Yuan
LI,
'Preparation
andcharacteristics of single-phase'57

17:10 - 17:35

Mariana SPODARYK, 'Gas atomized alloy electrodes'

59

17:35 - 18:15

Puru JENA,
STORAGE'HYDROGEN

61

WEDNESDAY
morning

Chair: Puru JENA

09:00 - 09:40

V.A. YARTYS, 'Nanostructured Mg-Based Hydrogen andEnergy Storage Materials Probed by In situ Synchrotron
and Neutron Powder Diffraction'

63

09:40 - 10:05

Xiangdong KANG, 'PROMOTED FORMATION OF METAL
BORIDES IN THE 2LiBH4-MgH2 COMPOSITES WITH
TRANSITION METAL ADDITIVES BY USING A NEW
THREE-STEP METHOD'

65

10:05 - 10:30

Jiangwen LIU, 'Enhancing effect of LPSO on thede/hydrogenation kinetics and structural transformationin Mg94Cu4Y2 Alloy'

67

10:30 - 10:55

Baozhong LIU, 'Microstructures and Hydrogen storage
properties of Mg-RE-Ni alloys'

69

Chair: Xingguo LI'NANOMATERIALS

electrochemical

FOR

Chair: V.A. YARTYS
11:20 - 11:45

Yongtao LI, 'Superlattice Structures and Hydrogen
Absorption/Desorption Characteristics of R-Mg-Ni
Compounds'

71

11:45 - 12:10

Renaud DELMELLE, 'Rethinking High-Pressure X-Ray
Photoelectron Spectroscopy for The Study of HydrideForming Materials'

73

12:10 -12:50

Liuzhang OUYANG, 'A NEW METHOD TO PREPARE MG
BASED HYDROGEN STORAGE MATERIALS WITH
IMPROVED DEHYDRIDING THERMODYNAMICS AND
KINETICS PROPERTIES'

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8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

THURSDAY
morning

Chair: Jun CHEN

09:00 - 09:40

Shin-ichi ORIMO,
Hydrides'in77

09:40 - 10:05

Fadime HOSOGLU, 'Catalytic Hydrogenation of CO2 toCH4 and CO over Pt-K-Ta/Ni/ Al2O3'

79

10:05 - 10:30

Hui WANG, 'FURTHER STUDY ON HYDROGENDEUTERIUMEXCHANGE
MECHANISM
DURINGDESORPTION OF LIBH4-MGD2 SYSTEM'

81

10:30 - 10:55

Fang FANG, 'Fast hydrogen-induced optical andelectrical transitions of Mg-based alloy thin films withamorphous structure''Transition

andConduction

Chair: Shin-ichi ORIMO
11:20 - 11:45

Yijing WANG, 'Synthesis and catalytic effects of tiB2/TiN@Graphaene nano sheets on hydrogen storage ofMagnesium hydride'83

11:45 - 12:10

Guanqiao LI, 'Dehydriding
Combined with Mg2FeH6'

LiBH4

85

12:10 - 12:50

Jun CHEN, 'Combination of Lightweight Hydrogen
Storage Materials and Nanostructures'

87

PROCEEDINGS

Propertiesof8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

TUESDAY
evening

Chairs: Min ZHU, Andreas ZÜTTEL

P01

Ping LI, 'Remarkable dehydrogenation improvement of
LiAlH4 catalyzed by CoFe2O4 nanoparticles '

89

P02

Yanshan LU, 'NOVEL MG-IN-NI TERNARY ALLOYS FOR
REVERSIBLE HYDROGEN STORAGE '

91

P03

Xiaoling
SHAN,'CARBON-SUPPORTED
NI3B
NANOPARTICLES AS CATALYSTS FOR HYDROGEN
GENERATION FROM HYDROLYSIS OF AMMONIABORANE'

93

P04

Jie SHAO, 'A SYNERGETIC EFFECT OFNANOCONFINEMENT AND NANOCATALYSIS FOR THE
ENHANCED REVERSIBLE HYDROGEN STORAGE OF
LIBH4 '

95

P05

Shumin HAN, 'Effect of the LaFeO3 on thehydrogenation/dehydrogenation properties of MgH2 '

97

P06

Zhijie CAO, 'Structural Characteristics and Hydrogen
Storage Properties of Sm2Co7'

99

P07

Huizhong YAN, 'Investigation of the Thermodynamic
and Kinetic Properties of La-Fe-B System HydrogenStorage Alloys'

101

P08

Xiaobao YANG, 'Theoretical investigations on the
structural stabilities of Magnesium nanostructures andthe applications for hydrogen storage'

103

P09

Jianmei HUANG, 'Increased air stability and decreased
dehydrogenation temperature of LiBH4 via modification
within poly (methylmethacrylate)'

105

P10

Weitong CAI, 'Remarkable irreversible and reversible
dehydrogenation of LiBH4 by doping nanosized Cobalt
metalloid compounds'

107

P11

Yixiao FU, 'Study on the hydrogen exchange behavior
in the metal hydride-LiBH4 composite'

P12

Huaijun LIN, 'Mg-based amorphous/nano-materials withsuperior hydrogen storage properties'

P13

Jie CUI, 'Remarkable enhancement of dehydrogenationof MgH2 by a nano-coating of multi-valence TM-based(TM=Ti, Nb, V, Co, Mo, Ni) catalysts'

P14

Hao ZHONG, 'Energy efficiency of the cycle of NaBH4hydrolysis and an inexpensive regeneration method'

PROCEEDINGS

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

P15

Yunfeng ZHU, 'Hydrogen Storage Properties of MgPd/MWCNTs Composite Prepared by Hydriding
Combustion Synthesis and Mechanical Milling'

P16

E.CALLINI, 'Vibrational properties of Vanadium andZirconium based metal hydrides'

P17

Lixian SUN, 'Microporous carbon derived from metalorganic framework with high CO2 and H2 adsorption
heat'

P18

Zhibao LI, 'Improved dehydrogenation performance of
LiBH4 destabilized by (NH4)2TiF6'

P19

Shumao WANG, 'Optimized design of hydrogen storage
tanks based on 2LiNH2-MgH2 using simulation'

SCIENCE OF HYDROGEN & ENERGY AWARD

109

List of Participants

127

Information

138

Notes

PROCEEDINGSTimetable

8th Int. Symposium Hydrogen & Energy

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Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

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Zhaoqing, P.R. China 2014

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

Abstracts1

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 20142

th

8 Int. Symposium Hydrogen & Energy

Zhaoquing, P.R. China 2014

CLOSING THE CYCLE WITH HYDROGEN
Andreas ZÜTTEL
EMPA Materials Sciences & Technology, Dübendorf, Switzerland
The world energy demand continues to increase, the reserves of fossil fuels are limited, the combustion of the fossile
fuels leads to an increase of the CO2 in the atmosphere and therefore to a climate change and finally the economy of theindustrialized world is dependent on the fossil fuels. Currently the world operates with an open cycle mining fuels andmaterials and finally releasing the CO2 into the atmosphere, polluting the water, creating nuclear waste deposits anddepositing carbage. The world economy can become a sustainable economy by closing the materials cycles especiallythe energy materials cycle. Therefore, hydrogen from renewable energy used the reduce CO2 from the atmosphere leads
to synthetic hydrocarbons in a CO2 neutral cycle.

Resources
Industrialization was based on an open cycle, i.e. miningof materials and fossil fuels, manufacturing the products
and disposal of the used materials as well as release of
the CO2 in the atmosphere.

as they are released and neutral products, e.g. water,
can be released or deposited without affecting thesustainability. There are just two ways to close the cycle[1]: remove the carbon from the energy cycle andintroduce hydrogen as an energy carrier for the solar
energy or to extract CO2 from the atmosphere and to
reduce it with hydrogen to synthetic fuels.

Fig. 1 Current economic system based on mining anddepositing.

The sustainability of the post industrialization era isdetermined by the ability to close the materials cycles i.e.
to change from fossil fuels as energy carriers to
renewable energy. Since renewable energy (solar,
geothermal and planet movement) occurs in energy
fluxes, an appropriate energy carrier has to besynthesized.

Closing the cycle
According to statistical considerations the world
population will stabilize at approx. 10 billion humans in
2050 thanks to growing wealth in the developing
countries. That is an increase in the number of people by
25% and a large increase in demand for resources if all
would reach the living standard of western Europe. Only
products, which are naturally recycled with the same rate

A. Züttel

Fig. 2 Future sustainable economy based on the closed cycle

The established routes for the reduction of CO2 are the
Sabatier reaction for methane, the reversed water gas
shift reaction for CO combined with the Fischer-Tropsch
synthesis for hydrocarbons and the reduction of CO2 tomethanolfor
dimethylether
andhydrocarbons.
Thermodynamicaly the hydrocarbons conserve approx.
76% (5470kJ/7145kJ) of the energy in the hydrogen used
to reduce the CO2.

References[1] A. Züttel, A. Remhof, A. Borgschulte, O. Friedrichs,
Phil. Trans. Royal Soc. A – Math. Phys. and Eng. Sci.
368 (2010), pp. 3329 - 3342

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf,
Switzerland. 1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr.
rer. nat. from the science faculty UniFR. 1994 Post doc "Amorphous hydrides and optical films" with
AT&T Bell Labs in Murray Hill, New Jersey, USA. 1997 Lecturer at the Physics Department UniFR.
2003 External professor at the Vrije Universiteit Amsterdam, Netherlands. 2004 Habilitation inexperimental physics at the science faculty UniFR. President of the Swiss Hydrogen Association„HYDROPOLE“. 2006 Head of the section “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics
department UniFR. 2009 Guest Professor at IMR, Tohoku University in Sendai, Japan. 2012 Visiting
Professor at Delft Technical University, The Netherlands. >200 publications, >300 talks, h-index: 44

Corresponding author: Andreas ZÜTTEL, email: andreas.zuettel@empa.ch, Tel. +41 79 484 2553

3

8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

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Zhaoqing, P.R. China 2014

The Application of Nanotechnology in Hydrogen Storage
Ziwei Tang, Guanglin Xia, Xuebin Yu
Department of Materials Science, Fudan University, Shanghai, China
Abstract: To implement the hydrogen-based propulsion
systems, a viable, high efficient, safe and inexpensivehydrogen storage method is stringently required. The main
challenge for hydrogen storage materials to be practical is torelease hydrogen at moderate temperature with high contents.
Nanotechnology plays an important role in advancing theproperties of hydrogen storage materials. In this presentation,wereportourlatestresultsonthesynthesis,

andFigure 2. Hydrogen storage properties of the electrospun

dehydrogenation properties of a series of hydrogen storage

LiNH2/LiH@carbon nanofibers.

materials that were modified with various nano-templates.

References:

These

1.

nanoconfinedcompounds

showedfavorable

dehydrogenation and rehydrogenation performances at ambient
temperature,[1-5]significantly

advanced

over

their

2.

corresponding bulk substances. The achieved favorable
properties of these materials make them promising candidates

3.

for advanced hydrogen storage.
4.

5.

Ziwei Tang, Hao Chen, Xiaowei Chen, Limin Wu,
Xuebin Yu, Journal of the American Chemical
Society 2012, 134, 5464-5467.
Guanglin Xia, Dan Li, Xiaowei Chen, Yingbin Tan, Ziwei
Tang, Zaiping Guo, Huakun Liu, Zongwen Liu andXuebin Yu, Advanced Materials 2013, 25, 6238-6244.
Guanglin Xia, Qing Meng, Zaiping Guo, Qinfen Gu,
Huakun Liu, Zongwen Liu, XuebinYu, Acta
Materialia 2013, 61, 6882-6893.
Ziwei Tang, Xiaowei Chen, Hao Chen, Limin Wu, andXuebin Yu,
Angewandte Chemie-International
Edition 2013, 52, 5832 –5835.
Ziwei Tang, Yingbin Tan, Xiaowei Chen, Liuzhang
Ouyang, Min Zhu, Dalin Sun, Xuebin Yu, Angewandte
Chemie-International Edition 2013, 125, 12891–12895.

Figure 1. SEM and TEM images for the electrospun
LiNH2/LiH@carbon nanofibers.
Professor Xuebin Yu, received his Ph.D. degree in Materials Physics and Chemistry from Shanghai Institute ofMicrosystem and Information Technology, CAS in 2004, M.S. degree and B.S. degree in Mineral Engineeringfrom Wuhan University of Technology in 2000 and 1997, respectively. He worked at the University of
Nottingham as a postdoc in 2005-2006 and joined the University of Wollongong as a research fellow in 2007.
Since 2008, he was employed in Fudan University as a full professor. His work focuses on synthesis andcharacteristics of novel light-weight hydrogen storage materials. Prof. Yu has published over 130 papers
including JACS, Angew. Chem. Int. Ed. and Adv. Mater., etc..
Xuebin Yu
Corresponding author: Xuebin Yu, email, yuxuebin@fudan.edu.cn; Tel. 021-55664581

58th Int. Symposium Hydrogen & Energy

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Catalytic Behaviour of Co-Zn-B/Graphene Composite in Hydrogen
Generation by Hydrolysis of Alkaline Sodium Borohydride
Yongjin Zou, Cuili Xiang, Huanzhi Zhang, Li-Xian Sun*, Fen Xu
Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, PR China
Abstract: Hydrogen was generated by hydrolysis of sodium borohydride (NaBH 4) using Co-Zn-B/Graphene composite inthis work. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy
dispersive X-ray spectrometry (EDX). The Co-Zn-B/Graphene nanocomposite catalyst was found to consist of
amorphous Co-Zn-B nanoparticles attached to the surface of graphene. The kinetics of hydrolysis of NaBH 4 wasinvestigated. The effect of temperature, NaBH4 concentration, catalyst concentration and stability of the composite onhydrogen generation was also explored.

Introduction
NaBH4 has received great attention owing to its
combined advantages of high hydrogen capacity, goodstorability in alkaline solution, moderate operation
temperature, et al. Catalyst is necessary to control
hydrogen generation from NaBH4 solution. Numbers ofmaterials have been examined to be effective toaccelerate the hydrolysis of NaBH4. However, most ofthem are noble metal catalysts, which restrained theiruse in practical applications. In this work, a highly active
Co-Zn-B/graphene composite was prepared and its
performance for catalyzing the hydrolysis of NaBH 4 wasinvestigated in detail.

Experimental
In a typical experiment, Co-Zn-B/graphene composite
was prepared by chemical reduction method. Graphene
was dispersed in CoSO4 and ZnSO4 solution andsonicated for 3 h. Subsequently, the alkaline NaBH4
solution was added in the above solution dropwisely withmagnetic stirring. The produced black suspension was
filtered and washed repeatedly using distilled water. Theocatalyst was then dried in vacuum at 60 C for 24 h. For
comparison, Co-B and Co-B/grapheme were also
prepared.

Results and Conclusion
Graphene supported Co-Zn-B catalyst demonstrated
higher catalytic activities than the unsupported Co-Zn-B
catalyst. The reaction rates of the alloys were Co-ZnB/grapheme>Co-Zn-B>Co-B. The volumes of hydrogengeneration on all catalysts increased linearly withreacting time, suggesting a zeroth order reaction withrespect to NaBH4 concentration. The activation energy
for different catalysts was also investigated. The low
activation energy of Co-Zn-B/grapheme causes its highactivity.

References[1] H. B. Dai, Y. Liang, P. Wang, H.M. Cheng, J. Power
Sources 177(2008)17-23.
[2] Y. C. Lu, M.S. Chen, Y.W. Chen, Int. J. Hydrogen
Energy, 37(2012)4254-4258.

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Dr. Zou received his PhD from Chinese Academy of Science in 2008. After three years postdoctoral
experience in University of Maryland. He became a faculty in Guilin University of Electronic
Technology in 2011. His research mainly fouses on nanoparticles catalyzed metal hydride andsensors.

Yongjin Zou
2 /1995, Guest researcher (STA fellowship), National Institute of Advanced Industrial Science andTechnology (AIST), Japan; 5/1995, Postdoc. (AvH fellowship), Jena University, Germany;19962002, Guest Professor (AIST/ITIT, NEDO, fellowship) at AIST; 9/2001-2012, Professor and Group
Leader of Material Thermochemistry, Dalian National Laboratory of Clean Energy (DNL), DICP,
CAS; 2009--2012, Director of Key Laboratory of Energy Materials & Thermochemistry, Liaoning
Province; 2012-present, Dean of School of Material Science and Engineering; Director of Key Lab.
of Guangxi Information, Guilin University of Electronic Technology

Corresponding author: Li-Xian Sun (sunlx@guet.edu.cn), Phone: 0773-2313763

Acknowledgement: The authors thank the financial supports from “ 973 Project ” (2010CB631303), NSFC
(51361005, 51371060, 51071146, 21173111, 51102230, 51101144, 51201042 and 51201041), the State Key Laboratoryof Explosion Science and Technology, Beijing Institute of Technology (KFJJ13-12M).

8th

8 Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

ALKALI AND ALKALINE-EARTH BOROHYDRIDES FOR HYDROGEN
STORAGE
Sheng GUO, Daniel Reed and David Book
School of Metallurgy and Materials, University of Birmingham, Birmingham, B15 2TT, United Kingdom
The development of a volumetrically and gravimetrically efficient on-board hydrogen store, would greatly accelerate theintroduction of hydrogen fuel cell vehicles. There is a range of complex hydrides that have intrinsically high hydrogenstorage capacities, but the challenge is to develop a rapidly reversible material with a low hydrogen sorption temperature.
We have investigated two types of borohydride materials: disordered Mg(BH4)2 and eutectic mixture LiBH4-Ca(BH4)2.

Magnesium Borohydride
Mg(BH4)2 has received attention as (or a component of) a
possible storage medium for mobile hydrogen stores, due
to its high gravimetric H2 density (up to 14.9 wt%) withpartial reversibility [1]. There are several polymorphs ofMg(BH4)2 stable at room temperature, obtained throughdifferent synthetic approaches [2]. However, the detailed
decomposition mechanism(s), as a function of conditions
and of the starting phase, is not clear.
An investigation of the structural and compositionalchange of the crystalline and disordered γ-Mg(BH4)2 as afunction of temperature has been carried out [3]. An
amorphous Mg(BH4)2 phase is produced after ball-milling(in 100 bar H2) γ-Mg(BH4)2 for 2 h. This disordered γMg(BH4)2 dehydrogenates via a pathway with release ofdiborane, which is different from crystalline γ-Mg(BH4)2.
Various unknown compounds are observed by in situ
XRD and Raman measurements, which might be related
to the formation of polyboranes during decomposition.
Mg, B and finally MgB2 are observed during heating to
600 °C.

Eutectic Mixture LiBH4-Ca(BH4)2
Mixed borohydride compounds, offer the prospect ofmore favourable thermodynamic properties and lower
decomposition temperatures, and so have been
considered as hydrogen storage media. In the binary
LiBH4-Ca(BH4)2 system, samples prepared by ball millingwere found to exist as physical mixtures, which exhibited
eutectic melting at around 200 °C [4]. An in situ NMR
study demonstrated that the LiBH4-Ca(BH4)2 mixture canform a solid solution below the eutectic melting point [5].

However, both the mechanism of the exchange of thecations between the borohydrides, and the reaction
pathways during decomposition at higher temperatures,
need further exploration.
In this work, the decomposition mechanism of a
0.68LiBH4+0.32Ca(BH4)2 mixture has been investigated,
utilising various techniques including in-situ XRD and
Raman spectroscopy. A new phase is observed when
heating and cooling the sample between phase changes
and eutectic points for three cycles. The identification ofthis phase is ongoing, however, it does not appear tocorrespond to known borohydrides or borohydrideborates. In which case, this phase may be tentatively
ascribed to a metastable dual-cation borohydride. A
series of phase and melting reactions and the formationof CaB6, Li2B12H12, CaB12H12 and amorphous boron are
observed in the Raman spectra.

References[1] H.W. Li, K. Kikuchi, Y. Nakamori, N. Ohba, K. Miwa, S.
Towata, & S. Orimo, Acta Mater., (2008) 56, 1342;[2] K. Chlopek, C. Frommen, A. Leon, O. Zabara, & M. Fichtner,
J. Mater. Chem., (2007) 17, 3496. Y. Filinchuk, B. Richter,
T.R. Jensen, V. Dmitriev, D. Chernyshov, & H. Hagemann,
Angew. Chem.-Int. Edit., (2011) 50, 11162.
[3] S. Guo, H.Y.L. Chan, D. Reed & D. Book, J. Alloys Comp.,(2013) 580, S296.
[4] J.Y. Lee, D. Ravnsbaek, Y.S. Lee, Y. Kim, Y. Cerenius, J.H.
Shim, T.R. Jensen, N.H. Hur, & Y.W. Cho, J. Phys. Chem. C,(2009), 113 15080. H.S. Lee, S.J. Hwang, H.K. Kim, Y.S.
Lee, J. Park, J.S. Yu & Y.W. Cho, (2012). 3 2922-2927.
[5] Y. Yan, A. Remhof, P. Mauron, D. Rentsch, Z. Lodziana, Y.S.
Lee, H.S. Lee, Y.W. Cho, and A. Züttel, (2013). 117 8878.

Born 1988 in Guiyang, China. Sheng is a PhD student of Metallurgy and Materials at University ofBirmingham since 2010 and is expected to complete the degree in 2014. Her research is focusing
on developing novel lithium, magnesium and calcium-based materials for hydrogen storage. Shengstudied at Central South University (CSU), China in 2006-2008, and was an exchange student atUniversity of Birmingham (UoB), UK in 2008-2010. She received Bachelor of Engineering instMetallurgy (1 Class Honours) from UoB in 2010, and Bachelor of Material Science and Engineeringfrom CSU in 2011.
Sheng Guo
Corresponding author: Sheng GUO, Email: sxg819@bham.ac.uk, guosheng7@icloud.com, Mobile: +44 (0)7594 622 858

98th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

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Zhaoquing, P.R. China 2014

HYDROGEN STORAGE PROPERTIES AND MECHANISMS OF ALKALIMEAL-ADDED LI-MG-N-H SYSTEM
Chao Li, Yongfeng Liu, Mingxia Gao, Hongge Pan
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China.

Abstract
Hydrogen is the most ideal fuel in the comprehensive
clean-energy concept. However, hydrogen storage is stilla major technical barrier for its on-board application as atransportation fuel. Recently, metal-N-H systems havebeen attracting significant attention owing to their highgravimetric hydrogen density. Among them, the Li-Mg-NH material is regarded as one of the very promisingsystems due to its good reversibility, comparatively highhydrogen content and favorable thermodynamic
properties. Unfortunately, a relatively high kinetic barrier
retards its practical applications for hydrogen storage. In
this work, we present our recent work on improving thehydrogen storage thermodynamics and kinetics of the LiMg-N-H system by adding the alkali metal compounds.
The K-based halides were first introduced into the
Mg(NH2)2-2LiNH2 system. It is found that the KF-added
sample exhibits superior hydrogen storage properties as~ 5.0 wt% of hydrogen can be reversibly stored in the
0.08KF-added sample via a two-stage reaction with an
onset dehydrogenation temperature of 80 ºC. However,hydrogen storage behaviours of the samples with KCl,
KBr and KI remain almost unchanged. The fact that KF
can readily react with LiH to convert to KH and LiF due tothe favorable thermodynamics during ball milling shouldbe the primary reason for its significant effects as thepresence of KH provides a synergetic thermodynamic
and kinetic destabilization in the hydrogen storage
reaction of the Mg(NH2)2-2LiH system by declining theactivation energy of the first-step dehydrogenation as acatalyst and reducing the desorption enthalpy change ofthe second step as a reactant. In addition, theintroduction of RbF also decreased the de-/hydrogenation temperatures and enhanced thehydrogen storage kinetics of the Mg(NH2)2-2LiH system.
At 130 ºC, ~ 70% of hydrogen was rapidly released fromthe 0.08RbF-doped sample within 180 min, and the fully
dehydrogenated sample could absorb ~ 4.8 wt% ofhydrogen at 120 ºC. Structural analyses revealed thatRbF reacted readily with LiH to convert to RbH and LiF
due to the favorable thermodynamics during ball milling.
The newly generated RbH participated in the following
dehydrogenation reaction, consequently resulting in adecrease in the reaction enthalpy change and activationenergy. The understanding on the role played by KF andRbF sheds light on how to further decrease the operating
temperature and enhance the hydrogen storage kineticsof the Metal-N-H system.

References[1] P. Chen, Z. Xiong, J. Luo, J. Lin, K. Tan, Nature 2002,
420, 302-304.
[2] Z. Xiong, G. Wu, J. Hu, P. Chen, Adv. Mater. 2004,
16, 1522-1525.
[3] W. Luo, J. Alloys Compd. 2004, 381, 284-287.
[4] Y. Liu, C. Li, B. Li, M. Gao, H. Pan, J. Phys. Chem. C
2013, 117, 866-875.
[5] C. Li, Y. Liu, Y. Gu, M. Gao, H. Pan, Chem. Asian J.
2013, 8, 2136-2143.

Yongfeng Liu received his PhD in Materials Science and Engineering from Zhejiang University in
2005. He then moved to National University of Singapore as a postdoctoral research fellow. He
joined Zhejiang University as an associate professor and was promoted to Professor in 2012. His
research is focused on solid-state hydrogen storage materials and electrode materials of
rechargeable batteries.

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

118th Int. Symposium Hydrogen & Energy

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Zhaoqing, P.R. China 2014

GEOMETRICAL EFFECT STUDY IN MG-BASED BCC STRUCTURE
MATERIALS FOR HYDROGEN STORAGE
Huaiyu Shao*, Aleksandar Staykov
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Japan
Abstract Mg-Co body-centred cubic (BCC) structure alloys synthesized by ball milling method show good hydrogen
absorption kinetics at even below room temperatures. Large surface area, short diffusion distance, numerous defects
introduced from the milling process and the BCC lattice structure are important factors for the kinetics enhancement.
Here we will report our unpulibshed data of experimental and compuational work on how the geomtrical size effect could
affect hydrogen occupancy in Mg-based BCC structure materials.

Introduction
Mg-based body-centred cubic (BCC) alloys have been
investigated for hydrogen storage research by the
1-3
authors intensively . Mg55Co45 BCC alloys synthesizedby ball milling method can absorb hydrogen at 258 K witha hydrogen capacity around 3.2 wt% without any
2
activation process . The absorption temperature of 258 K
is the lowest one reported so far for Mg-based materials
to absorb hydrogen. In this paper, we will present our
results on how the geometrical size effect could affecthydrogen storage properties in Mg-Co BCC structurenano-materials.

Results and Discussion
The Mg50Co50 alloy milled for 100 h shows BCC
1structure with a lattice parameter of 0.300(1) nm . The
BCC structure can be confirmed from electron diffraction
pattern. The SEM image shows a particle size around 1-3
micrometers and the dark-field TEM image indicates a
1grain size around a few nanometers . The micrometerscale particle size and nanometer scale grain size means
much larger surface area and shorter diffusion distancefor hydrogen absorption.
Up to date, the highest two H/M ratios found for BCC
2
metal lattice hydrides are 1.28 for Mg55Co45H128 and4
1.33 for Mg2CaV3H8 . This can be explained fromgeometrical size effect in BCC metal lattice interstitial
hydrides with a lattice parameter about 0.30 nm (Figure1). It will be discussed from both experimental andcomputational aspects in this presentation.

Huaiyu Shaoe-Figure 1. Proposed hydrogen occupancy positions andcalculated electron charge mapping in BCC structure
hydrides with lattice parameter around 0.30 nm.

References[1] Shao, H.; Asano, K.; Enoki, H.; Akiba, E. Scripta
Materialia 2009, 60, 818.
[2] Shao, H.; Xin, G.; Zheng, J.; Li, X.; Akiba, E. Nano
Energy 2012, 1, 590.
[3] Shao, H. Y.; Matsuda, J.; Li, H. W.; Akiba, E.; Jain, A.;
Ichikawa, T.; Kojima, Y. Int J Hydrogen Energy 2013,
38, 7070.
[4] Kondo, T.; Sakurai, Y. J Alloy Compd 2006, 417, 164.

● May 2011-present, assistant professor, International Institute for Carbon-Neutral Energy Research(WPI-I2CNER), Kyushu University, Japan.
● Apr. 2009-Apr. 2011, Postdoc, Research Group of Prof. Dr. Ferdi Schüth, Department of
Heterogeneous Catalysis, Max-Planck-Institut für Kohlenforschung, Germany (with Dr. Michael
Felderhoff, Prof. Ferdi Schüth, Prof. Borislav Bogdanović).
● Jul. 2005-Mar. 2009, Postdoc, Energy Technology Research Institute, National Institute ofAdvanced Industrial Science and Technology, Japan (with Dr. Etsuo Akiba).
● Ph.D. in Chemistry, Peking University, China, Jun. 2005 (supervisor: Prof. Xingguo Li).
● B.S. in Chemistry, Peking University, China, Jul. 2000.

Corresponding author: Huaiyu Shao, h.shao@i2cner.kyushu-u.ac.jp, Tel. 0081-92-802-6733.

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8th Int. Symposium Hydrogen & Energy

Zhaoquing, P.R. China 2014

CONTROL OF THERMODYNAMIC AND KINETIC PROPERTIES OFMETAL HYDRIDE COMPOSITE CONFINED IN MESOPORE CAGESYoung-Su Lee, Hyun-Sook Lee, Jinyoo Suh, Jae-Hyeok Shim, Young Whan Cho
High Temperature Energy Materials Research Center
Korea Institute of Science and Technology,
Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791
Republic of Korea
Light metal complex hydrides such as LiBH4, Mg(BH4)2, and Ca(BH4)2, have high reversible hydrogen storage
capacities but dehydrogenation temperature and rehydrogenation reaction kinetics as well as sorption cycle performanceare rather poor. There are some possible ways to improve thermodynamic and/or reaction kinetic properties of these
metal hydride. They include cation or anion exchange, size reduction and interface control by nano-confinement, mutual
destabilization by mixing different hydrides, and combination of these for further improvement. Here our recent work on
size reduction and interface control with LiBH4-Ca(BH4)2 eutectic composites infiltrated into different mesopore cages will
be presented together with some preliminary explanations.

We have recently observed enhanced hydrogen
desorption and absorption properties for a eutectic
0.68LiBH4 + 0.32Ca(BH4)2 composite (LC) co-infiltrated
into CMK-3, an ordered mesoporous carbon[1-3]. The
dehydrogenation process was accelerated, and thedesorption temperature was significantly reduced toabout 300 °C, compared with ~ 400 °C for pure LC. In
addition, the XRD peak intensity of the borohydrides
decreased and the eutectic melting was hardly seen in
the DSC curve even after the composite was ball-milledwith CMK-3. The DSC peaks were completely
disappeared after melt infiltration. Nuclear magnetic
resonance (NMR) spectroscopy is indispensable inunderstanding these phenomena and in probing the local
environment of the [BH4]− anions. The system was foundto be suitable for the application of in situ variabletemperature (VT) NMR because of the lowered melting
temperatures of the two borohydrides (∼200 °C) and thewide separation of the 11B NMR shifts for the [BH4]−
anions ( ∼ 10 ppm) in LiBH4 and Ca(BH4)2. Because
nanoconfinement is often achieved through theintroduction of hydride particles into host scaffold poresusing a melt infiltration method, such in situ
spectroscopic observation is believed to be highly
valuable. In the present work, we used solid-state magic
angle spinning (MAS) NMR to elucidate the local
environment of the ionic species in the LC composite andthe way in which they interact with various mesopore
support materials. The composite borohydrides,
combined with the mesopore scaffold materials with awide range of porosities, were carefully examined indifferent stages during heating by in situ and ex situ NMR.
We also demonstrate the nanoconfinement effect on thehydrogen storage properties of the composite material
investigated.

References[1] Hyun-Sook Lee, Son-Jong Hwang, Hoon Kee Kim,
Young-Su Lee, Jinsol Park, Jong-Sung Yu, Young Whan
Cho, “In Situ NMR Study on the Interaction between
LiBH4−Ca(BH4)2 and Mesoporous Scaffolds“, J. Phys.
Chem. Lett., 2012, 3, 2922−2927.
[2] Hyun-Sook Lee, Young-Su Lee, Jin-Yoo Suh, Minwoo
Kim, Jong-Sung Yu, Young Whan Cho, ”Enhanced
Desorption and Absorption Properties of Eutectic LiBH4Ca(BH4)2 Infiltrated into Mesoporous Carbon”, J. Phys.
Chem. C, 2011, 115, 20027–20035.
[3] Yigang Yan, Arndt Remhof, Philippe Mauron, Daniel
Rentsch, Zbigniew Lodziana, Young-Su Lee, Hyun-Sook
Lee,,ttel, “Controlling the
Dehydrogenation Reaction toward Reversibility of the
LiBH4−Ca(BH4)2 Eutectic System,” J. Phys. Chem. C
2013, 117, 8878−8886.

Dr. Young Whan Cho is presently a principal research scientist at Korea Institute of Science andTechnology and the head of Nanomaterials Science and Engineering at University of Science andTechnology. He received a MEng degree from Seoul National University and completed his PhD at
Department of Materials Science and Metallurgy of Cambridge University in 1990. His researchinterests lie at metal hydrides for reversible hydrogen storage and the design and preparation ofheterogeneous catalysts for synthetic fuels. Dr. Cho’s research group has published over 90 papers
on hydrogen storage materials and alloys for hydrogen separation membrane for the last 10 years.
Young Whan Cho
Corresponding author: Young Whan Cho, oze@kist.re.kr, +82-2-958-5465

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8th Int. Symposium Hydrogen & Energy

Zhaoquing, P.R. China 2014

NANOPOROUS FRAMEWORKS FOR HYDROGEN STORAGE AND H2/D2
ISOTOPE SEPARATION
Michael Hirscher, Maurice Schlichtenmayer, Julia Teufel, Hyunchul Oh
Max Planck Institute for Intelligent Systems, Stuttgart, Germany
Highly porous coordination polymers or framework materials show high gravimetric hydrogen uptake by physisorption at
low temperatures which can be utilized in cryo-adsorption tank systems. Furthermore, the uniform pore size distribution
and small apertures can be applied for separation of light isotopes by quantum sieving. Mainly experimental results will
be shown on the characterization of hydrogen storage properties and on newest achievements in isotope separation by
quantum sieving.

Nanoporous Frameworks
The field of coordination polymers or framework materials
has tremendously grown, since the stability of thesestructures could be shown after removal of the solvent
molecules, exhibiting a nanoporous framework with ultrahigh porosity and large specific surface area [1]. Different
classes of these novel highly porous structures, e.g.,
metal-organic frameworks (MOFs), zeolitic imidazolate
frameworks (ZIFs) or covalent organic frameworks(COFs), have been extensively studied for applications ingas storage. Beside their large surface area, thesecrystalline frameworks possess well defined pore sizes
having a uniform distribution. Frameworks with small
pores and/or even smaller apertures can be designed
enabling sieving effects for gas separation. Recently,
quantum sieving in nanopores with a diameter near the
kinetic extension of the hydrogen molecule was proposed
as one promising possibility for separating D2/H2 isotope
efficiently and effectively [2].

Hydrogen Storage
For the maximum hydrogen uptake at high pressure and77 K an almost linear correlation with the specific surface
area is found for many different nanoporous frameworkmaterials [3]. Furthermore, frameworks possessing
smaller pores show typically a higher heat of adsorption.
Both, maximum hydrogen storage capacity and heat ofadsorption have to be considered to optimize thematerials for their potential application [4]. The
presentation will give a short overview and focus on a
new method to determine experimentally the maximum
gravimetric and volumetric hydrogen storage capacity formonoliths of porous
measurement [5].

materials

inone

isothermal

H2/D2 Isotope Separation
Separating gaseous mixtures of light gas isotopes,
especially H2/D2, is a difficult task since size, shape andthermodynamic properties share each other. Quantum
sieving [1] in these new crystalline frameworks withuniform pore size which can be tailored may be one
solution. Experimental results obtained by low-pressurehigh-resolution isotherms and cryogenic thermal
desorption spectroscopy (TDS) directly on isotope
mixtures will show the potential of these frameworks andthe importance of pore size and aperture for effective
quantum sieving. The experimental findings arerationalized by first-principles calculations in the group ofThomas Heine, Jacobs University, Bremen, Germany, toreach a detailed microscopic picture of the underlying
elementary processes [6].

References[1] G. Férey, Chem. Soc. Rev., 37 (2008) 191; S.
Kitagawa et al., Angew. Chem. Int. Ed., 43 (2004)
2334; O.M. Yaghi et al., Nature, 423 (2003) 705.
[2] J.J.M. Beenakker et al., Chem. Phys. Lett., 232(1995) 379.
[3] M. Hirscher, Angew. Chem. Int. Ed. 50 (2011) 581.
[4] M. Hirscher, M. Schlichtenmayer, J. Mater. Chem.,
22 (2012) 10134.
[5] H. Oh et al., RSC Adv. 4 (2014) 2648.
[6] J. Teufel et al., Adv. Mater. 25 (2013) 635.

Michael Hirscher is group leader at the Max Planck Institute for Intelligent Systems, Stuttgart,
Germany. He studied physics at the University of Stuttgart, Germany and at the Oregon State
University, Corvallis, USA, receiving a Master’s degree, a Diploma, and Ph.D. degree in 1982, 1984,
and 1987, respectively. For his achievements he was awarded the Otto Hahn Medal of the Max
Planck Society in 1988. Prior to taking his position in Stuttgart, he spent a post-doctoral fellowship at
the University of Pennsylvania, Philadelphia, USA. He published over 100 papers and edited
recently the “Handbook of Hydrogen Storage”. His current research interests focus on nanoporousand nanoscale materials for gas storage and separation.
M. Hirscher
Corresponding author: Michael Hirscher, hirscher@is.mpg.de, Tel. +49-711-689-180817

8th Int. Symposium Hydrogen & Energy

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Zhaoquing, P.R. China 2014

NEW METHOD TO FORM Mg(BH4)2 NANOSTRUCUTRES
1Yigang YAN, 1Arndt Remhof, 1Andreas Züttel, 2Daniel Rentsch, 3Yuen S. Au, 3Petra E.de Jongh

1

EMPA, Hydrogen & Energy, Dübendorf, Switzerland
EMPA, Functional Polymers, Dübendorf, Switzerland
3
Inorganic Chemistry and Catalysis, Utrecht University, Utrecht, the Netherlands
2

Nanoparticles of complex hydrides are usually synthesized via solution impregnation or melt infiltration in nanoporous
scaffold. The former suffers from solvent residue and the latter is hindered when a compound (e.g. Mg(BH4)2)
decomposes before melting. We developed a new method to synthesize Mg(BH4)2 nanoparticles via the gas-solid
reaction between B2H6 and MgH2 nanoparticles. This method has also been successfully applied to synthesize othercompounds such as MgB12H12.
11

Introduction
Metal borohydrides, with high gravimetric and volumetricdensities of hydrogen, have been extensively
investigated for solid state hydrogen storage. Amongthem, Mg(BH4)2 shows a hydrogen capacity of 14.9 wt%
and an attractive enthalpy change of -39 kJ/mol H2 indehydrogenation reaction.[1]Solution impregnation of Mg(BH4)2 in nanoporous
scaffolds, such as activated carbon and CMK3, has been
investigated.[2, 3] The drawbacks of solvent residue andunconfined Mg(BH4)2 were reported in this method andthe reversible hydrogen sorption was not achieved. Here,
we reported a new method to synthesize Mg(BH4)2
nanoparticles via the reaction between MgH2
nanoparticles and B2H6 according to the following
reaction.[4]MgH2 + B2H6 → Mg(BH4)2

Figure 1 shows B MAS NMR spectrum of the assynthesized Mg(BH4)2/carbon nanocomposite. The
resonance at -41 ppm was assigned to the [BH4] species.
MgB12H12 was observed as a side product which was
located at -16 ppm. The nanocomposite showed areduced desorption temperature to 100 ºC and reversiblehydrogen absorption under mild conditions.

Mg(BH4)2/carbon

K2B12H12
40

20

0

-20

-40

-60

-80

11

Experimental

δ B / ppm

MgH2 nanoparticles supported on carbon aerogel, with a
MgH2 loading ratio of 10 wt%, were prepared via melt
infiltration. The reaction between MgH2 nanoparticles andB2H6 was carried out at room temperature and promoted
by ball milling. MgH2 supported on nonporous graphite
was investigated to compare the role of carbon matrix.
11
B MAS NMR, TEM/EELS/EDX, X-ray diffraction, N2physisorption and TPD-MS were used to characterize thesamples.

Results

Mg(BH4)2

Figure 1. 11B MAS NMR spectrum of the as-synthesizednanocomposite,
comparedwith
Mg(BH4)2/carbon
references Mg(BH4)2 and K2B12H12.

References[1] S.I. Orimo et al., Chem Rev, 107 (2007) 4111-4132.
[2] M.A. Wahab et al., J Mater Chem A, 1 (2013) 34713478.
[3] M. Fichtner et al., Nanotechnology, 20 (2009).
[4] Y. Yan et al., J Mater Chem A, 1 (2013) 11177-11183.

2004-07 PhD student at Institute of materials science and engineering, Sichuan University, China.
2007-08 Senior engineer at SAE Magnetics (H.K.) Ltd, China.
2008-09 Postdoctoral Fellowship at Institute for Materials Research, Tohoku University, Japan.
2009-11 JSPS Postdoctoral Fellowship at Institute for Materials Research, Tohoku University, Japan.
2011-12 Postdoctoral Fellowship at EMPA, Switzerland.
2012
Visiting Scientist in Utrecht University, the Netherlands.
2012Research Fellow at EMPA, Switzerland.
Corresponding author: Yigang YAN, yigang.yan@empa.ch, +41 58 765 40 82

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Increased air stability and decreased dehydrogenation temperature of
LiBH4 via modification within poly(methylmethacrylate)
Jianmei Huang, Yurong Yan, Liuzhang Ouyang*, Hui Wang, Jiangwen Liu, Min Zhu
School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, People’s
Republic of China;
Abstract: An air-stable LiBH4 polymeric composite was successfully prepared by modifying LiBH4 with a gas-barrier
polymer matrix--Poly (methylmethacrylate) (PMMA). The nanoconfinement of LiBH4 in the PMMA network pore structure
leaded to fast H2 release from LiBH4 molecules at low temperature. Meanwhile, PMMA can not only protect LiBH4 fromwater and oxygen but also let hydrogen get in and out freely. LiBH4@PMMA composite show the good hydrogenoodesorption property, which started to dehydrogenate at 53 C and released 5.2 wt.% of hydrogen at 162 C within 1 h. It
could be concluded that PMMA can increase the stability of LiBH4 in the atmosphere and reduce the dehydrogenation
temperatureof
LiBH4.

Introduction
Nanoengineering had been demonstrated to be a useful
methodtoreducethedehydriding/rehydriding
temperature of LiBH4. Nanoscale LiBH4 is too reactive,
so it is necessary to stabilize it for commercial utilization.
PMMA had the better gas selectivity than othercommonly polymer, with a high permeability ratio of[1]
H2/O2 . Hence, it was used in hydrogen storage to keepaway the water and oxygen but let the hydrogen get in orout freely. In this work, LiBH4 was nanoconfined by
PMMA with fine network pore structure for the first time,
which protected from the water and oxygen anddecreased the dehydrogenation temperature significantly(scheme1).

weaker and completely disappeared in the end. The firstpeak could be contributed to decomposing behavior of
the LiBH4 nanoconfined by the PMMA network pore
structure, and the second peak was corresponding to theunconfined LiBH4 outside the PMMA network pore
structure. The above results confirmed that PMMA canprotect LiBH4 from the water and air but let the hydrogen
get out freely, and significantly lower the stability of LiBH4.
Morever, comparing with that the pure LiBH4 onlyoreleased 0.6 wt.% of H2 within 4 h at 260 C,
LiBH4@PMMA composites could release 5.2 wt.% ofhydrogen in 1 h and 5.6 wt.% of hydrogen in 4 h at 162oC, respectively.

Figure 1. MS hydrogensignals of the LiBH4@PMMA
composite(c) and after
exposure the LiBH4@PMMA
composite to air for 1h (d),4h (e), 8h (f). compared withthe pure PMMA (a) and
LiBH4(b).

Scheme 1. Schematic
illustration of LiBH4
protected from oxygen
and water by PMMA

Result
The LiBH4 particles had a diameter distribution of 19-73
nm in the crosslinked network pore structure of PMMA,and showed an amorphous structure. The resuts
indicated that the particle size of LiBH4 was significantly
refined by modifying with PMMA. The LiBH4@PMMAocomposite presents a lower onset temperature of 53 C,
and with two mian dehydrogenation peaks (figure 1). As
the exposure time extending, the intensity of peak at 360o
C became

References[1] K. J. Jeon, H. R. Moon, A. M. Ruminski, B. Jiang, C.
Kisielowski, R. Bardhan and J. J. Urban, Nat. Mater.,
2011, 10, 286.

Jianmei Huang is a PhD candidate in Materials Processing from the South China University ofTechnology. Her current research interests are focused on the metal borohydrides for hydrogenstorage.

Jianmei Huang
Corresponding author: Liuzhang Ouyang, meouyang@scut.edu.cn, +86 2087114253

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Development and characterization of gas separation membranes
for alkaline water electrolysis
U. F. Vogta,b, M. Schluppa, D. Burnata, A. Züttela
For introducing Hydrogen as emission-free energy carrier, hydrogen production via water electrolysis is regaining
attention in the global search for alternative energy carriers nowadays. Efficiency enhancement for the Alkaline
Electrolysis by means of reducing the electric power consumption is a pre-condition for a successful application of thispromising technology. A crucial part of the electrolyser cell is the membrane, which is responsible for separatinghydrogen and oxygen gases during the electrolysis process. It has to ensure a high ion conductivity and likewise an
excellent chemical stability in 30 wt% KOH at 100°C for long term operation at 30 bar.

Introduction
Although the process of water electrolysis has been
known for over two hundred years [1], it is now gaining
increased attention as a means of energy storage forstrongly fluctuating renewable sources in periods ofexcess energy production on a MW scale. For the wellengineered Lurgi-Zdansky type high-pressure alkaline
electrolyser, increase of efficiency as well as cost
reduction is a big issue for future commercialization.

Membrane Development & Characteristics
The separation membrane serves as ionic conductor, but
electronic insulators and simultaneously prevents theintermixing of hydrogen and oxygen gases produced at
cathode and anode side.
2 H2O (l) + 2 e- H2 (g) + 2OH (aq)-resistance despite increased current densities (zero-gap
cells, low-resistance diaphragms), higher operating
temperatures(increased
electrolyte
conductivity,
decreased electrode overpotentials), new electrocatalysts
to reduce anodic and cathodic overpotentials [4].
Novel membrane developments and their characteristics
for low resistance diaphragms will be demonstrated.
[1] T. Smolinka. In J. Garche (editor), Encyclopedia ofElectrochemical Power Sources. Elsevier, Amsterdam (2009)
394–413.
[2] C. Sillen, E. Barendrecht, L. Janssen, S. van Stralen. Int. J.
Hydrogen Energy 7 (1982) 577–587. ISSN 0360-3199[3] M. Caspersen, J. B. Kirkegaard. International Journal of
Hydrogen Energy 37 (2012) 7436–7441[4] O. Ulleberg. Int. J. Hydrogen Energy 28 (2003) PII S0360–
3199 (02) 00033–2(cathode)

2 OH (aq) ½ O2 (g) + H2O (l) + 2 e (anode)--------------------------------------------------H2O (l) H2 (g) + ½ O2 (g) (overall reaction)---

The OH conductivity of gas separation membranes
strongly influences the efficiency of the electrolysis
process. This is influenced by the formation of gas
bubbles at the electrodes, which act as physical/electricalresistors in the electrolyte, thus redistributing andreducing current fields and decreasing the electrolyte
conductivity [2]. The influence of gas bubbles can be
reduced by increasing pressure [3] and by introducing
separator materials featuring good wettability and a low
sticking coefficient for gas bubbles.
Approaches to improve the efficiency of alkaline
electrolysers are the reduction of the surface-specific cell

Lurgi-Zdansky type alkaline electrolyser at Giovanola, Monthey
Working conditions: 32bar, 85°C, 25wt-% KOH
Production rate:
760 m³/h H2, equ. to 3.3 Mwel
Energy Consumption: 4.3 – 4.6 kWh/m³ H2Partial load:
25 - 100 % of nominal capacity
H2 purity:
99.5 - 99.8 vol%O2 purity:
99.3 - 99.6 vol%PD Dr. Ulrich Vogt is Senior Scientist at the EMPA laboratory “Hydrogen & Energy” and leader of thegroup electrolysis & membranes. He received his PhD and his PD at the Albert-Ludwig-University
Freiburg, Germany. Topics of his research work are hydrogen production via “high temperature
steam electrolysis”, “new membrane materials for low temperature alkaline water electrolysis” andcatalytic hydrogen combustion for cooking and heating applications by a newly developed catalytichydrogen burner system. He authored over 50 SCI publications and 10 patents. He is lecturer at the
University of Freiburg, with the topic Modern Ceramics, Cements, and Glasses.
Dr. Ulrich Vogt
Corresponding author: PD Dr. Ulrich Vogt, ulrich.vogt@empa.ch, Tel. +41 (0) 58 765 4160

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THE MYSTERY OF DIBORANE EVOLUTION DURING THE
DECOMPOSITION OF Γ-PHASE MAGNESIUM BOROHYDRIDE
Nicholas Stadie, Elsa Callini, Renaud Delmelle, Andreas Borgschulte, and Andreas Züttel
Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland

Abstract: Upon heating, light metal borohydrides decompose to release a large amount (up to 18 wt%) of hydrogen1
which can be used as a fuel for mobility. While their reversibility and the specific reaction path of dehydrogenation
remains under investigation in numerous systems, it is known that the hydrogen evolution is accompanied by diborane
release inversely related to the stability of the borohydride.2 This makes quantification of the hydrogen amount an
important task; we solve this using a combination of infrared spectroscopy and gravimetry under gas flow. Magnesiumborohydride (Mg(BH4)2), which exists in numerous meta-stable phases at ambient conditions, is thought to be a memberof the stable borohydride family (materials which do not emit diborane). However, we do in fact measure a significant,specific fraction of diborane released during the heating of the porous γ-phase between 300-500 K. To address the originof this diborane emission, we use numerous techniques in an attempt to separate the borane impurities from the sample
before heating (e.g. if simply a byproduct of synthesis), such as ball-milling and supercritical carbon dioxide drying.

Infrared (IR) Spectroscopy: Quantification

Results

IR absorption spectra of the gaseous products of reaction
can be effectively used to quantify and determine their
specific contribution to mass loss in the sample.

All materials investigated were weighed during heating in
H2 flow, and the mass loss deconstructed as in Figure 2.
The H2 and B2H6 (specific) mass loss are shown below.

Figure 1. Quantities of diborane emitted from various samplesof Mg(BH4)2 during decomposition, including the (pure) α-, β-,and γ-phases, as well as treated γ-phases.

Total

Diboranen-Butane

Other

Remainder (H2)

γ-MBH (AU)

10.7

1.9

1.1-1.2

0.0

7.6-7.7

γ-MBH (SA)

9.1

2.3

0.1-0.6

0.0

6.2-6.7

α-MBH

9.8

0.1

1.4

0.0

8.3

β-MBH

8.5

0.0

0.3

--

8.2

BM-γ-MBH

8.4

1.9

--

--

6.5

SCC-γ-MBH

25.6

0.0

--

17-20

5.6-8.6

Table 1. Comparison of the (calculated) hydrogen mass loss andthe measured impurity mass losses between 30-300 °C during
the first heating cycle.

Conclusions
Magnetic Suspension Gravimetry + IR

Figure 2. An example deconstruction of the total mass loss datacollected by gravimetry after IR analysis of the reaction productgases, in this case predominantly diborane and n-butane.

Nicholas Stadie

Supercritical CO2 drying pre-treatment techniques weresuccessful at suppressing the emission of diborane in γphase Mg(BH4)2 during heating, within detection limits ofa downstream IR spectrometer. This may be anindication that diborane exists in an adsorbed state within
the pores of the material after synthesis. A
solvent/diborane-free route to the porous, γ-phase
Mg(BH4)2 has been presented, yielding a material that
decomposes to release very high quantities of H2.

References
1. A. Züttel et al., J. Power Sources 118, 1 (2003).
2. E. Callini at al., Dalton Trans. 42, 719 (2013)

Nick was born in 1985 in Calgary, Alberta, Canada. He received a BS in chemistry from ArizonaState University in Tempe, Arizona, USA in 2007. He received a MS and PhD in materials science at
Caltech in Pasadena, California, USA with Prof. Brent Fultz and Dr. Channing Ahn, focusing on
synthesis and thermodynamic characterization of physisorptive materials for hydrogen storage. In
2013, he joined Empa as a postdoc, and is supported by the EU program Bor4Store, studying newtechniques for characterizing the decomposition pathways of light metal complex hydrides.

Corresponding author: Nicholas Stadie, nicholas.stadie@empa.ch, +41 58 765 4153

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TOWARDS EASY AND FULLY REVERSIBLE DEHYDROGENATION OF
LIBH4 BY CATALYZING OF HIERARCHIC NANOSTRUCTURED COB
Weitong
Cai1,2,
Hui
Wang1,2,
Wang3,*,LiuzhangOuyang1,2, Min Zhu1,2,*

Jiangwen

Liu1,2,Lifang

Jiao3,

Yijing1 School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P.R.China
2 Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou 510640, P. R. China
3 Institute of New Material Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai
University, Tianjin 300071, P. R. China
Abstract: LiBH4 is one of the most promising hydrogen storage materials due to its high gravimetric hydrogen density
3(18.5wt.%) and volumetric density (121kg/m )[1,2]. However, LiBH4 suffers from high thermodynamic stability, kinetics
barriers and the resultant poor irreversibility which hinder its practical utilization. In this work, hierarchic nanostructured
rod-like, flake-like, chain-like, waxberry-like and mulberry-like CoB catalyst was synthesised and doped into LiBH4 by ball
milling. It was revealed that CoB possessed extraordinary catalytic effect, dependent on its morphology, to improve thehydrogen storage properties of LiBH4. Its dehydrogenation was dramatically facilitated under lower temperature, and therehydrogenation was easily realized under mild conditions. Almost full reversibility was achieved with the assistance ofmulberry-like CoB.

Hydrogen storage properties of LiBH4-CoB
systemNanostructured CoB with different morphology of rodlike, flake-like, chain-like, waxberry-like and mulberry-like,
was synthesized by controlling chemical reduction
method[3], and then was mechanically milled with LiBH4
in a weight ratio of 1:1. Figure 1 shows thedehydrogenation kinetics of LiBH4-CoB system. It was
found that CoB played as a pure catalyst facilitating thedehydrogenation of LiBH4, and its morphology influenced
greatly catalytic activity. The catalytic effect of those CoB
is approximately in the order of mulberry-like > waxberrylike > chain-like > flake-like > rod-like, which is inaccordance with their specific surface area from high tolow. This led to the different dehydrogenation
performance of those CoB doped LiBH4 at 350°C. Among
those nanostructured CoB, mulberry-like CoB showed
the best catalytic effect. With its catalyzing, 10.4wt.%
hydrogen was liberated from LiBH4 with 1 h, which was
faster than that of pristine LiBH4 (Figure 1 left). By tuning
the rehydrogenation conditions of hydrogen pressure andtemperature, a almost full reversibility was achieved
under 400°C and 10MPa, remaining stable 9.6wt.%
hydrogen capacity at the fourth cycle (Figure 1 right).
Conclusively, almost fully reversible dehydrogenation of

LiBH4 has been realized under rather mild condition byusing nanostructured CoB catalyst.

Figure 1 Dehydrogenation kinetics of LiBH4-CoB systemwith different morphology (left), cyclic dehydrogenation ofmulberry-like CoB doped LiBH4 (right). Hydrogencapacity was calculated with respect to LiBH4.

References[1] L. Schlapbach, A. Züttel. Nature, 2001, 414, 353-358.
[2] P. Chen, M.Zhu. Materials today, 2008, 11, 36-43.
[3] Q. H. Wang, L. F. Jiao, H. M. Du, D. W. Song, W. X.
Peng, Y. C. Si, Y. J. Wang, H. T. Yuan.
Electrochimica Acta, 2010, 55, 7199-70203.

WeitongCai was born on 20 Nov. 1986 in Guangdong, P. R. China. 2005 Bachelor in School ofMaterials Science and Engineering, South China University of Technology, Guangzhou 510640,
P.R.China.
At present, he is a Ph.D. candidate at the Key Laboratory of Advanced Energy Storage Materials of
Guangdong Province, Guangzhou 510640, P. R. China.
His research field is complex hydrides (LiBH4).
WeitongCai
Corresponding authors: Min Zhu, memzhu@scut.edu.cn, +86-20-87113924; Yijing Wang, wangyj@scut.edu.cn, +86-2223503639.

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THE STUDY OF THE INTEGRATED HYDROGEN STORAGE SYSTEM OF METALHYDRIDE FOR THE APPLICATION OF FUEL CELL
Fangming Xiao , Renheng Tang, Tai Sun, Ying Wang
Division of Rare Metal, Guangzhou Research Institute of Non-ferrous Metals, 510650

Abstract:
Fuel Cell system is a truly zero-emission source of electricity. The Energy conversion process is quiet,
pollution-free and two to three times more efficient than combustion. As long as the fuel, the ideal
choice of which is hydrogen, is supplied, fuel cells can continuously generate electricity. According to
the “2012 Fuel Cell Technologies Market Report” published by U.S. Department of Energy (DOE), thecost of per kilowatt (kW) for high volume production of transportation fuel cells moved closer to DOE’s
target of $30 per kW. As a result, the development of fuel cells calls for suitable hydrogen storage
system for commercialize application.
Our study focus on the research of rare-earth based metal hydrides, which has both high capacity andlow production cost, prepared by rapid quenching method in medium frequency induction furnace. The
hydrogen storage capacity of the alloy reach 1.6wt% with flat and broad plateau pressure after heattreatment as show in figure 1. The discharge capacity of the hydrogen storage canister ST2800L filledwith the alloy is 2578.04NL with an efficiency of c.a. 92.07% at 30 ℃. As shown in figure 2, thedischarge properties of 14Nm3 integrated hydrogen storage system composed by 5 ST2800L canisters
is tested at 20 ℃ in water bath. The whole system discharges 12196.42NL of hydrogen with anefficiency of 87.12%..
10

1

0.1

After Heat-treatment
Before Heat-treatment

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Capacity (wt.%)
Figure 1. The PCT curves of the hydrogen storage
alloy.

Pressure (H2, atm)

Pressure (H2, atm)

10

1

0.1
0

3000

6000

9000

12000

Hydrogen Discharge (NL)
Figure 2. The discharge properties of the 14Nm
integrated hydrogen storage system at 20℃ in water bath3

Short CV: Prof. Xiao’s Research Expertise is mainly focus on developing Energy storage
materials and nanotechnology, including metal hydrides, Ni-MH batteries, Li-ions batteries andmagnetic materials. In the past five years, his research team was granted by several key
projects funded by the China National Natural Science foundation and Guangdong governmenton the research of areas mentioned above, and published over 40 academic articles in
professional journals.

Corresponding author: Fangming Xiao, email: xfmworld@163.com, Tel: +86-20-37238536

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COMPUTATIONAL DESIGN OF NANOPARTICLE CATALYSTS FORSUSTAINABLE PRODUCTION OF SYNTHETIC FUELS
Tejs Vegge, Jakob G. Howalt, Jón Steinar G. Mýrdal, Steen Lysgaard
Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej 399, DK-4000
Roskilde, Denmark
Emerging technologies for conversion and storage of energy from renewable and intermittent sources like wind and solar
energy remain non-competitive on commercial terms, due to poor activity, selectivity, efficiency, stability or cost. The
ability to improve and ultimately design superior materials is therefore paramount in the development of more efficientsustainable energy technologies. Computational methods like density functional theory (DFT) have reached a level,
where predictive accuracy can be reached by linking complex morphologies and structures to the functionality.

Materials Predictors for Catalyst Design
We present results using model structures and materials
predictors that link the complex functionality of thematerials to simple atomic parameters such as thebinding energy of critical reaction intermediates, e.g. thenitrogen binding energy on nanoparticle catalysts forelectrochemical fixation of N2 into NH3 (Figure 1) [1].

Figure 1 Genetic algorithm based prediction of the coreshell configuration of 309 atoms Cu-Ni nanoparticle [2].
The authors acknowledge support from the Catalysis
Sustainable Energy (CASE) initiative funded by theDanish Ministry of Science, Technology and Innovationand the European Commission under the FP7 FCH JTI
project SMARTCat (FP7-2012-JTI-FCH-325327).
Figure 2 The onset potential for electrochemicalammonia production on transition metal nano-clusters,plotted as a function of the nitrogen binding energy [1].	
  Genetic Algorithms for Stability Design
We combine the approaches with database methods andevolutionary algorithms to predict and design superiorand stable catalysts, e.g., for the Oxygen Reduction
Reaction (ORR) or nanoparticle electrocatalysts for
fixation of CO2 into methane or methanol with improved
stability under operational conditions (Figure 2) [2].

Tejs Vegge

References[1] Jakob G. Howalt, Thomas Bligaard, Jan Rossmeisl
and Tejs Vegge, DFT based study of transition metal
nano-clusters for electrochemical NH3 production,
Phys. Chem. Chem. Phys. 15, 7785 (2013).
[2] S. Lysgaard, D.D. Landis, T. Bligaard and T. Vegge,
Genetic algorithm procreation operators for alloy
nanoparticle catalysts, Topics in Catalysis, DOI:
10.1007/s11244-013-0160-9 (2013).

Tejs Vegge is a Professor at Department of Energy Conversion and Storage at the Technical
University of Denmark, where he is also Head of Section for Atomic Scale Modeling and Materials.
His research activities are centered round integrated computational and experimental design and insitu characterization of novel materials for energy conversion and storage, e.g. DFT-based materials
design from model structures, predictors and genetic algorithms, nanoparticle (electro)catalysts forsustainable production of synthetic fuels and ammonia, batteries and materials for hydrogenstorage. Among other things, Prof. Vegge is project manager for “Electrochemical fixation of N2 andCO2 into fuels”, under the UNIK project Catalysis for Sustainable Energy (CASE).

Corresponding author: Prof. Tejs Vegge, teve@dtu.dk, Tel. +45 4677 5818

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AMIDOBORANES – FORMATION AND APPLICATIONS
Yongshen CHUA, Weiliang XU, Lin LIU, Guotao WU, Zhitao XIONG, Ping CHEN
Dalian Institute of Chemical Physics, Dalian, CHINA, 116023
Abstract: Alkali or alkaline earth amidoboranes can be prepared via the reactions between ammonia borane and metal
hydrides or amides. A variety of mono- and bi-metallic amidoboranes have been synthesized and exhibit interesting
dehydrogenation properties and tuneable thermodynamics. On top of that, those high hydrogen content chemicals also
have unique applications in selective hydrogenation and exfoliation of layered materials.

Amidobranes for H2 storage
The interaction between ammonia borane (AB) and metal
hydride or amides has been widely explored in thesynthesis of amidoboranes. LiH or NaH reacts with ABgiving rise to LiNH2BH3 or NaNH2BH3, which releases
large amount of hydrogen exothermically. By forming bimetallic amidoboranes, such as Na2Mg(NH2BH3)4 andK2Mg(NH2BH3)4,
thedehydrogenation
becomes
endothermic. The reason for that is due to the formationof more stable reactant (see Fig. 1).

alcohols. Mechanistic study indicates that the reduction isthrough double hydrogen transfer process. Theoreticalinvestigations show that the first and rate-determining
step of reduction is the elimination of LiH from LiAB
followed by the transfer of H(Li) to C site of unsaturated
bond.

Ammonia Borane as efficient exfoliation
agent
Nearly quantitative yield in which ca. 25% is single-layer
graphene can be obtained by ball milling of graphite withAB (see Fig. 2). Due to the interaction between NH3BH3
2
and the sp carbon lattice network of graphite, NH3BH3
molecules can be readily adsorbed/spread on the surfaceof graphite under ball milling condition resulting in theweakened interlayer van der Waals interactions andallowing graphene sheets easily to be exfoliated.

Fig. 1 Energy changes in the formation of bimetallic
amidoboranes and their dehydrogenation.

Selective hydrogenation
O
R1

OH

LiAB
R2

THF

R1

R2

Lithium amidoborane (LiAB) shows superior reduction
capability in reducing ketones or imines directly tocorresponding secondary alcohols or amines at room
temperature. More importantly, it can chemoselectively
reduce -unsaturated carbonyl compounds to allylic

Fig. 2 SEM images of pristine graphite particles (a) andgraphene sheets (b); TEM image (c) and HRTEM image(d) of graphene sheets.

References[1] YS Chua, W Li et al Chem. Mater., 24 (2012) 3574.
[2] WL XU, GT Wu et al. Chem. Eur. J. 18 (2012) 13885.
[3] L Liu, ZT Xiong, DQ Hu et al Chem. Comm 49 (2013)
7890.

Ping Chen，is a professor at the Dalian Institute of Chemical Physics (DICP), CAS. Chen received a
PhD degree in Chemistry 1997 from Xiamen University, China. Before joining DICP she was the
Associate Professor at Department of Chemistry and Department of Physics, National University ofSingapore. Her primary research interests include the development of chemical and complex
hydrides for hydrogen storage, catalysis, and materials chemistry. She and her team pioneered theresearch in hydrogen storage over amide-hydride composite and amidoborane system.
Corresponding author: Ping CHEN, pchen@dicp.ac.cn, 0411-84379905

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BOROHYDRIDES: NEW INSIGHTS FROM NMR
Arndt Remhof1, Yigang Yan1, Daniel Rentsch2, Andreas Züttel1, Zbigniew Łodziana3
1

Empa, Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, 8600 DÜbendorf,
2
Switzerland; Empa, Swiss Federal Laboratories for Materials Science and Technology, Functional Polymers, 8600
3
Dübendorf, Switzerland, INP, Polish Academy of Sciences, ul. Radzikowskiego 152, PL-31-342 Kraków, Poland.
Nuclear Magnetic Resonance (NMR) has been intensively used to unveil sorption pathways of borohydrides and otherhydrogen storage materials. Based on solid state and solution state NMR, we identified the [B3H8] species as majorintermediate in the hydrogen release reaction of Y(BH4)3. In a broader context, we show that NMR data, combined withelectronic and structural data provide deeper understanding to the properties of bulk and to nano-sized structures.

-

Reaction Pathways
Understanding and controlling the sorption pathways is
crucial for the applicability of a hydrogen storage
material. In the hydrogen uptake and release reactions ofborohydrides
stableintermediatessuchasdodecaborates or volatile boranes such as B2H6 act asboron sinks and reduce reversibility.

cation and [BH4] , indicative of a more covalent nature of
the bond.

We investigated intermediate products and the solid
residue of the hydrogen release reaction of Y(BH4)3 bysolid state and solution state NMR, Raman spectroscopy
and by X-ray diffraction [1]. Y(BH4)3 decomposed via the22[B3H8] species, while the [B12H12] and [B10H10] species
were not detected. We therefore conclude the followinghydrogen release pathway for Y(BH4)3:Y(BH4)3 → 1/3Y(B3H8)3 + 2/3YH3 + H2 (1)-Hydrogen release pathways via [B3H8] are favourable forreversible hydrogen storage [2], making Y(BH4)3 an
attractive hydrogen storage material.

Chemical shifts
NMR is more than a powerful fingerprint technique for thephase identification and quantification in chemical
analysis. The key parameter in NMR spectroscopy, thechemical shift, is related to the shielding of the coreelectrons. In Figure 1 we present the relation between
11
the B chemical shift and the total charge of an individual[BH4] ion based on the Bader method [3]. The larger
11
charge on [BH4] , the larger B chemical shift can beobserved for most compounds. Compounds that show
deviation from the linear correlation between Bader11
charge and B chemical shift, such as Al(BH4)3 andZr(BH4)4, possess more directional bonds between metal

Figure 1. The B chemical shift δ with respect to theBader charge of the (BH4) unit for selected metalborohydrides.
11

References[1] Yigang Yan et al, Chem. Commun., 2013, 49, 5234.
[2] M. Chong et al., Chem. Commun., 2011, 47, 1330.
[3] Z. Lodziana et al., submitted.

1994
University Diploma with distinction of the University of Kent at Canterbury, UK.
1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France.
1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany.
1999
Guest scientist at the Universidade São Francisco in Itatiba, São Paulo, Brazil.
2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands.
2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum.
From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.”
2010
Guest scientist at the Tohoku University in Sendai, Japan
Arndt Remhof
Corresponding author: Arndt Remhof, arndt.remhof@empa.ch +41587654369

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TRANSITION METAL CATALYZED DEHYDROGENATION OF B-N-H
BASED MATERIALS IN SOLID STATE
Teng He, Junhu Wang, Guotao Wu, Zhitao Xiong, Tao Zhang, Ping Chen*
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457#, Zhongshan Road, Dalian, China (116023)
Abstract: Nano-sized transition metal (Fe, Co or Ni) catalyst was successfully synthesized by introducing precursors into
B-N-H based hydrogen storage materials (ammonia borane, borohydride ammoniates and borohydride hydrazinates etal.). The experiment results show that the dehydrogenation temperatures of B-N-H based materials decreased
dramatically compared with the pristine materials. Characteristic results, i.e. Mössbauer and PDF techniques, reveal thatmetal-boron amorphous alloy is the activity species during the dehydrogenation of B-N-H based materials.

Introduction
Compounds or complexes with high hydrogen content
are viewed as potential hydrogen storage materials.
Among them, the B-N-H based materials are promising
candidates, for example, Ammonia borane (NH3BH3, AB
in short), borohydride ammoniate (MBH4·NH3) andborohydride hydrazinate (MBH4·nN2H4) et al. However
the dehydrogenation of these compounds occurs at
relatively high temperature with releasing volatile
byproducts (NH3, N2, N2H4 and borazine et al.). Thus, inthis paper, in situ synthesized metal-boron alloy catalyst
was introduced into these B-N-H based materials todecrease the dehydrogenation temperature.

Results
We developed a “co-precipitation” method to introduce
nanosized transition metal (Fe, Co and Ni) catalysts into
AB in solid state without scarifying hydrogen content. The
experimental results show that about one equivalenthydrogen can be released from doped-AB at atemperature as low as 60 °C with the depression of
byproducts (NH3 and borazine) and sample foaming. In
contrast to dehydrogenation of neat AB that yields noncrystalline
products,
thesolid-statecatalyzed
dehydrogenation of AB yields
the crystalline
polyaminoborane (PAB) as a major product. Mössbauer
spectroscopy and X-ray atomic Pair Distribution
Functions (PDFs) characterizations show that the metalboron (M-B) alloy is the active center to the catalytic
dehydrogenation.
A new class of hydrogen storage materials, borohydride
hydrazinates(forexample,LiBH4·nN2H4),
wassuccessfully synthesized. In particular, the bidentate
NH2NH2 coordinates with LiBH4 in molar ratios of 1:1 and
1:2 giving rise to a monoclinic LiBH4•NH2NH2 andorthorhombic LiBH4•2NH2NH2, respectively. Around 13.0
wt % H2 can be released from LiBH4•NH2NH2 at 140 ºC in
the presence of Fe-based catalysts. From XRD, FTIR,GC and Raman analysis, we can conclude that theoverall decomposition of LiBH4•NH2NH2 in the presenceof Fe-based catalyst may follow the reaction R1:
3(LiBH4·N2H4)→Li3BN2+2BN+N2+12H2

R1

XAFS and Mössbauer results show that Fe-B alloy is thefunctional species catalyzing the dehydrogenation of
LiBH4•N2H4.

Conclusions
In situ synthesized transition metal (Fe, Co and Ni)-boron
alloy was successfully introduced into B-N-H basedmaterials. The as-prepared metal-boron alloy is anefficient catalyst for the dehydrogenation of B-N-H basedhydrogen storage materials.

References[1] T. He, H. Wu, G. Wu, J. Wang, W. Zhou, Z. Xiong, J.
Chen, T. Zhang, P. Chen, Energy Environ. Sci., 5(2012) 5686.
[2] T. He, Z. Xiong, G. Wu, H. Chu, C. Wu, T. Zhang, P.
Chen, Chem. Mater., 21 (2009) 2315.
[3] T. He, J. Wang, G. Wu, H. Kim, Th. Proffen, A. Wu, W.
Li, T. Liu, Z. Xiong, C. Wu, H. Chu, J. Guo, T. Autrey,
T. Zhang, P. Chen, Chem. Euro. J., 16 (2010) 12814.

Dr. Teng HE received his PhD degree from Dalian Institute of Chemical Physics, Chinese Academyof Sciences (DICP, CAS) under the supervision of Prof. Ping CHEN and Prof. Tao Zhang in 2012
and then was exceptionally promoted to be an associate professor in DICP. His research interests
include: 1) synthesis and characterization of B, N based materials for hydrogen storage; 2) catalytic
dehydrogenation of B-N-H based hydrogen storage materials; 3) catalytic de/hydrogenation oforganic compounds.

Teng HE
Corresponding author: Prof. Ping Chen, pchen@dicp.ac.cn, Tel.: 0411-84379905

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CETI2AL20: A CATALYST-REACTANT INTEGRAL AGENT TO NAALH4SYNTHESIS
Cun-Ke Huang, Feng-chui Zhao, Hao Dai, Jin Guo
College of Physics Science and Technology, Guangxi University, Nanning 530004, China
The cooperative catalytic effect of Ti(3d)–Ce(4f) on the hydrogen storage properties of NaAlH4 was studied. Target
and reference samples were prepared by in situ high-energy-vibration ball-milling. In the preparation stage, the degree ofreaction and reaction rate with the target system (CeTi2Al20-Al-NaH) were much higher than those observed with theother reference samples. The target sample is also the best in the dehydriding/rehydriding performances. In particular,
use of this sample 1) markedly decreased the onset temperature of the reaction, and 2) markedly increased the reaction
rate and hydrogen storage capacity. Loose Ti–Ce coupling resulted in a cooperative catalytic effect on
dehydriding/rehydriding of NaAlH4 that was weaker than that due to strong Ti–Ce coupling. CeTi2Al20 is a catalystreactant integral agent to NaAlH4 synthesis; related highly cooperative catalytic effects are closely associated with strong
Ce–Ti–Al coupling.

Fig. 1 XRD profiles of as-BM samples with highenergy-vibration ball-milling under 8MPa hydrogenpressure. No.1: NaH+Al, BM 48h; No.2: Ti+Al+NaH, BM
12h; No.3: Ce+Al+NaH, BM 12h; No.4: Ce+Ti+Al+NaH,
BM 12h; No.5: CeTi2Al20+Al+NaH, BM 12h. All the moleratio of catalytic element to Al was 1:20 and Al to Na was
1:1. For samples No. 4 and No. 5, the mole ratio of Ce to
Ti was 1:2. Only NaAlH4 can be distinguished in No.5
situation.

Fig. 2 Dehydriding/rehydriding kinetic profiles ofsamples. (a) non-isothermal (heating-up speed 1K/min)dehydriding kinetic profiles of samples; (b) isothermal
rehydriding kinetic profiles of samples in 383K under
8MPa initial hydrogen pressure. No.1: NaH+Al, BM 48h;
No.2: Ti+Al+NaH, BM 12h; No.3: Ce+Al+NaH, BM 12h;
No.4: Ce+Ti+Al+NaH, BM 12h; No.5: CeTi2Al20+Al+NaH,
BM 12h. Hydriding/dehydriding kinetics properties of
No.5 is remarkable better than that of other four samples.

References[1] Xiao X, Chen L, Wang X, etal. Int J Hydrogen Energy
2008; 33:64-73;[2] Schmidt T, Röntzsch L, J Alloys Compds 2010; 496:
L38-L40.

Cun-Ke Huang was born in Nanning, China, in 1975. He made his Ph.D degree in the South China
University of Technology, major in Material processing engineer with Prof. Min Zhu. He received his
Ph.D. degree in 2009, for his study on equilibrium phase relation and defect thermodynamics of Ti
doped NaAlH4 with first-principles method. He Now he works in College of Physics Science andTechnology, Guangxi University, and he make researcher focus on some new energy functional
materials by theoretical and experimental methods.
Cun-Ke Huang
Corresponding author: Prof. Jin Guo; email: guojin@gxu.edu.cn; Tel: (+86)0771-3237386.

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EFFECT OF MICROWAVE IRRADIATION ON THE
DESORPTION PROPERTIES OF MGH2/LIBH4 COMPOSITEHYDROGEN

Haiyan Leng, Jia Wei, Qian Li, Kuo-Chih Chou
Shanghai Key Laboratory of Modern Metallurgy & Materials Processing, Shanghai University, Shanghai 200072, China
Abstract: The effect of microwave irradiation on the hydrogen desorption properties of MgH 2/LiBH4 composite wasinvestigated. It is shown that the composite can be heated rapidly with the addition of LiBH 4 by microwave heating whichbrings about a fast dehydrogenation of MgH2. The hydrogen released from MgH2+10 wt% LiBH4 under microwave is 5otimes more than that under conventional heating at 300 C in 30 min. The sample can be heated even more rapidly by
microwave heating after cycling. These results demonstrate that the microwave heating is an effective technology for
improving the hydrogen desorption kinetics of MgH 2/LiBH4 composite with high energy efficiency.

Introduction

Results

Mg and Mg-based solid hydrogen storage materials are
considered to be the most promising solid hydrogenstorage media, contributed to their light weight, low cost,and large hydrogen storage capacity [1]. However, highdehydrogenation temperature and relatively slow
absorption and desorption dynamics make it unsuitablefor practical application. Considering the rapid heating
property of LiBH4 under microwave [2], we added LiBH4
into MgH2 and studed the effect of microwave radiationon MgH2/LiBH4 composite system, in order to improve
the hydrogen storage performance of the composite.

The temperature curves of the samples under microwave
against heating time were measured. For the samples
with LiBH4 addition, the heating rates at initial stage areslow, but when the temperature is higher than the latticeotransformation temperature (around 107 C) of LiBH4, thecomposites are rapidly heated since LiBH4 acts as astrong microwave absorbent. The isothermal desorptionokinetics of MgH2-10wt% LiBH4 sample at 300 C heatedby microwave irradiation and conventional heating were
measured. The results showed that the sample desorbed
only 0.5 wt% H2 under conventional heating within 30 min,while desorbed 3 wt% H2 under microwave heating,which is about 5 times more than that under theconventional heating. Furthermore, the samples after
cycling were heated by microwave heating. The results
showed that after 2 and 5 cycles, the rehydrogenatedosamples can be heated even more rapidly up to 500 C
under microwave irradiation, and the slow heating rateostage below 107 C disappeared. The improved
microwave heating performance of the samples after
cycling was proposed to be contributed to Li2B12H12,
which was formed by LiBH4 during the cycling.

Experimental
The composites of MgH2-xLiBH4 (x=5-30wt%) wereprepared by ball milling method. The dehydrogenation of
the samples under microwave irradiation was carried out
as follows: about 0.5 g of sample was placed in a crucibleof BN which was placed in a hermetic Teflon container.
The container equipped with a K-type thermocouple, airinlet and outlet, was inserted into the cavity of multi-mode
microwave instrument (SYNO-THERM WG3/2.45). In
order to investigate the effect of microwave irradiation on
the hydrogen desorption properties of MgH2/LiBH4
composites, the isothermal desorption kinetics of thesamples both under microwave heating and conventional
electrical resistant heating were measured by volumetricmethod. The samples before and after microwave
irradiation were examined by XRD, FTIR measurements.
To prevent sample oxidation, all handlings were
performed in a glove box (MBraun Labstar) under highpurity Ar.

References[1] M. Dornheim, S. Doppiu, G. Barkhordarian, U.
Boesenberg, T. Klassen, O. Gutfleisch, R. Bormann,
Scripta Materialia, 56 (2007) 841-846.
[2] Y. Nakamori, M. Matsuo, K. Yamada, T. Tsutaoka, S.
Orimo, J. Alloys and Comp., 446 (2007) 698-702.

Haiyan Leng obtained her PhD from Institute of Metal Research in 2003, and worked in Hiroshima
University (Japan) as a JSPS postdoctoral fellow from 2004 to 2006, in AIST (Japan) as a research
fellow in 2007, in Institute of Nanotechnology (Germany) as a guest scientist in 2008, and in
Shanghai Institute of Microsystem and Information Technology from 2009 to 2011. Now she is anassociate professor in Shanghai University. She has published more than 20 SCI cited papers injournals like J. Power Sources, J. Phys. Chem. B, and Int. J. Hydrogen Energy, and several Chinese
and international patents. Her interesting research focuses on hydrogen storage materials of lightelements, such as Mg-based materials, Amide and Borohydride.
Haiyan Leng
Haiyan Leng, lenghaiyan@shu.edu.cn , 021-56334045

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Calcium Borohydride Modified by N-H Group for Hydrogen Storage
Hailiang Chu,a* Shujun Qiu,a Yongjin Zou,a Cuili Xiang,a Fen Xu,a Lixian Sun,a* Ping ChenbaSchool of Materials Science and Engineering, Guilin University of Electronic Technology, 1 Jinji Road, Guilin 541004,
Chinab

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China

Abstract: In order to decrease the dehydrogenation temperature, the interaction between calcium borohydride and metalamides (LiNH2, Mg(NH2)2 and Ca(NH2)2, etc.) and ammonia was systematically investigated and some addictives were
doped to further decrease dehydrogenation temperature. More than 4.5 and 7 wt% of hydrogen can be released attemperatures as low as ca. 165 and 178 °C from the cobalt-catalyzed Ca(BH4)2-4LiNH2 system, respectively. In addition,
isothermal volumetric release measurement at 250 °C of Ca(BH 4)2•2NH3 shows that it can also desorb 6 equiv. H2 (11.5wt%). The presence of adductive NH3 in Ca(BH4)2•2NH3 leads to a shortened N-H•••H-B dihydrogen bond in the
structure and may facilitate low-temperature dehydrogenation.

More recently, Ca(BH4)2, which has more favorable
1
thermodynamics (32 kJ/mol H2, estimated by density
functional theory) than LiBH4, while maintaining attractivehydrogen capacity (11.4 wt %), has been acknowledged
2as one of the potential candidates for hydrogen storage
3
However, the decomposition for hydrogen release ofCa(BH4)2 is at a temperature as high as 350 °C.
In order to decrease the dehydrogenation
temperature,theinteraction
betweencalciumborohydride and metal amides (LiNH2, Mg(NH2)2 andCa(NH2)2, etc.) was systematically investigated and someaddictives
were
doped
to
furtherdecreasedehydrogenation temperature. More than 4.5 and 7 wt%
of hydrogen can be released at temperatures as low as
ca. 165 and 178 °C from the cobalt-catalyzed Ca(BH4)24
4LiNH2 system, respectively.
The Ca(BH4)2–2Mg(NH2)2 and Ca(BH4)2–2Ca(NH2)2
composites are thereby synthesized. It is found that thebinarycombined
systems
exhibitanonsetdehydrogenation temperature of about 220 °C, which isabout 100 °C lower than that of pristine Ca(BH 4)2. The
hydrogen release measurements for Ca(BH4)2–
2Mg(NH2)2 and Ca(BH4)2–2Ca(NH2)2 samples below
480 °C show desorption amounts of 8.3 and 6.8 wt %hydrogen, respectively, in the pathways of Ca(BH4)2 + 2
Mg(NH2)2 → 1/3 [Ca3Mg6(BN2)6] + 8 H2 and Ca(BH4)2 + 2
5Ca(NH2)2 → 1/3 Ca9(BN2)6 + 8 H2, respectively.

mode where gaseous product(s) can be removed
immediately from the solid reactant, Ca(BH4)2•2NH3
undergoes deammoniation though two steps and forms
Ca(BH4)2•NH3 and Ca(BH4)2, respectively. However, thethermal decomposition is conducted in a close system
where the gaseous product is kept in the vicinity of thesolid reactant, Ca(BH4)2•2NH3 can release 6 equiv. H2(11.5 wt %) in the temperature range of 100-500 °C
according to reaction: Ca(BH4)2•2NH3 → 1/4 Ca(BH4)2 +1/4 Ca3(BN2)2 + BN + 6 H2, showing the participation of
NH3 in the H2 production. Isothermal volumetric releasemeasurement at 250 °C of Ca(BH4)2•2NH3 shows that it
can also desorb 6 equiv. H2 for 100 h. The presence ofadductive NH3 in Ca(BH4)2•2NH3 leads to a shortened NH•••H-B dihydrogen bond in the structure and may
6
facilitate low-temperature dehydrogenation.

References[1] K. Miwa, et al, Phys. Rev. B, 2006, 74, 155122.
[2] J. H. Kim, et al, Scripta Mater., 2008, 58, 481.
[3] E. Ronnebro, J. Phys. Chem. B, 2007, 111, 12045.
[4] H. L. Chu, et al, Chem. Asian J., 2010, 5, 1594.
[5] H. L. Chu, et al, J. Phys. Chem. C, 2011, 115, 18035.
[6] H. L. Chu, et al, Chem. Mater, 2010, 22, 6021.

In addition, a new compound Ca(BH4)2•2NH3 wassynthesized through gas-solid reaction. Thermal
decomposition analyses show that, under a dynamic flow

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Dr. Hailiang Chu

Zhaoqing, P.R. China 2014

Hailiang Chu was born in Shandong province, China in 1980. He received his B.S. in chemistry from
Qufu Normal University in 2002 and Ph.D. in physical chemistry under supervision of Professor
Lixian Sun in 2008 from Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP,
CAS). After graduation, he joined DICP as an Assistant Researcher in Professor Ping Chen’s group.
In 2012, He joined Guilin University of Electronic Technology and was awarded associate
professorship. His research interest focuses on the synthesis and application of high capacityhydrogen storage materials, including alloys, metal borohydrides, metal-N-H materials, ammonia
boranes and their derivatives.
2 /1995, Guest researcher (STA fellowship), National Institute of Advanced Industrial Science andTechnology (AIST), Japan; 5/1995, Postdoc. (AvH fellowship), Jena University, Germany;19962002, Guest Professor (AIST/ITIT, NEDO, fellowship) at AIST; 9/2001-2012, Professor and Group
Leader of Material Thermochemistry, Dalian National Laboratory of Clean Energy (DNL), DICP,
CAS; 2009--2012, Director of Key Laboratory of Energy Materials & Thermochemistry, Liaoning
Province; 2012-present, Dean of School of Material Science and Engineering; Director of Key Lab.
of Guangxi Information, Guilin University of Electronic Technology

Corresponding author: Hailiang Chu, chuhailiang@guet.edu.cn, +86 773-2216607.
Li-Xian SUN, lxsun@dicp.ac.cn

Acknowledgement: The authors thank the financial supports from “ 973 Project ” (2010CB631303), NSFC
(51361005, 51371060, 51071146, 21173111, 51102230, 51101144, 51201042 and 51201041), the State Key Laboratoryof Explosion Science and Technology, Beijing Institute of Technology (KFJJ13-12M).
The authors thank the financial supports from “973 Project” (2010CB631303), NSFC (51101144 and 51361006).

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NANOPARTICLE CATALYSIS OF HYDROGEN EVOLUTION
Hannes Jónsson
University of Iceland and Aalto University
Abstract: DFT calculations have been carried out for hydrogen evolution reaction and hydrogen oxidation reaction atedges on Pt nano-particles and the results compared with the Pt(110)-2x1 surfaces and stepped surfaces.

Introduction
The interaction of hydrogen with the surface of platinum
metal is of fundamental importance to a wide range ofenergy technologies including electrolysis of water andhydrogen fuel cells. The metal is typically dispersed as
small particles embedded in a matrix. The active sites ofsuch particles can be under-coordinated atoms at edges
where crystal facets meet, or at corners where edges
meet. A 2 nm particle, which is at the lower end of thesize range used in fuel cells today, contains on the orderof 1000 atoms. Density functional theory (DFT)
calculations of the catalytic activity of a whole
nanoparticle of this size generally require a prohibitively
large computational effort. An alternative approach is toconstruct a periodic array of the sites of interest, such asedges between micro-facets.

of edges between two (111) micro-facets or edges
between (111) and (100) micro-facets. The width of the
facets in the periodic representations was systematicallyincreased to reach converged results for binding andactivation energy. Under typical electrochemical
conditions (for small applied voltage vs. SHE), edges
between (111) micro-facets were found to be several
orders of magnitude more active than edges between(100) and (111) micro-facets or at terraces.
The
desorption mechanism on the former edge involves theformation of a Kubas complex which apparently lowers
the desorption barrier. Unlike the missing row Pt(110)-(2x 1) surface, which has sometimes been used as asimple model for edges between (111) micro-facets, theconverged edge model does not show the recently
reported reentrant behavior in desorption mechanism [1].

References
HER/HOR at Pt nanoparticle edges
The missing-row reconstructed Pt(110)-(1x2) surface canbe considered a very small model of edges between (111)facets and has been studied both experimentally andtheoretically [1,2]. In the current work [3], the associativedesorption of hydrogen at edges and facets on Pt
nanoparticles was studied using DFT. The goal was to
identify catalytically active sites on Pt nanoparticles forthe hydrogen evolution reaction as well as the hydrogenoxidation reaction. The adsorption sites were modeled byperiodic, face centered cubic slabs representing an array

Education:[1],
Phys. Rev. Lett, 108, 156101 (2012).

[2], Phys. Chem. Chem. Phys.
15, 6323 (2013).

[3]

, J.
Hussain, A. L. Garden and H.
, Topics inCatalysis, DOI: 10.1007/s11244-013-0182-3 (2013).

B.S. 1980 University of Iceland
Ph.D. 1985 University of California San Diego
Post-doc 1986-1988 Stanford University

Employment:

1988 Assistant, associate, full professor, University of Washington, Seattle, USA
2000 Professor, University of Iceland2013 FiDi Professor, Aalto University, Finland

HannesJónssonhj@hi.isphone: +354 8923560

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TITLE SYNTHESIS AND PROPERTIES OF NANOSTRUCTUREDHYDROGEN STORAGE MATERIALS
L. Xie, X.Z. Zhang, Y.Q. Li, J. Zheng and Xingguo Li*
The College of Chemistry and Molecular Engineering, Peking University, 100871, Beijing, China
Abstract:
We developed a method to prepare ultrafine Mg
nanoparticles around 40 nm by acetylene plasma,
which is a revised approach for the traditional hydrogen
metal plasma reaction. Due to the short diffusion
distance and large specific surface area, the kinetics ofhydrogenation and dehydrogenation of the small Mg
nanoparticles were improved.
Li2NH and Mg(NH2)2 hollow nanospheres with diameterof 100 nm and thickness of 10 nm were prepared byplasma metal reaction based on the Kirkendall effect inorder to improve their hydrogen storage properties. In
the synthesis, the bulk lithium and magnesium werevaporized and reacted with ammonia to obtain thehollow nanostructure directly. The results show that thestructure dramatically enhanced the hydrogen
desorption kinetics because of their short diffusion
distance and large specific surface area.
The combination of the use of MOFs as the catalyst
precursors and the in situ generation of catalytically
active sites leads to dramatically improved H2 releasing
rates from AB systems at the operation temperature of
proton exchange membrane fuel cells. In the hydrolysis
of AB, the MOF based catalyst (MOF1cat) exhibits highcatalytic activity and good recycling properties at room
temperature in the air.

Name

Figure 1. TEM images of Mg nanoparticles preparedwith acetylene fraction of (a) 28 %, (b) 21.7 %, (c)14.3 %, (d) 5.3 %, (e) 0 %, and the particle size
distribution of Mg nanoparticles prepared with 21.7 %acetylene (f).

Short CV: Xingguo Li is Professor and Director of New Energy and Nano materials Laboratory,
deputy chair of the Inorganic Chemistry Institute at Peking University. His research interests
focus on hydrogen storage materials, hydrogen generation and purification, battery electrodematerials and nano materials. He has carried out more than 30 projects supported by NSFC,
MOE, MOST and other organizations and companies as well as Japanese NEDO. Prof. Li has
already published more than 200 papers in important journals such as Adv. Mater., Nano
Letter, Nano Energy, ACS Nano, Small, Biomaterials, Chem. Mater., Chem. Eur. J., Chem
Commun., Applied Catalysis B,APL, JPCB, JPCC, Crystal Growth & Design, Inter. J. Hydrogen
Energy, Acta Materialia, Langmuir, Nanotechnology, contributed chapters to two books
published by Nova Science Publishers, Inc. and American Scientific Publishers, and applied 18
patents. He has presented over 140 talks around the world with over twenty plenary andkeynote lectures. He has received the National Distinguished Young Investigator Fund (2000),
Lectureship Award of Japan Research Institute of Material Technology (2002) and GM
foundation Science & Technology Achievement Award (2005).

Corresponding author: Xingguo Li, email:xgli@pku.edu.cn, Tel: 86-10-6276 5930

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SPONTANEOUS DEHYDROGENATION REACTIONS INVESTIGATED BY
IN-SITU SPECTROSCOPY
E. Callini1*, Nicholas Stadie1, Renaud Delmelle1, Fadime Hosoglu1, A. Borgschulte1 and A.
Züttel1
1

Empa, Materials Sciences and Technology, CH-8600 Dübendorf, Switzerland

Abstract
Several new transition metal borohydrides e.g. Ti(BH4)3 have been synthesized and the dehydrogenation reaction wasinvestigated in view of the thermodynamics and intermediate products formed by means of thermo gravimetry, mass
spectroscopy and IR-spectroscopy. The hydrogen desorption kinetics was analyzed and the intermediate products wereidentified.

Synthesis of Ti(BH4)3The new compound Ti(BH4)3 was synthesized by themetathesis reaction and reactive milling. Theintermediates and/or products formed during thehydrogen desorption reactions are thermodynamicallyunstable. Their characterization and measurement as afunction of time and temperature is a key challenge tounderstand the reaction mechanisms and the upscaling.
[1].
We analysed the formation of intermediate species,
studying LiBH4, one of the materials with the highest
gravimetric hydrogen density considered for hydrogenstorage. The following reaction was investigated:
TiCl3 + 3 LiBH4  Ti(BH4)3 + 3 LiCl  3/2 B2H6 + 1/2
H2 + TiH2 + 3 LiCl
The identification and characterization of Ti(BH4)3 is atechnical issue because it is extremely reactive in air,spontaneously decomposes within few hours at room
temperature and it is volatile. Therefore, different in situ
techniques i.e. thermogravimetric balance, mass and IRspectroscopy were combined in order to determine thethermodynamics of the reaction, the emitted and theintermediate products. [2]Stability and the Intermediate Species

it is an intermediate phase in the dehydrogenation
reaction of TiCl3 added LiBH4. Ti(BH4)3 is stable at room
temperature for few hours and therefore its detection ispossible. This species, under these experimental
conditions, does not catalyze the decomposition reactionof LiBH4. These findings open a new perspective in the
research of additives to destabilize complex hydrides.

Related compounds
Several intermediate species have been theoretically
predicted but never experimentally shown: V(BH4)3 orZn(BH4)2. The spontaneous release of gas species fromthe products of the reaction of LiBH4 with AlCl3 [3], ZnCl2,
and VCl3, will be analyzed. A comprehensive bulk,
surface and gas phase analysis of the reactions products
and eventually formed intermediate species will bepresented, pointing out the route towards the control of
spontaneous dehydrogenation reactions and thestabilization of the intermediate species.

References[1] E. Callini, et al., Dalton Transactions 42, 719 (2013).
[2] A. Borgschulte, et al., J. Phys. Chem. C 115 (34),17220 (2011).
[3] I. Lindemann, et al., Int. J. of Hydrogen Energy 38,
2790 (2013).

We found that the metathesis product, Ti(BH4)3,
decomposes into diborane, hydrogen and TiH2. Therefore

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

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RAPID SOLIDIFICATION TO AFFECT ON PROPERTIES OF V-BASEDHYDROGEN STORAGE ALLOYS
Wu Chaoling, Yang Fei, Luo Linshan, Chen YunguiCollege of Materials Science and Engineering, Sichuan University, Chengdu, 610064, China

Abstract The V-based BCC alloys have high reversible hydrogen capacities around 2~3mass% at room temperature
and are therefore expected to be applied as on-board hydrogen storage materials. During the first 10hydrogenation/dehydrogenation cycles, the capacities decrease markedly by about 10~15%, which hinders the largescale application of the alloys. One of the reasons is accumulating of microstrain in the lattice during cycles. In order toreduce the microstain, rapid solidification method to manufacuture the alloy was investigated. Both the grain size and theinitial dehydrogenation capacity are reduced comparing with those of the arc-melted ingot. However, after homogenizing
heat treatment at high temperature, the needle-like alloy shows higher initial dehydrogenation capacity with an increaseof the annealing temperature. Stress relief annealing at 673K was also discussed. The initial dehydrogenation capacity
does not change much. However, after 10 hydrogenation/dehydrogenation cycles, the microstrain in the lattice isreduced to a degree, indicating that the cycle stability is improved.

References[1] Y.G. Yan, et al. J. Alloys Compds, 2008, 454: 427.
[2]C.B. Wan, el al. Inter J Hydrogen Energy,
2009,348:944.
[3] C.L.Wu, et al. Inter J Hydrogen Energy,2010, 35:8130.
4] C.L.Wu, et al. J. Alloys Compds, 2013, 580:S156.

Fig. 1 Rapid solidified V-Ti-Cr-Fe alloys: a) without
annealing; b) 1373K for 0.5h; c) 1473K for 0.5h; d) 1573K
for 0.5h.

Wu Chaoling

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

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

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Zhaoquing, P.R. China 2014OXYNITROGENOGRAPHY: THE SEARCH FOR OXYNITRIDES FORSOLAR WATER SPLITTING
Moreno DE RESPINIS1, Fatwa ABDI1, Jeroen VAN VLIET1, Wilson SMITH1, Bernard
DAM1, Roel VAN DE KROL2
1

Delft University of Technology, Chemical Engineering, Materials for Energy Conversion and Storage (MECS), The
2
Netherlands; Helmholtz-Zentrum Berlin für Materialien und Energie Gmbh, Institute for Solar Fuels, Berlin, Germany
Abstract The solar hydrogen production via photoelectrochemical (PEC) water splitting requires an ideal semiconductormaterial with a high stability and a good absorption of the solar spectrum. Oxides are generally stable in aqueous
solutions, but their bandgap is usually too large to efficiently absorb sunlight. Nitrides, on the other hand, have ideal
bandgaps but they are prone to corrosion. Oxynitrides are therefore potential candidates to obtain the best of both worlds:
the oxide’s stability and the nitride’s strong light absorption. One of the most promising oxynitrides for solar water splitting
is tantalum oxynitride (β-TaON). Due to its favorable band positions, it is thermodynamically able to split water without
any external bias. However, its synthesis is very challenging. In this study, we propose ‘oxynitrogenography’ as an
approach towards the controlled and reproducible synthesis of any Ta-O-N phase, including the desired β-TaON phase.
Tantalum oxide thin films were nitridated in a tube furnace under controlled flows of ammonia, water and hydrogen, while
following the optical transmission of the film in-situ. The optical absorption changes in the film can be directly correlated
to the presence of different phases (Ta2O5, TaOxNy, Ta3N5), due to their different absorption edges. As a result, thethermodynamic equilibrium conditions to obtain these various phases were determined, and a phase diagram wasconstructed. The physical characteristics, electronic properties, and PEC performance of these phases were investigated.
It was found out that the stability of the TaOxNy samples was a major challenge, which was tackled by the addition of
convenient graphite-based protective layers and the deposition of a surface catalysts such as NiOOH.

Reference[1] Dabirian, A.; et al. Energy Procedia 2012, 22, 15-22.

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Moreno de Respinis received his bachelor degree in physics at the University of Milan in
2008, and earned his master degree in sustainable energy with study line hydrogen andfuel cells at the Technical University of Denmark (DTU) in 2011. He concluded his masterwith a fellowship at the Lawrence Berkeley National Laboratory (LBNL) in Dr. Heinz M.
Frei’s group, where he performed mechanistic studies of water photo-oxidation byvisible-light driven Co3O4 catalyst. He is currently a Ph.D. student at the Delft Universityof Technology (TUDelft) where he is researching on hydrogen production and storage via
photo-electrochemical solar water splitting.
Corresponding author: Moreno de Respinis, m.derespinis@tudelft.nl.

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RECENT STUDY ON HYDROGEN STORAGE PROPERTIES OF MGBASED MATERIALS PREPARED BY HCS+MM
Y.F. Zhu, L.J. Wei, J.G. Yuan, L.Q. Li
College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009, China
Abstract: Mg-based material is still an attractive material for hydrogen storage due to its high hydrogen storage capacity,
abundant resources, low cost and low environmental impact [1]. However, the sluggish hydrogen absorption/desorption
kinetics at moderate temperatures and the high thermodynamic stability of MgH2 hinder its application. We havedeveloped a method, namely hydriding combustion synthesis plus mechanical milling (HCS+MM), to prepare advanced
Mg-based hydrogen storage materials for hydrogen storage and hydrogen production [2-4]. The process of HCS+MM
has the advantages of low energy consumption, short processing time and high activity of the product. Here we present
some recent studies on hydrogen storage properties of Mg-based materials prepared by HCS+MM in our group.

Mg95Ni5-Zr0.7Ti0.3Mn2-MWCNT system
In order to improve the hydrogen storage properties of
Mg-based material, the Laves phase compound
Zr0.7Ti0.3Mn2 and MWCNT were co-added to form an
Mg95Ni5-Zr0.7Ti0.3Mn2-MWCNT composite by the processof HCS+MM. For comparison, the composites of Mg95Ni5,
Mg95Ni5-Zr0.7Ti0.3Mn2 and Mg95Ni5-MWCNT were also
prepared by HCS+MM. It is found that the Mg95Ni5-10
wt.% Zr0.7Ti0.3Mn2-3 wt.% MWCNT composite shows thebest hydriding/dehydriding properties, which absorbs
6.07 wt.% hydrogen within 100 s at 373 K and desorbs
95.1% hydrogen within 1800 s at 523 K. Moreover, thecomposite also has a good stability of hydriding kinetics
at 423 K under 3 MPa hydrogen pressure. As shown in
Fig. 1, after 10 hydrogen absorption/desorption cycles,
the composite can still absorb 5.58 wt.% hydrogen within
100 s. The dehydrogenation activation energy of thecomposite is 83.7 kJ/mol, which is much lower than thatof as-received MgH2 (153 kJ/mol). The improvedhydrogen storage properties are related to the structuralfeatures derived from the HCS+MM process and thesynergistic catalytic effect of nanosized Zr0.7Ti0.3Mn2 and
MWCNT.

Mg-M/MWCNT (M=Ni, Pd) system
Two systems of Mg-Ni/MWCNT and Mg-Pd/MWCNT
have been investigated. Ni or Pd nano-particles were first
loaded uniformly on the surface of MWCNT, then the asprepared Ni/MWCNT or Pd/MWCNT was added to Mg toform Mg-M/MWCNT (M=Ni, Pd) composites by theprocess of HCS+MM. The structural and hydrogenstorage properties of the composites have been

investigated
by
XRD,
SEM,
TEM
and
hydriding/dehydriding measurements. Preliminary studies
show both of the Ni/MWCNT and Pd/MWCNT can
improve greatly the hydrogen storage properties of Mg.
The mechanism of the improvement has been discussed.

Fig. 1 Cyclic hydriding kinetics of the Mg95Ni5Zr0.7Ti0.3Mn2-MWCNT composite prepared by HCS+MM
measured at 423 K under 3 MPa hydrogen pressure.

References[1] L. Schlapbach, A. Züttel. Nature, 2001, 414, 353-358.
[2] Y.F. Zhu, Z.B. Liu, Y. Yang, H. Gu, L.Q. Li, M. Cai. Int
J Hydrogen Energy, 2010, 35, 6350-6355.
[3] Z.L. Zhao, Y.F. Zhu, L.Q. Li. Chemical Communication,
2012, 48(44), 5509-5511.
[4] L.J. Wei, Y.F. Zhu, L.Q. Li. J Alloys Compds, 2012,
539, 215-220.

Yunfeng Zhu was born on 25 Dec 1977 in Jingjiang, China. 1998 Bachelor in Department ofMaterials, Zhejiang University, Hangzhou, China. 2003 Ph.D. in College of Materials Science andEngineering, Zhejiang University, Hangzhou, China. 2004 Postdoctor in AIST, Tsukuba, Japan.
2009 Professor in College of Materials Science and Engineering, Nanjing University of Technology,
Nanjing, China. Research field: hydrogen storage materials, hydrogen storage electrode alloys,
hydrogen production, nickel/metal hydride (Ni/MH) secondary battery.
Yunfeng Zhu
Corresponding author: Yunfeng Zhu, yfzhu@njut.edu.cn, +86-25-83587242

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Preparation and electrochemical characteristics of single-phase
La–Mg–Ni-based alloys with super-stacking structures
Jingjing Liub, Yuan Lib, Lu Zhangb, Juling Zhangb, Yumeng Zhaob, Shumin Hana,b,*abState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, P. R. China
Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao 066004, P. R. China

Abstract: La–Mg–Ni-based hydrogen storage alloys are considered as a promising negative electrode candidate to
replace traditional AB5-type alloys due to their large discharge capacity [1]. The preparation of single-phase La–Mg–Nibased alloys is necessary for systematic investigation but this is of full of difficulty and the reports on the single-phasealloys are rare. Our group explored the formation mechanism of the super-stacking phases and succeeded in preparing
single-phase AB3-, A2B7- and A5B19-type La–Mg–Ni-based alloys by step-wise sintering and long-time annealing method[2-4]. The phase conversions during hydrogen absorption/desorption and the relationship between the super-stacking
structures and the electrochemical properties are investigated. The single-phase PuNi3-type La2MgNi9 alloy can be
activated within just two cycles, but the discharge retention after 100 cycles (S100) decreases to 66.1%. The maximum–1discharge capacity (Cmax) of the single-phase Ce2Ni7-type La0.6Mg0.4Ni3.5 alloy is as high as 398 mAh g and the S100 is
82.8%, which is much higher than that of the single PuNi3-type alloy. The Ce2Ni7-type crystal structure remains
unchanged after initial hydrogen absorption/desorption cycles. But it decomposes into amorphous La and Mg andnanocrystalline LaNi5 and Ni phases after 20 cycles. The La4MgNi19 alloy with a single Pr5Co19-type phase gains a Cmax
of 364 mAh g–1 and a good high rate dsichargeabiliiy (HRD) of 67.2% at 900 mA g–1. The appearance of minor phases
cases obvious effects on the electrochemical properties of the alloys. It is found that when the abundance ratio of PuNi3to Ce2Ni7-type phases is close to 1:1, the alloy possesses good electrochemical performances. Small amount of LaNi5phase appearing in the A2B7-type phase improves HRD. The alloy with 80 wt.% of Pr5Co19-type phase and 20 wt.% ofCe2Ni7-type phase presents better electrochemical properties than the single Pr5Co19-type alloy.
B

B

B

(a)

(b)

Rwp = 13.72
RP = 10.58

Ni (311)Ni (222)Ni (220)
Ni (200)
Ni (111)

LaH3 (420)
MgH2 (002)
MgH2 (200)0.2 µm

100 nmnm

S = 2.01.
LaNi5H5.6(100)
LaH3 (200)Ni (200)
Ni (220)

Amorphous
LaNi5 (111)

5 1/nm5 1/nmFig. 1 Rieveld analysis of the single
Ce2Ni7-type La0.6Mg0.4Ni3.5 alloy

Fig. 2 TEM results of the single Ce2Ni7-type La0.6Mg0.4Ni3.5 alloy
after 20 charge/discharge cycles

References[1] Z.W. Dong, L.Q. Ma, Y.M. Wu, L.M. Wang, X.D.
Shen, Int. J. Hydrogen Energy 36 (2011) 30163021.

[3] J.L. Zhang, S.M. Han, Y. Li, J.J. Liu, S.Q. Yang,
L. Zhang, J. Wang, J Alloy Compd. 581 (2013) 693698.

[2] J.J. Liu, S.M. Han, Y. Li, J.L. Zhang, Y.M. Zhao,
L. Che, Int. J. Hydrogen Energy 38 (2013) 1490314911.

[4] L. Zhang, S.M. Han, Y. Li, J.J. Liu, J.L. Zhang,
J.D. Wang, S.Q. Yang, J. Hydrogen Energy, 38(2013) 10431-10437.

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials,
and rare earth chemistry.
In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogenstorage alloys, light weight hydrogen strorage materials and rare earth–Mg–Ni-based electrodematerials.
Shumin Han
Corresponding author: Shumin Han, Email: hanshm@ysu.edu.cn

Tel./fax: +86-335-8074648

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GAS ATOMIZED ALLOY ELECTRODESMariana Spodaryk1*, Larisa Shcherbakova1, Anatoliy Samelyk1, Yurii Solonin1
Valentina Zakaznova-Herzog2, Beat Braem2, Philippe Mauron2, Arndt Remhof2, Andreas
Züttel 2
1
2

Institute for Problems of Materials Science, NAS of Ukraine, 3, Krzhyzhanovsky Str., 03680, Kyiv-142, Ukraine, Switzerland

AB5 type gas atomized alloy powders are non-equilibrium materials for nickel metal hydride batteries. The
investigated gas atomized alloy electrodes activate within a few cycles, show high rate discharge kinetics up to 1C and acycle stability comparable with cast alloy. The effect of the production technology and the composition of the alloys on
the electrode properties are discussed in detail.

Introduction
High pressure gas atomization (HPGA) is asynthesis method, allowing to produce spherical AB5 typealloy particles in the micrometer size range with a high6
cooling rate of approx. 10 K/s. The particle surface
possesses enhanced corrosion resistance, e.g. leading toan increased cycle stability [1]. The HPGA technology
can produce a large quantity of alloy particles (1g – 10 kg/h) with a wide range in particle-size and a well-definedsurface and morphology. Therefore, applying thistechnology results directly in small particles and reduces
the standard long route for manufacturing the AB5 typematerials for battery electrodes. [1, 2]
The effect of the HPGA method on the properties ofthe electrode materials is discussed controversially.
Bowmann et al. found no significant difference inhydrogen storage capacity and stability, i.e. equilibriumpressure, between gas atomized alloys and as castalloys [3]. Lim et al. reported a reduced specific hydrogenstorage capacity and slower activation with cycling for
gas-atomized compared to cast alloy material [4].
Therefore, the relationship between the production
method, the resulting surface and bulk materials
characteristics and the electrochemical properties isinvestigated and analyzed in great detail.

Results
The phase composition, morphology, structure,and the surface state of gas atomized and as cast
LaNi4.5Al0.5 and LaNi2.5Co2.4Al0.1 alloy powders have been
investigated. All investigated samples exhibit thehexagonal CaCu5−type structure. The powder particles ofgas atomized alloy have mostly a spherical shape with aloose, grainy structure and a typical diameter of approx.
200 µm.

However, the shape of particles is also dependent
on the alloy composition.
The reaction resistance was investigated bymeans of Tafel plot and impedance spectroscopy. The
reaction resistance is not dependent on the charge stateof the electrode and is around 0.43 Ω and 0.69 Ω
LaNi4.5Al0.5 and LaNi2.5Co2.4Al0.1, respectively. The
resistance of the alloy electrode has a strong effect on
the high current discharge capacity, 50% of the maximum
discharge capacity, i.e. 300 mAh/g and 275 mAh/g, wasfound at 12C and 2C discharge rate for LaNi4.5Al0.5 andLaNi2.5Co2.4Al0.1, respectively. The cycle stability ofelectrodes made from LaNi2.5Co2.4Al0.1 alloy powders ishigher than that of LaNi4.5Al0.5 electrodes

References[1] Solonin YuM, Savin VV, Solonin SM, Skorokhod VV,
Bratanich TI. Gas atomized powders of hydrideforming alloys and their application in rechargeable
batteries. J Alloys Comp 253–254 (1997), 594–597.
[2] Young K, Ouchi T, Banik A, Koch J, Fetcenko MA,
Bendersky LA, Wang K, Vaudin M. Gas atomizationof Cu-modified AB5 metal hydride alloys. J Alloys
Comp 509:10 (2011), 4896–4904.
[3] Bowmann Jr RC, Witham C, Fultz B, Ratnakumar BV,
Ellis TW, Anderson IE. Hidriding behavior of gasatomised AB5 alloys. J Alloys Comp 253–254 (1997),
613-616.
[4] Lim HS, Zelter GR, Allison DU, Haun RE.
Characteristics of nickel-metal hydride cells
containing metal hydride alloys prepared by anatomization technique. J Power Sources 66:1-2(1997), 101–105.

Short CV of Mariana SPODARYKthBorn 17 of October 1988 in Ivano-Frankivsk, Ukraine.
2011 Master Degree on Technical Electrochemistry in Kyiv National University of Technology and
Design, Ukraine
2011 - 2014 PhD student in the Institute for Problems of Materials Science, Ukraine National
Academy of Science in Kyiv
2013 Guest Scientist at EMPA Materials Science & Technology, Switzerland
Mariana Spodaryk
Corresponding author: Mariana Spodaryk, email: poshtamary@ukr.net, Tel. (+38) (68) 5417935

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TITLE

NANOMATERIALS FOR HYDROGEN STORAGE

Name(s)Puru Jena

Affiliation

Virginia Commonwealth University

The limited supply of fossil fuels, its adverse effect on the environment, and growing worldwide
demand for energy has necessitated the search for new and clean sources of energy. Hydrogen, the third
most abundant element on Earth, is considered as an alternative to fossil fuels. However, hydrogen, likeelectricity, is not an energy source but an energy carrier. It needs to be produced. While considerable
challenges need to be overcome for its production, distribution, and use in fuel cells, it’s safe, efficient, andeconomical storage is considered to be critical for a successful hydrogen economy. For the mobile industry
which is responsible for nearly 80% of our oil needs, hydrogen storage materials need to have highgravimetric and volumetric density and operate at ambient thermodynamic conditions, as the current
methods for storing hydrogen as a compressed gas or liquid are not suitable for wide commercial
applications. In order for the host materials to have gravimetric density of about 10 wt%, they have to consistof elements lighter than Aluminum. Unfortunately, the bonding of hydrogen in these materials is either too
strong or too weak. Ways must, therefore, be found to tune the hydrogen bond strength so that hostmaterials composed of light elements can be used as effective hydrogen storage materials.
This talk will discuss how the novel properties of materials at the nanoscale can improve thethermodynamics and kinetics of hydrogen. In particular, I will discuss how carbon based nanostructures
such as nanotubes and fullerenes can not only be used as catalysts to improve hydrogen uptake and releasein complex light metal hydrides such as sodium alanate, but also how they can be functionalized with metaland B atoms to adsorb hydrogen in a novel quasi-molecular form. Such a bonding can improve the kinetics
and thermodynamics of hydrogen sorption. I will also discuss the role of electric field in hydrogen storage.
These results, based upon density functional theory and quantum molecular dynamics, provide afundamental understanding of the interaction of molecular hydrogen with hosts consisting of light elements. It
is hoped that the understanding gained here can be useful in designing better materials for hydrogenstorage. Results will be compared with available experimental data.

References[1] Jena, P.: “Materials for Hydrogen Storage: Past, Present, andFuture”, J. Phys. Chem. Letters (invited) 2, 206 (2011).
Dr. Jena received his B.Sc. (Hons) and M. Sc. in Physics from Utkal University in India in
1964 and 1966, respectively, and Ph. D. in Physics from the University of California, Riverside in1970. He is currently Distinguished Professor of Physics in Virginia Commonwealth University. He
has also served as a Program Director at the National Science Foundation as well as Jefferson
Science Fellow and Senior Science Advisor at the US Department of State. He works in wide rangeof fields in physics, chemistry, and materials science dealing with structure-property relationships ofmaterials in 0, 1, 2, and 3- dimensions. He is the author of about 500 papers including 12 edited
books. Among many honors he has received are: Virginia Commonwealth University’s Outstanding
Scholar Award in 1987, the University Award of Excellence, its highest academic honor, in 1993,
Virginia’s Outstanding Faculty Award from the Governor of Virginia in 2001, Jefferson Science
Fellow in 2007, Member of the Presidential Commission to Russia in 2010, and Virginia
Commonwealth’s Presidential Medallion in 2011.

Corresponding author: Puru Jena, pjena@vcu.edu, 804 828 8991

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Zhaoquing, P.R. China 2014NANOSTRUCTURED Mg-BASED HYDROGEN AND
ENERGY STORAGE MATERIALS PROBED BY IN SITU SYNCHROTRONAND NEUTRON POWDER DIFFRACTION
Volodymyr A. Yartys1,2 and Roman V. Denys1
Institute for Energy Technology, P.O. Box 40, Kjeller, NO 2027, NORWAY
Norwegian University of Science and Technology, Trondheim, NO 7491, NORWAY
Abstract. Complementarity of high flux SR XRD and NPD in situ experiments performed in real conditions, i.e. in
operando, allows time resolved measurements probing phase-structural transformations proceeding at fast rates, in justseconds, and gives a basic understanding of the systems in question. This work was focused on studies of Mg-basedmaterials for hydrogen and energy storage including (a) Catalyzed nanostructured Mg-hydride based materials; (b)Ternary AB3/A2B7 (La,Pr,Nd)-Mg-Ni intermetallics were magnesium improves performance of the electrodes of therechargeable Ni-MH batteries; (c) High pressure hydrides for “hybrid” H storage.

Nanostructured Mg-based hydrides
Studies of MgH2-based systems are aimed on achieving
faster H exchange and tailoring the thermodynamics ofthe Mg-H interactions. Nanostructuring of the Mg-Rare
Earth-Ni systems, by utilizing Reactive Ball Milling in H2,
Rapid Solidification, Equal Channel Angular Pressing and
Powder Metallurgy processing proved to be effective inreaching these objectives. Time resolved in situ SR XRD,
NPD studied and TEM investigations were used tocharacterise the mechanism and kinetics of the phasestructuraltransformations
inthematerials.
Nanostructuring increases the hydrogenation rates anddecreases the stabilities of the hydrides, in some cases
dramatically, by several hundred K [1,2].

RE-Mg-Ni alloys for Ni/MH batteries
For the ternary AB3/A2B7 RE-Mg-Ni intermetallics
magnesium strongly affects the crystal structures, H
storage capacities, and thermodynamics of their hydrides
allowing improved capacity and high energy density
performance in the rechargeable Ni-MH batteries. Partial
substitution of Mg for RE enhances electrochemical
discharge capacity becoming 25% greater than that of
the commercial AB5-type based electrodes. These
compounds are composed of individual Laves type andHaucke type layers. In present study structural, hydrogenstorage and electrochemical properties of a newcompounds (La,Pr,Nd)3-xMgxNi9 (PuNi3 type) are reported.
In situ NPD of the saturated deuterides revealed: a)nearly equal distribution of H atoms within the REMgNi4
and RENi5 layers; b) preferred filling of the Mg- and Nisurrounded sites within the REMgNi4 layers; c) local
hydrogen ordering with the H-sublattice built from astacking of the MgH6 octahedra and NiH4 tetrahedra,

indicating a directional metal–hydrogen bonding in thestudied
RE2MgNi9H12-13 deuterides. Pr and Ndcompounds show significantly lower thermodynamic
stability as compared to La2MgNi9H13 [2-4].

High pressure hydrides
While LaNi3 is prone to the hydrogen-induced
disproportionation, Mg-containing LaMg2Ni9 intermetallic
reversibly forms a stable during cycling hydride with
Hdes=24.0 kJ/molH2 and equilibrium pressure of H2
desorption of 18 bar at 20 oC. The overall chemicalcomposition LaMg2Ni9H9.5 can be presented as LaNi5H5.7+ 2*MgNi2H1.9 and indicates that the hydrogenation of the
MgNi2 slab proceeds at rather mild H2/D2 pressure
conditions as compared to individual MgNi2 (2 kBar H2).
A partial filling by D atoms of the four types of thetetrahedral interstices takes place in the MgNi2 slab;these include two types of the available [MgNi3] and two
types of the [Mg2Ni2] tetrahedra [5].

References[1] R.V.Denys, A.B.Riabov, J.P.Maehlen, M.V.Lototsky,
J.K.Solberg, V.A.Yartys. Acta Materialia, 57 (2009) 3989;
58 (2010) 2510.
[2] R.V. Denys, V.A. Yartys.// Inorg. Chem., 51 (2012)4231.
[3] Ch. C. Nwakwuo, T. Holm, R.V. Denys, J. P. Maehlen,
J. K. Solberg and V. A. Yartys. // J. Alloys andCompounds, 555 (2013) 201.
[4] Weikang Hu, T. Holm, R.V. Denys, J. P. Maehlen and
V. A. Yartys.// Electrochimica Acta, 96 (2013) 27.
[5] R. V. Denys, V. A. Yartys , and C. J. Webb. MH2012,
Kyoto, Japan, October 2012. MoP38. Coll. Abstracts.
P.92.

Prof. V.A. Yartys is professor of materials science and hydrogen technologies at Institute for Energy
Technology and Norwegian University of Science and Technology, Norway. PhD in inorganic
chemistry (Lomonosov Moscow State University,1980). Doctor of Sciences in inorganic chemistry(Lviv University, 1995). Professor in inorganic chemistry (1998). He is working in the fields ofmaterials science of nanomaterials, hydrogen and energy storage with a focus on: (a) Rechargeable
Batteries; (b) Hydrogen as an Energy Carrier; (c) Novel Materials for Hydrogen Storage and Battery
Applications; (d) Hydrogen storage systems; (e) Use of metal hydrides in energy management. V.A.
Yartys is an author of 405 publications (196 papers in peer refereed academic journals, 6 patents and
V.A. Yartys
three books). V.A. Yartys acted as a project leader in the research projects funded by EU, Norwegian
Research Council, Nordic Energy Research, industry. V.A. Yartys is Secretary General of theInternational Steering Committee of the International Symposia on the Metal-Hydrogen Systems.
Corresponding author: V.A. Yartys; e-mail: volodymyr.yartys@ife.no; Tel. +47 63 80 64 53.

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PROMOTED FORMATION OF METAL BORIDES IN THE 2LIBH4-MGH2
COMPOSITES WITH TRANSITION METAL ADDITIVES BY USING A NEW
THREE-STEP METHOD
Xiang-dong Kang, Kui-kui Wang, Ping Wang
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences,
Shenyang, P.R. China.
Abstract
The tailored formation of MgB2 in the dehydrogenation process of 2LiBH4-MgH2 composite is a prerequisite for the
improved reversible dehydrogenation property. But the formation of MgB 2 is retarded by a long incubation period. Recent
studies have demonstrated that addition of transition metal (TM) compounds can properly address this problem.
Mechanistic studies suggest that TM additives act as precursors for the formation TM borides, which provide
heterogeneous nucleation sites for the MgB2 product and consequently, enhances the dehydrogenation kinetics of thecomposite. Therefore, novel methods for efficiently and homogeneously incorporating the TM boride nanoparticles,
preferably between the LiBH4-Mg phase boundaries, are highly desirable. Herein, we report a new three-step method forincorporating TM boride nanoparticles into the 2LiBH 4-MgH2 composite. Specifically, two representative TM additives(TiF3 and Nb2O5) are selected to demonstrate the new three-step method effective in improving the dehydrogenation
property of the 2LiBH4-MgH2 composite. Overall, in comparison with the conventional one-step milling method, the threestep method can effectively promote the formation of TM boride and meanwhile, ensure its homogeneous dispersion in
the composite matrix. As a result, the composite sample prepared by the new method exhibits a favourable combinationof high hydrogen capacity, fast reaction kinetics and satisfactory cyclic stability.

References[1] X.D. Kang, K.K. Wang, Y.J. Zhong, B. Yang, P. Wang, Phys. Chem. Chem. Phys., 2013, 15, 2153.
[2] K.K. Wang, X.D. Kang, Q. Kang, Y.J. Zhong, C.H. Hu, P. Wang, J. Mater. Chem. A., 2014, In press.

Xiang-dong Kang received his Ph. D. degree in Materials Science in 2007 from Institute of Metal
Research, Chinese Academy of Sciences. He then jointed the group of Prof. Ping Wang. Currently,
he is an associate professor in IMR. CAS. His research focuses on light-metal complex hydrides andamineborane-related materials for reversible/irreversible hydrogen storage.

Xiang-dong
Kang
Corresponding author: X.D. Kang, xdkang@imr.ac.cn, Tel: 86-24-8397 0722.

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Enhancing effect of LPSO on the de/hydrogenation kinetics andstructural transformation in Mg94Cu4Y2 Alloy
Jiangwen Liu, Changcheng Zou, Hui Wang, Liuzhang Ouyang, and Min Zhu
Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology,
Guangzhou 510640, China
Abstract: We report the hydrogen storage properties and structural transformations of an Mg94Cu4Y2 alloy during thehydrogen absorption/desorption cycles. The alloy shows good reversible hydrogen capacities and fast dehydrogenation
kinetics, and rather complex microstructural transformation. The nanocomposite produced by decomposition of LPSO
promoted de/hydrogenation reactions.

Introduction
Mg-Ni-Y alloys containing long period ordered structure(LPSO) present rather good hydrogen storage properties[1-3]. The structural mechanism of LPSO alloy duringde/hydrogenation reactions was studied using careful[3]
TEM study . In this work, we designed an Mg94Cu4Y2
LPSO alloy. The purpose of the research is to evaluate
the hydrogen storage properties of the alloy, and to
explore the mechanism of microstructural effecting on
de/hydrogenation kinetics of Mg94Cu4Y2 LPSO alloy.

Experimental
The alloy Mg94Cu4Y2 was prepared by vacuum induction
melting, then mechanically cut and pulverized to about
400 um followed by 2 hours of ball milling under argon
atmosphere. The de/hydrogenation kinetics, and cycle
stability were measured using Advanced Materials
Corporation gas reaction controller at 250-350 ℃ . The
microstructures of the samples were characterized using
XRD (Philips X’pert Pro), SEM (Zeiss Supra 40), andTEM (JEM2100).

Results and Discussion
The microstructure of the cast alloy consists of about 50%
LPSO(18R- and14H-type), 35% Mg and 15% Mg2Cu(Fig.1a,b). XRD and TEM studies (Fig.1b, c) indicate thatthede/hydrogenation
reactionsandstructuraltransformations in the alloy can be describes as follows:First Hydrogenation:
LPSO (Mg,Cu,Y)+H MgH2+MgCu2+YH3
Mg+H2 MgH2

Mg2Cu+H2 MgCu2+MgH2
De/hydrogenation cycles:
MgH2 Mg+H2
MgH2+MgCu2Mg2Cu+H2
YH3 YH2+H2
The reversible hydrogen absorption/desorption capacitiesof the alloy is about 5wt% at 300℃. Approximate 4.5wt%
hydrogen can be released at 300C in 180 min as shownin Fig. 1d. The good hydrogen storage performance isrelated to the special LPSO structure. The decompositionof LPSO during the first hydrogenation provides highly
even distributed nanocomposite (MgH2+ MgCu2 + YHx).
This type of microstructure acts as inner catalytic effects
and promotes the dehydrogenation property. Also the
MgH2+MgCu2Mg2Cu+H2 reaction affect the overall
de/hydrogenation kinetics of alloy.

Acknowledgements
The authors are grateful to the National Basic Research
Program of China (973 Program No. 2010CB631300)
and Guangdong Natural Science Foundation (No.
10151064101000013).

References[1] S. Kalinichenka, L. Rontzsch, B. Lieback, Int. J.
Hydrogen Energ. 34(2009) 7749..
[2] Q. A. Zhang, D. D. Liu, Q. Q. Wang, F. Fang, D. L.
Sun, L. Z. Ouyang, M. Zhu, Scr Mater. 65(2011) 233.
[3] J.W. Liu, C.C. Zou, H. Wang, L.Z. Ouyang, M. Zhu, Int.
J. Hydrogen Energ. 38(2013) 10438.

Fig.1 (a)SEM morphology of the as cast alloy;(b)XRD Patterns with the states of as cast, hydrogenated anddehydrogenated;(c)HRTEM micrograph of the dehydrogenated sample;(d)Isothermal dehydrogenation kinetics.
Dr. Jiangwen LIU is a professor at School of Materials Science and Engineering, South China University ofTechnology. He received BEng and MEng degree from Shanghai Jiaotong University, and completed his
PhD at School of Mechanical Engineering of SCUT in 1998. His current research is focused on electron
microscopy and hydrogen storage materials.
Corresponding author: Jiangwen LIU, mejwliu@scut.edu.cn, Min ZHU, memzhu@scut.edu.cn, +86-2087112830.

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MICROSTRUCTURES AND HYDROGEN STORAGE PROPERTIES OF
MG-RE-NI ALLOYS
Baozhong Liu2, Xin Zhao1, Yuan Li1, Lin Hu1, Shumin Han1,2,*
1 College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 China
2 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004
China
Abstract Mg-RE-Ni alloys have attracted lots attention due to the excellent hydrogen storage properties. Recently, we
have prepared various La-Mg-Ni multiphase Mg-bases alloy in terms of La-Mg-Ni ternary phase diagram by different
methods (as-casting, copper-mould-casting, ultrahigh pressure (UHP), etc.), and investigated the phase compositions,
phase morphologies and hydrogen storage properties of the alloys.

Both pure magnesium (Mg) and Mg-based alloys are
attractive candidate materials for reversible hydrogenstorage due to their high hydrogen storage capacity,
outstanding reversibility and low cost. Unfortunately, thehydrogen desorption temperature of Mg-based alloys is
usually very high due to the strong affinity between
magnesium and hydrogen. Another reason is that thedehydrogenation kinetics of MgH2 is poor at moderatetemperatures. Both of them slow down the application
rhythm of Mg-based alloys as hydrogen storage materials.
Alloying Mg with rare-earth (RE) elements and nickel is
one of the effective approaches to enhance the reaction
thermodynamics and kinetics [1]. The multiphase La-MgNi alloys exhibit excellent hydrogen sorption kinetics,
which is regarded as a potential hydrogen storage
material.

hydrogen storage properties of the alloy due to the better
catalytic effect among RE hydride, Mg2Ni phase and Mg
phase and more phase boundary as hydrogen diffusion
channel, which should be ascribed to the morehomogeneous distribution of La hydride, Mg2NiH4 and
MgH2 phases. The dehydriding onset temperature of the
UHP sample (5 GPa and 973 K) is about 490 K andobviously lower than that of the as-cast alloy (560 K). The
amount of hydrogen desorption in the UHP alloy (5 GPa
at 973 K) is 2.69 wt.% at 573 K, which corresponds to
89.6% of the saturated capacity. However, thecorresponding values change to 1.75 wt.% and 58.3% in
the as-cast alloy, respectively. It is confirmed the refining
the microstrucure is one of effective approaches to tune
the hydrogen storage performances of those rare earthmagnesium-nickel alloys.

The phase transformation and phase interaction of LaMg-Ni alloys has been investigated. The results showedthat the simultaneous interaction between in situ forming
Mg and Mg2Ni phase and the catalytic effect of in situ
forming RE hydride can obviously reduce the hydrogen
sorption temperature and enhance the hydrogen sorption
kinetics [2,3]. Moreover, TEM results show that he LaH2.3
phase was distributed homogeneously throughout the Mgphase and that the Mg crystals were coated with LaH2.3
crystals in the matrix. This microstructure exhibited an
obvious volume contraction and resulted in a distinct
strain of MgH2 when the LaH3 phase released H2, which
effectively promotes the hydrogen desorption of MgH2 [4].
In addition, refining the microstructure by UHP [5] andcopper-mould-casting can obviously improve theReferences[1] LZ Ouyang, FX Qin, M Zhu. Scripta Mater. 2006; 55:
1075–8.
[2] BZ Liu, JH Li, SM Han, L Hu, LC Pei, MZ Wang. J.
Alloys Compd. 2012; 526: 6-10
[3] XL Zhu, LC Pei, ZY Zhao, BZ Liu, SM Han, RB Wang.
J. Alloys Compd. 2013; 577: 64-9
[4] L Hu, SM Han, JH Li, C Yang, Y Li, MZ Wang, Mater.
Sci. Eng. B 2010; 166: 209-212[5] XY Peng, BZ Liu, X Zhao, YP Fan, QM Peng, SM Han.
Int. J. Hydrogen Energy 2013; 38: 14661-14667

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials,
and rare earth chemistry.
In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogenstorage alloys, light weight hydrogen storage materials and rare earth–Mg–Ni-based electrodematerials.
Shumin Han
Corresponding author: Shumin Han, Email: hanshm@ysu.edu.cn

Tel./fax: +86-335-8074648

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SUPERLATTICE STRUCTURES AND HYDROGEN ABSORPTION/
DESORPTION CHARACTERISTICS OF R-MG-NI COMPOUNDS
Yongtao Li, Tingzhi Si, Dongming Liu and Qingan Zhang*
School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, China

Abstract The realization of supper-lattice rearrangement in X-Mg-Ni (X = Ca, Y, and rare earth metals) alloys is achallenge for obtaining better hydrogen storage properties. In this report, we reveal the correlation between composition,
structural features, lattice strains and hydrogen absorption/desorption behaviors of ternary X-Mg-Ni compounds, which
would help us to understand the nature of hydrogen storage in other metal hydrides.

BackgroundAs compared to highly H-containing chemical hydrides
such as NaAlH4, LiBH4, BH3NH3, and their related[1]
derivatives,
the advantages of using the hydrideforming intermetallics as hydrogen storage materials lie
in simpler chemical process, better reversibility, higherhydrogen purity and lower working temperature. However,to meet the demands for practical onboard application,
the development of new intermetallics with higher
capacity is quite necessary, which could be achieved by
the substitution of light metals for heavy ones. For
instance, ternary X-Mg-Ni (X = Ca, Y and rare earth
metals) compounds have been developed from[2]
corresponding binary X-Ni compounds. The X-Mg-Ni
have layered structures where [XMgNi4] and [XNi5] units
stack along the c-axis alternatively according to certain
combination. Hence, fundamental understanding of thissupper-lattice nature is necessary for improving hydrogenstorage properties of ternary X-Mg-Ni compounds.

Present work
In the present work, a systematic study of the ternary XMg-Ni (X = Ca, Y, and rare earth metals) compounds was
carried out to determine the structural features andhydrogen absorption-desorption characteristics. First, thecrystal structure of the ternary X-Mg-Ni (X = Ca, Y, andrare earth metals) compounds derived from XNi3 andX2Ni7 are presented for comparison. In the meantime, theexistence of the 2H and 3R variants was confirmed by
crystallographic analyses. The polymorphic transition
between the 2H and 3R phases was subsequently

revealed by quenching the X-Mg-Ni samples at various
temperatures, and a crystallographic model for thistransition was proposed. The enthalpy changes for thehydrogen absorption and desorption of ternary X-Mg-Ni
compounds were then determined from the P-C
isotherms measured at different temperatures. The
possibility of improving the hydrogen storage properties
by adjusting the X(Ca)/Mg ratio is also reported. Finally,both gaseous and electrochemical hydrogen absorption
and desorption behaviors were analyzed to reveal thechange in the hydriding/dehydriding process.

Summary(1) Ternary R-Mg-Ni compounds with supper-lattice
structures are more interesting than other hydrogenstorage alloys.
(2) Their fundamental investigations can help us tounderstand the complex nature of hydrogen storage inother metal hydrides.
(3) Ternary R-Mg-Ni compounds have larger hydrogencapacities than LaNi5-based alloys, thus exhibiting great
potential applications for MH/Ni batteries.

References[1] Li, Y.; Zhou, G.; Fang, F.; Yu, X.; Zhang, Q.; Ouyang,
L.; Zhu, M.; Sun, D. Acta Mater. 2011, 59, 1829–1838.
[2] Kadir, K.; Sakai, T.; Uehara, I. J. Alloys Compd. 1999,
287, 264–270.

Qing-An Zhang is a professor of School of Materials Science and Engineering, Anhui University ofTechnology. He received his Ph.D. in Materials Science from Zhejiang University in 2000. His
research interests focus mainly on new energy materials and novel structure materials.

Corresponding author: Qing-An Zhang, E: qazhang@ahut.edu.cn, Tel.: +(86) 0555 2311 871.

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Zhaoquing, P.R. China 2014RETHINKING HIGH-PRESSURE X-RAY PHOTOELECTRON
SPECTROSCOPY FOR THE STUDY OF HYDRIDE-FORMING MATERIALS
Renaud Delmelle*, Jeffrey Gehrig, Elsa Callini, Nicholas Stadie, Fadime Hosoglu, Andreas
Borgschulte and Andreas Züttel
Laboratory for Hydrogen and Energy, Swiss Federal Laboratories for Materials Science and Technology (Empa)Überlandstrasse 129, CH-8600 Dübendorf, Switzerland

Abstract
We report on the development of a new in-situ experimental approach for the surface analysis of hydride-forming
materials by means of X-ray photoelectron spectroscopy (XPS). This new set-up allows to expose specimens to highhydrogen pressures while keeping the analysis chamber in high vacuum conditions, and is thereby a simple, effective
and cheap alternative to existing environmental XPS techniques.

XPS is a powerful tool for the surface analysis of various
materials, providing insightful information about theelements present on a given surface, including theirrespective chemical state and concentrations across a
few up to a few tens of atomic layers. Therefore, XPS is a
key experimental technique regarding the understandingof surface phenomena occurring during the formation anddecomposition of hydrides, provided that the latter
critically influence the efficiency of applications such as
solid-state hydrogen storage, hydrogen permeation andhydrogen sensors. However, the short mean free path ofelectrons with energies below 1500 eV in a gas atambient pressure does not allow XPS analyses to be
performed in realistic experimental conditions from theapplications point of view. So does the required vacuum
levels for X-ray anodes and channeltrons.
These problems can be overcome by performing socalled “environmental”, “ambient-pressure” or “highpressure” XPS [1]. These techniques rely on the use ofdifferential pumping stages, the minimization of thesample-aperture distance in the high pressure regions
and, for the most recent systems, on the addition ofelectrostatic lenses to focus the electrons through thedifferential pumping scheme [2]. Nonetheless, thesetechniques suffer from drawbacks, i.e. reduction of theenergy resolution and sample freedom of movement,high cost and accessibility of the facilities due to the factthat most of them have been developed for operation atsynchrotron light sources.

A new experimental approach is proposed here in orderto study materials exposed to high hydrogen pressureswhile keeping the analysis chamber in high vacuum. A
new type of sample holder has been designed in thisrespect, consisting of a Pd-Ag membrane fed on one sidewith a high hydrogen pressure, and exposed on the otherside to the X-ray beam at UHV compatible pressures.
Since this alloy exhibits low dissociation barrier, theproper hydrogen absorption enthalpy and fast hydrogen
diffusion kinetics, monoatomic hydrogen is rapidly
generated and transferred through the bulk of themembrane to the surface exposed to vacuum. Moreover,this also results in a high hydrogen concentration on that
surface, because the hydrogen permeation is limited bydesorption from the low pressure side of the membrane.
By capping the membrane with any hydride-forming
material, one is then able to study hydrides by means of
XPS with realistic hydrogen concentrations.
This new experimental approach will be presented, withparticular focus on the effect of the surface properties on
the hydrogen permeation through Pd-Ag membranes.

References[1] F. Mangolini et al., Rev. Sci. Instrum. 83 (2012)093112/1-10.
[2] M. Salmeron and R. Schögl, Surf. Sci. Rep. 63 (2008)
169-199.

Born 1984 in Charleroi, Belgium. 2002-2008: B. Sc. And M. Sc. degrees in Materials Science
Engineering at Université catholique de Louvain, Louvain-la-Neuve, Belgium. Master Thesis: “Insitu monitoring of the hydriding kinetics of Pd thin films.” 2008-2012: Ph. D. degree at Université
catholique de Louvain. Ph. D. Thesis: “Effect of internal stress and microstructure on the hydridingof Pd thin films.” 10/2012-02/2013: Post. Doc. at Université catholique de Louvain. Since 2013:
Post. Doc. at Empa, Dübendorf, Switzerland.
Renaud Delmelle*Corresponding author: Renaud Delmelle, Renaud.Delmelle@empa.ch, +41 587656541.

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A NEW METHOD TO PREPARE MG BASED HYDROGEN STORAGE MATERIALSWITH IMPROVED DEHYDRIDING THERMODYNAMICS AND KINETICS PROPERTIES
L. Z. Ouyang*, Z. J. Cao, H. Wang, J. W. Liu, M. Zhu
School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China
Abstract:
The reversible formation of Mg(In) solid solution provides a new way to tune the dehydriding thermodynamics of MgH 2.
However, the preparation of this solid solution is quite difficult and its dehydriding kinetics is rather sluggish. This work
offers a novel technique, plasma milling (P-milling), to solve the two problems simultaneously. The efficiency of thesynthesis of Mg(In) solid solution, with a hydrogen capacity of up to 5.16 wt.%, is improved significantly. Meanwhile, thekinetics is also modified by the catalyzing effect of in situ synthesized MgF2. Mg2In0.1Ni solid solution with an Mg2Ni-type
structure has also been synthesized and its hydrogen storage properties have been investigated. The results showedthat the introduction of In into Mg2Ni not only significantly improved the dehydrogenation kinetics but also greatly lowered
the thermodynamic stability.
Enhanced thermodynamic and kinetic properties of
Mg-In- MgF2 system prepared by dielectric barrierdischarge plasma assisted millingMg based alloys suffers from a large reaction enthalpy
and a large activation energy. The sluggish kinetic
property has been solved in recent years but the tuningof the enthalpy unavoidably leads to sluggish kinetic
properties. Therefore, the dual tuning of both thethermodynamic and kinetic properties is the key issue tobe solved. This work shows that both the desorption
thermodynamic properties and the kinetic properties of
MgH2 could be tuned via the introduction of In using
dielectric barrier discharge plasma-assisted ball milling(denoted here as DBDP milling). Mg-In system catalyzed
with in situ formed MgF2 was prepared by DBDP milling.
MgH2 is thermodynamically destabilized via theintroduction of In by DBDP milling (∆H=69.2 kJ/mol H2).
Mg-In system produced using DBDP milling shows
improved desorption kinetics (Ea=127.7 kJ/mol). Dualtuning of the thermodynamic and kinetic properties of
MgH2 is realized.

change (∆H) decreased from 80 kJ/mol and 64.5 kJ/mol
H2 to 28.9 kJ/mol and 38.4 kJ/mol H2, respectively. The
obtained results point to a method for improving not only
the thermodynamic but also the kinetic properties ofhydrogen storage materials.This work may also have agreat impact on the advancement of hydrogen towards
on-board applications.

Dual-tuning effect of In on the dehydriding
kinetics and thermodynamics properties of
Mg2Ni
Mg2In0.1Ni solid solution with an Mg2Ni-type structure isprepared. The results show that the incorporation of In
into the lattice of Mg2Ni could realize this goal and thisstudy suggests a means of improving both the kinetics
and thermodynamics of hydrogen storage materials. The
dehydrogenation activation energy (Ea) and enthalpy

References[1] L. Z. Ouyang et al., J. Alloys Compd., 586 (2014)
113-117[2] L. Z. Ouyang et al., Int J Hydrogen Energ, 38(2013)
8881-8887.

Short CV: Liuzhang Ouyang is Professor and Head of department of metallic materials scienceand technology at South China University of Technology. He received his B.S. in Metallic
Materials from Yanshan University at Hebei province in 1994. Professor Ouyang received his
Ph.D. from South China University of Technology (SCUT) in 2001 and joined SCUT faculty in
1987. Current research projects focus on hydrogen storage and hydrogen generation materialsof light metal hydrides, light metal complex hydrides and their composites, La-Mg-Ni-basedhydrogen storage, nickel/metal hydrides (Ni/MH) secondary batteries electrode alloys etc..
Prof. Ouyang has already published more than 100 papers in important journals such as APL,
JPCC, Acta Materialia etc..
Corresponding author: Liuzhang Ouyang, email:meouyang@scut.edu.cn, Tel: 86-20-87114253

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Transition and Conduction in Hydrides
Shin-ichi Orimo1,3
1
2

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

Recent progresses on hydrides, relating to high-density hydrogen storage as well as Li/Na fast-ionic conduction andhigh-performance battery devices using complex hydrides, will be presented in the lecture.

Transition of Bonding States in Hydridesfor Hydrogen Storage

Conduction in Complex Hydrides
for Electrochemical-Energy Storage

We have been focusing on transition between bonding
states of hydrogen, to increase hydrogen density inhydrides [1-4].

We have reported that, the LiBH 4 based complex
hydrides show Li and Na fast-ionic conductivities, andthat, the function can be applied to various battery
devices [5]. Actually, bulk-type all-solid-state lithium
solid
rechargeable
batteryusing
LiBH 4 -based
electrolytes allows noticeable charge–discharge cycles[6].

An example of the transition was found in YMn 2 hydrides,that is, the hydrides showed the continuous transition
from the metal hydride YMn 2 H x to the complex hydride
5YMn 2 H 6 with [MnH 6 ] complex anion, even under rather
mild conditions. Some computational and experimental
studies including EXAFS have been carried out to extend
the novel property; “increasing hydrogen densities ofmetal hydrides by using continuous transition into
complex hydrides”.
Adjustment of imbalanced charge is of great importanceto promote the transition of bonding states. It was
experimentally demonstrated that the addition of Li (orLiH) enabled the formation of new complex hydride
4−
YLiFeH 6 with the [FeH 6 ] complex anion from theintermetallic compound YFe 2 which has not been
considered to transform into a complex hydride on its
own. The method can be applied to many otherintermetallic compounds even if they are composed ofonly elements that do not form intermetallic compounds
or solid solution alloys with Li, which will greatly
contribute to the increase in the variety of complex
hydrides.

References[1] M. Matsuo, K. Miwa, S. Semboshi, H.-W. Li, M. Kano,
S. Orimo, Appl. Phys. Lett. 98, 221908 (2011).
[2] S. Takagi, K. Miwa, T. Ikeshoji, M. Matsuo, M. Kano,
S. Orimo, Appl. Phys. Lett. 100, 021908 (2012).
[3] M. Matsuo, D. Matsumura, Y. Nishihata, G.-Q. Li, N.
Hiyama, S. Semboshi, S. Orimo, Appl. Phys. Lett. 100,
044101 (2012).
[4] M. Matsuo, H. Saitoh, A. Machida, R. Sato, S. Takagi,
K. Miwa, T. Watanuki, Y. Katayama, K. Aoki, S. Orimo,
RSC Adv. 3, 1013 (2013).
[5] M. Matsuo, S. Orimo, Adv. Energy Mater. 1, 161(2011): Review[6] A. Unemoto, M. Matsuo, S. Orimo, Adv. Functional
Mater. in press (DOI: 10.1002/adfm.201303147): Feature Article

Shin-ichi ORIMO received his Ph. D. in materials science/physics from Hiroshima University in
1995. He was a JSPS research fellow (1993-1995), a research associate in Hiroshima University(1995-2002), and a guest researcher of Max-Planck Institute for Metal Research awarded byAlexander von Humboldt Fellowship and MEXT Fellowship (1998-1999); and is a professor of
WPI-AIMR / IMR, and a Special Advisor to the University President, Tohoku University. His
research interests are fundamentals and energy-related applications of hydrides. He was awarded“The Prize for Science and Technology (Research Category), The Commendation for Science andTechnology by the Minister, MEXT (2012)”.
Shin-ichi ORIMO

http://www.hydrogen.imr.tohoku.ac.jp/

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

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Catalytic Hydrogenation of CO2 to CH4 and CO over Pt-K-Ta/Ni/ Al2O3
Fadime Hosoglua, Andreas Borgschulte a, Andreas Zuettel a
Hydrogen & Energy Empa Swiss Federal Laboratories for Materials Testing and Research, Uberlandstrasse 129, CH8600 Dübendorf, SwitzerlandaCorresponding author: e-mail: fadime.@empa.ch; Tel: +41 (0) 58 765 40 38
Abstract: The catalytic hydrogenations of CO2 over bimetallic catalyst were investigated. Bimetallic catalysts XNi/Al2O3 (x= Pt, K and Ta) were synthesized as precursors of mixed oxides by co precipitation method. The samples
were extensively characterized by XRD, SEM, N2-physisorption, porosity and tested for the catalytic conversion of CO 2
through the hydrogenation reaction. CO2 hydrogenation over bimetallic catalysts was analyzed by catalytic activity
measurement with a flow reactor completed by Infrared spectroscopy. We validate that for the hydrogenation of CO2
reaction, the effect of the different promoter catalyst.

Introduction

Results

Recently, CO2 accumulation in the atmospherewhich comes from combustion of fossil fuels is feared as
the major cause of greenhouse effect. Therefore, there
are several possible strategies to control amount of theCO2 such as: CO2 separation and collection technology,
CO2 capture technology, utilization of CO2 and reducingof CO2.In this context, catalytic conversion of CO2 oversuitable catalyst has been widely explored [1,2].
Hydrogen has greatest properties for the storage
and transportation of energy provided it can be efficiently
produced from renewable energy sources .Hydrogen canbe also found in many organic compounds, such ashydrocarbons, gasoline, natural gas and methanol.
Recently, catalytic conversion of carbon dioxide byhydrogenation is one of the most efficient ways in orderto produce energy and store hydrogen. Hydrogen canalso be stored on to the materials by adsorption such as
metal hydrides.
Reducing CO2 accumulation would be the chemicaltransformation of CO2 into valuable compounds using
suitable catalysts. Catalyst system for the hydrogenationof CO2 has been developed to obtain more valuable
chemical feedstock such as light olefins, liquidhydrocarbons, CH4 and CO.

Conversion of the CO2 as a function oftemperature is presented on Figure1. For all catalysts
the catalytic activity in term of the percentage of CO2
conversion showed progressive increment with theincreasing reaction temperature. At low temperature PtNi/Al2O3 is higher than other catalysts. At hightemperature conversion of CO2 over Pt is maximum (90%) and Ta-Ni/Al2O3 has similar catalytic conversion of
CO2.

Experimental set up
The catalytic reaction is occurred in a stainlesssteel tubular reactor which has a diameter of 18 mm anda length of 450 mm. Quantity of the catalyst was 1g. The
gas flows were controlled by thermal mass flow metersfrom MKS Instruments connected to a Lab view interface.
Flow rates CO2 were 40 ml/min and for 200 ml/min H2.

Figure 1: Conversion of CO2 as a function of T °C.

Conclusions
It was observed that catalytic conversion of CO2
by hydrogenation is more active at low temperature overPt-Ni/Al2O3. On the other hand for CO2 hydrogenation Ta
can be an alternative promoter catalyst due to its highcatalytic activity according to Pt catalyst.

References
1 X. D. Xu and J. A. Moulijin, Energy Fuels, 1996, 10,305-325
2 W. Wang, S. Wang and J. Gong, Chem. Soc. Rev.,
2011, 40, 3703-3727

Dr. Fadime Hosoglu has finished school of Engineering in the Environmental engineering in university of
Mersin on 2008. During Engineering school have studied Polytechnic of Valencia on 2005. I have studied
my Master at University Marne La Vallée in environmental department on 2009. After my master, I havestudied my PhD about: “Production of 1-propanol and 1-butanol from the mixture methanol and ethanol
over hydrotalcite catalyst” at university Science and Technology of Lille 1 on 2012. Actually I have postdoc position in theteam of Hydrogen and Energy at Empa in Switzerland.

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FURTHERSTUDYON
HYDROGEN-DEUTERIUMEXCHANGE
MECHANISM DURING DESORPTION OF LIBH4-MGD2 SYSTEM
Y. X. Fu a,b, J. Y. Zhu a,b, H. Wang a,b, and M. Zhu a,babSchool of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China
Key Laboratory of Advanced Energy Storage Materials of Guangdong Province

Abstract: This work aims to further understand the dynamic process of hydrogen exchange mechanism in LiBH 4-MgD2
system. By investigating the different decomposition behaviour in LiBH4-MgD2, NaBH4-MgD2 and LiBH4-VD2 systems, it
is found that the hydrogen exchange is strongly dependent on the gap between the melting point of complex hydride andthe decomposition temperature of metal hydride. As a result, the dynamic hydrogen exchange process is proposed.

Introduction
The previous study [1] has proposed the concept of“hydrogen-exchange” in the LiBH4-MgD2 system, which
was proven in LiBH4 by the detection of B-D vibration.
The so-called hydrogen-exchange mechanism isbelieved to increase the decomposition temperature of
MgH2, but lower the decomposition temperature of LiBH4.
To further investigate the dynamic process of hydrogenexchange, the decomposition of LiBH4-MgD2, NaBH4MgD2 and LiBH4-VD2 systems, which are prepared byhand milling for 5 minutes under identical conditions, areinvestigated by TPD-MS and FTIR.

happens, and H atoms in the LiBH4 become free andescape from the molten LiBH4 to form H2 gas. In addition,
partial H atoms also combine with D atoms to form HD
gas.

Results
TPD-MS results (Figure 1) show different D release
behaviour for three samples. In the LiBH4-MgD2 system,
the majority of D releases in the form of HD, whereas
major D2 could be detected in the NaBH4-MgD2 system,
indicating weak hydrogen exchange between NaBH4 and
MgD2. We believe the difference should be due to higher
melting point for the NaBH4 than that of LiBH4. For the
LiBH4-VD2 system, the decomposition temperature of VD2
is lower than the melting point of LiBH4. As shown in
Figure 1, the on-set decomposition of pure VD2 isindicated by the D2 peak at 275C, however, the intensityof D2 signal significantly decreases and HD signal
appears in intensive strength, which should be due to themelting of LiBH4 and the resultant intensive H-D
exchange. Above results clearly indicate the influence of
LiBH4 melting in H-D exchange.

Figure 1 TPD-MS results of LiBH4-MgD2, NaBH4-MgD2
and LiBH4-VD2 systems.

References[1] L. Zeng, H. Miyaoka, T. Ichikawa, and Y. Kojima: J.
Phys. Chem. C, 2010, 114, 131-132.

As a result, a hydrogen exchange mechanism in LiBH4MgD2 system is proposed as follows: The released D
atoms from MgD2 diffuse to its surface but trapped by themolten layer of LiBH4, thus the D atoms recombination isconsiderably inhibited. Afterwards, the H-D exchange

Hui Wang was born on 24 August 1974 in Hengyang city, China. 1997 Bachelor in Metallic
Materials and Heat Treatment, Tianjin University, Tianjin, China. 2003 PhD in Materials Processing
and Engineering, South China University of Technology, Guangzhou, China. Currently A.P.
Professor at the Key Laboratory of Advanced Energy Storage Materials of Guangdong Province,
South China University of Technology, Guangzhou, China.
His research interest is focused on reversible hydrogen storage of MgH2 modified withnanostructure, core-shell structure, compositing structure, alloying and catalyst doping.
Hui Wang
Corresponding author: Hui Wang, email: mehwang@scut.edu.cn, Tel.: +86-20-39380578.

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SYNTHESIS AND CATALYTIC EFFECTS OF TIB2/TIN @GRAPHAENE
NANO SHEETS ON HYDROGEN STORAGE OF MAGNESIUM HYDRIDE
Ying Wang, Guang Liu,Yijing Wang*, Lifang Jiao, Huatang Yuan
Institute of New Energy Material Chemistry, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Key Laboratory of Advanced Energy Materials Chemistry (MOE), Tianjin Key Lab of Metal and Molecule–based
Material Chemistry, Nankai University, Tianjin 300071, P.R. China
Abstract: Magnesium hydride has attracted much attention for hydrogen storage applications because of its high3
gravimetric (7.6 wt%) and volumetric (110 kg/m ) capacity as well as low cost[1]. However, the high hydrogen desorption
temperature >300℃ and sluggish sorption kinetics of MgH2 have limited its practical applications [2]. In the presented
work, a series of transition metal compound decorated highly crumpled graphene nanosheets (GNSs) have beensuccessfully synthesised and their catalytic effect on the sorption performance of MgH2 has been systematically
discussed. Experimental measurements confirm that the peak desorption temperature of MgH 2-5wt%TiB2/GNSs
composites can be lowered more than 44 ℃ than the pure as-milled MgH2 (DSC measurement). And thedehydrogenation kinetics of TiB2/GNSs-doped MgH2 is severalfold acceleration compares to the pure as-milled MgH2.
After adding TiN@GNSs, the as-prepared MgH2-TiN@GNSs sample can release hydrogen at remarkable lowerotemperature (about 167 C). X-Ray diffraction and XPS results reveal that as-prepared TiN@GNSs nanopowders
possess excellent catalytic stability. HP–DSC analysis clearly shows that excellent performances for H2 desorption andabsorption can be obtained upon the addition of TiN@GNSs catalyst.

Introduction
Developing a safe and efﬁcient hydrogen storage
medium has become an urgent issue for realizing thehydrogen economy and various hydrogen storage
materials have been investigated in the last decades.
Among these options, one of the most promisingmaterials is MgH2. However, the practical application of
MgH2 is limited by high thermal stability and sluggish
sorption kinetics. To overcome these drawbacks,
numerous efforts have been paid including alloying [3],nano-confinement [4], doping[5] and so on. Anothernotable method to modify the hydrogen storage
properties of MgH2 is to combine MgH2 with different
catalysts. Here, we report the synthesis of amorphous
TiB2 nanoparticles on GNSs and TiN@GNSs
nanohybrids. Their catalytic effect on the kinetics andthermodynamics of MgH2 have been investigated.

Results and conclusion
The prepared TiB2/GNSs exhibits an excellent catalytic
effect on dehydrogenation of MgH2 compares with thepure milled MgH2, and much better than the individualcomponent of TiB2 or GNSs. It is demonstrated that thepeak desorption temperature of MgH2-TiB2/GNSs
nanocomposites decreases ~44 ℃ by means ofdifferential scanning calorimetry (DSC) measurement,
and the dehydrogenation kinetics of MgH2-TiB2/GNSs
nanocomposites
is further improved. Microstructure
measurements and modeling study indicate that
TiB2/GNSs is highly efficient for dehydrogenation kineticsof MgH2, and the synergistic effect of nano-GNSs and
TiB2 nanoparticles contributes to the excellent
dehydrogenation performance.

GNSs. Thermodynamics and isothermal decomposition
experiment show that adding TiN@rGO to the MgH2 cansignificantly facilitate the dehydrogenation of MgH2.

Acknowledgment
We are grateful to the MOST project (2010CB631303,
2012AA051901), NSFC (51071087, 51171083), 111
project (B12015) and Nature Science Foundation of
Tianjin (11JCYBJC07700) for financial support of thiswork.

References[1] Schlapbach L, Zuttel A. Hydrogen-storage materials
for mobile applications. Nature. 2001;414:353-8.
[2] Grochala W, Edwards PP. Thermal Decomposition of
the Non-Interstitial Hydrides for the Storage andProduction of Hydrogen. Chem Rev. 2004;104:1283316.
[3] Shao HY, Liu T, Li XG, Zhang LF. Preparation of
Mg2Ni intermetallic compound from nanoparticles.
Scripta Mater. 2003;49:595-9.
[4]Lim DW, Yoon JW, Ryu KY, Suh MP. Magnesium
nanocrystals embedded in a metal-organic framework:
hybrid hydrogen storage with synergistic effect on
physi- and chemisorption. Angew Chem Int Edit.
2012;51:9814-7.
[5] Liang G, Huot J, Boily S, Schulz R. Hydrogen
desorption kinetics of a mechanically milled
MgH2+5at.%V nanocomposite. J Alloys Compd.
2000;305:239-45.

TEM and SEM experiment demonstrate that TiNnanocrystals uniformly anchored onto the surface of

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Prof. Dr. Wang has worked as Postdoctoral fellow at Research Center for Advanced Science andTechnology, Tokyo University, Japan from 2002 to 2004. Since 1994 employed in the Institute of
New Energy Material Chemistry, Nankai University, She has over 100 scientific publications and 6
patents. Her major Research Interests are focus on：Synthesis and Characteristics of Hydrogen
Storage Materials and High-performance Electrode Material.

Yijing Wang
Corresponding author:
Name: Yijing Wang, E-mail: wangyj@nankai.edu.cn, Tel.: 022-23503639.
.

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Dehydriding Properties of LiBH4 Combined with Mg2FeH6
Guanqiao Li1, Motoaki Matsuo1, Stefano Deledda2, Ryutaro Sato1, Toyoto Sato1, Bjørn C.
Hauback2, Shin-ichi Orimo1,3.
1Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
Physics Department, Institute for Energy Technology, Kjeller NO-2027, Norway
3
WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan2

By mechanically milling LiBH4 with Mg2FeH6, an unreported solid solution having both non-metal based complex anion
4[BH4]－ and transition metal based complex anion [FeH6] － may have formed. The dehydriding properties and crystal
structures of the LiBH4 and Mg2FeH6 combined samples are investigated and discussed.

Introduction
Combining hydrides with different characteristics is aneffective method to develop new materials having betterhydrogen storage properties or disclose novel
functionalities. New compounds having both [BH4]－ and[NH2] － complex anions have been synthesized by
combining LiBH4 with LiNH2. The new compounds haveion conductivity 4 orders of magnitude higher than LiBH4
and release pure hydrogen without undesired ammonia
or borane [1].
Mg2FeH6 is one of the most prospective hydrogenstorage materials in transition metal based complex
hydrides [2]. Although the formation of new hydride has
been revealed by combining Mg2FeH6 with the othertransition metal based complex hydride Mg2CoH5 [3],hydrides having both non-metal based complex anion
and transition metal complex anion have not beenreported.
Therefore, we have made an attempt at synthesizing newcomplex hydrides by combining the non-metal based
complex hydride LiBH4 with Mg2FeH6 as well as
investigating the hydrogen storage properties of the
combined system.

Synthesis and characterization of xLiBH4 +(1-x)Mg2FeH6Home synthesized Mg2FeH6 (> 95 %) is mixed with LiBH4(95 %, Aldrich) at molar ratios range from 9:1 (x = 0.1) to
1:5 (x = 0.83) by mechanical milling for 5 h under argon.
The dehydriding properties are examined by Thermogravimetric analysis-mass spectrometry (Rigaku TG8120,
He flow of 150 ml/min, heating rate of 5 K/min). Crystal
structure analysis is achieved by both ex-situ X-ray
diffraction (PANalytical X’Pert-Pro, CuK) and in-situ

high-resolution synchrotron X-ray diffraction (the SwissNorwegian Beam Line, BM01B).

Results and discussion
The dehydriding reaction of pure LiBH4 and Mg2FeH6
each starts approximately at 650 and 450 K, 12.5 and 4.3
mass% hydrogen are released respectively. The
dehydriding behavior changes drastically in the LiBH4
and Mg2FeH6 combined samples. Within the composition
range 0.1 ≤ x ≤ 0.5, LiBH4 and Mg2FeH6 releasehydrogen simultaneously. The dehydriding temperaturesand quantities of released hydrogen shift along with x.
The lattice parameter of Mg2FeH6 phase in the combined
samples measured by in-situ high-resolution synchrotron
X-ray diffraction suggests the possibility of forming solid
solution LixMg2-2x(BH4)x(FeH6)1-x having both [BH4]－ and4[FeH6] － complex anions [4].
This research is funded by Funding Program for Next
Generation World-Leading Researchers (GR008), Grantin-Aid for Scientific Research (S) and the Integrated
Project of ICC-IMR.

References[1] M. Aoki, K. Miwa, T. Noritake, G. Kitahara,
Y. Nakamori, S. Orimo, S. Towata, Appl. Phys. A., 80(2005) 1409.
[2] B. Bogdanović, A. Reiser, K. Schlichte, B. Spliethoff,
B. Tesche, J. Alloys Compd., 345 (2002) 77.
[3] S. Deledda and B.C. Hauback, Nanotech., 20 (2009)
204010.
[4] G. Li, M. Matsuo, S. Deledda, R. Sato, B.C. Hauback,
S. Orimo, Mater. Trans., 54 (2013) 1532.

2003-2006, undergraduate student of College of Chemistry and Molecular Engineering, Peking
University. 2006, bachelor of science. 2011-2013, master course in the Graduate School ofEnvironmental Studies, Tohoku University. 2013, master of interdisciplinary studies. 2013 until now,Ph. D student in the Graduate School of Environmental Studies, Tohoku University. Research oncomplex hydrides for hydrogen storage materials in Prof. Orimo-Shin-ichi’s lab.
http://www.hydrogen.imr.tohoku.ac.jp/
Guanqiao Li
Corresponding author: Guanqiao Li, Email: likk@imr.tohoku.ac.jp, Tel. (+81)22-215-2094.

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COMBINATION OF LIGHTWEIGHT HYDROGEN STORAGE MATERIALSAND NANOSTRUCTURES
Jun Chen*
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry; Collaborative
Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, China
Abstract: Efficient hydrogen storage plays an important role in ideal hydrogen economy. However, it still remains achallenge to develop hydrogen storage materials with high capacity and fast kinetics. To achieve this target, thecombination of lightweight materials and nanostructures should offer great opportunities. Our studies focus on enhancing
the hydrogen storage properties of lightweight Mg/MgH2 system and ammonia borane (NH3BH3, AB) with nanostructures.

Introduction
Hydrogen as a clean fuel has received worldwide
attention. Unfortunately, the practical application of thehydrogen storage system is plagued by several factors. A
major challenge is the development of on-boardhydrogen storage materials with high hydrogen density[1]. In this regard, many hydrogen storage materials havebeen exploited and investigated. Among them, special
attention is paid to Mg/MgH2 system and AB because
both of them belong to lightweight materials and have thepotential to store a significant percent of hydrogen. Our
attempts are aiming at increasing their hydrogengeneration rates and lowering the desorption temperature
with the combination of lightweight hydrogen storage
materials and nanistructures.

Efficient hydrogen storage with Mg/MgH2
and AB
MgH2 contains 7.6wt% hydrogen, making it an attractive
lightweight hydrogen storage material. However, thesluggish kinetics and high operation temperature limit its
practical application [2]. To overcome the drawbacks,
special attention has been paid to Mg-based
nanomaterials. We synthesized Mg nanowires withdifferent diameters and studied their size-dependenthydrogen storage properties. The results show that thethinner Mg/MgH2 nanowires have a much lower
desorption energy than that of thicker nanowires or bulk
Mg/MgH2, indicating that combination of lightweightsystem and nanostructures offers the potential to achieve
efficient hydrogen storage [3].
AB, as an on-board hydrogen storage material, contains
19.6wt% hydrogen. H2 can be released through pyrolysis
or hydrolysis route [4]. In the aspect of pyrolysis, we used

Jun Chenthe materials such as silica hollow nanospheres [5],porous MnO2 hollow cubes [6] and poly (methyl acrylate)[7] to confine AB. Those approaches efficiently lower thehydrogen release temperature. For hydrolysis of AB, wehave prepared Pt-Ni alloy (such as Ni1-xPtx, Co1-x@Ptx
and Ni1-x@Ptx nanoparticles [8,9,10]), nanoporous Ni and
Ni-Fe catalysts [11] to improve the hydrolytic
performance of AB. The results show that AB
nanoconfinement and catalyst additives are essential forthe enhancement of hydrogen releasing.

Conclusion
Efforts have been dedicated to investigate the hydrogenstorage performance of lightweight materials. The results
shed light onto the application of Mg/MgH2 and AB as
efficient hydrogen storage materials.

References[1] Schlapbach, L.et al; Nature 2001, 414, 353.
[2] Grochala, W.et al; Chem. Rev. 2004, 104, 1283.
[3] Li, W.et al; J Am Chem Soc 2007, 129, 6710.
[4] Peng, B.et al; Energy Environ Sci 2008, 1, 479.
[5] Zhang, T.et al; Phys Chem Chem Phys 2011, 13,
18592.
[6] Yang, Z.et al; Micropor Mesopor Mat 2012, 161, 40.
[7] Zhao, J.et al; Adv Mater 2010, 22, 394.
[8] Cheng, F.et al; Inorg Chem 2007, 46, 788.
[9] Yang, X.et al; J Power Sources 2011, 196, 2785.
[10] Yang, X.et al; Int J Hydrogen Energy 2011, 36, 1984.
[11] Du, J.et al; Int J Hydrogen Energy 2013, 38, 5768.

Jun Chen is a Cheung Kong Scholar Professor, the Director of Key Laboratory of Advanced Energy
Materials Chemistry (Ministry of Education) at Nankai University (China), and the Vice Chairman of
the Chinese Society of Electrochemistry. He obtained his B.Sc. and M.Sc. degrees from Nankai
University in 1989 and 1992, respectively, and his Ph.D. from Wollongong University (Australia) in
1999. He held the NEDO fellowship at National Institute of AIST Kansai Center (Japan) from 1999 to
2002. His research activity focuses on nanomaterials electrochemistry, batteries, fuel cells and solar
cells with efficient energy storage & conversion. He has published more than 150 SCI journal papers(such as those in Nat Chem, Chem Soc Rev, Acc Chem Res, Coord Chem Rev, Angew Chem Int
Ed, Adv Mater, JACS, Nano Lett, Energy Environ Sci) with citation times exceeding 8000.

Corresponding author: Jun Chen, email: chenabc@nankai.edu.cn, Tel: +86-22-23506808.

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Remarkable dehydrogenation improvement of LiAlH4 catalyzed by
CoFe2O4 nanoparticles
Ziliang Li a, Fuqiang Zhai b, Ping Li a,*, Qi Wan a, Xuanhui Qu aa

Institute for Advanced Materials and Technology, University of Science and Technology Beijing,

Beijing 100083, Chinab

Departament Física Aplicada, EETAC, Universitat Politècnica de Catalunya- BarcelonaTech,

08860 Castelldefels, Spain
Corresponding author: ustbliping@126.com (Ping Li); Tel: +86-10-82377286; Fax: +86-1062334311.

Abstract：The catalytic effects of CoFe2O4 nanoparticles on the dehydrogenation properties of LiAlH4, preparedby ball-milling, are investigated for the ﬁrst time. The onset desorption temperature of 2 mol% CoFe2O4 doped
LiAlH4 for the first two stages is 65 °C, 90 °C lower than those of the as-received LiAlH4, with approximately 7.2
wt% hydrogen released by 250 °C. Isothermal desorption results at 120 °C reveal that 2 mol% CoFe2O4 doped
sample can release 6.8 wt% of hydrogen within 160 min, which is 6.1 wt% higher than that of the pristine LiAlH4
under the same conditions, indicating signiﬁcantly improved dehydrogenation properties. Through the differential
scanning calorimetry (DSC) and the Kissinger desorption kinetics analyses, the apparent activation energies Ea of
the 2 mol% CoFe2O4 doped sample are calculated to be 73.1 kJ/mol and 86.1 kJ/mol, for the first two
decomposition reactions, which are 41.2 kJ/mol and 86.5 kJ/mol lower than those of pristine LiAlH4, respectively,
indicating a considerably decreased desorption barrier compared with other reported catalysts. Through Fouriertransform infrared (FTIR), and X-ray diffraction (XRD) analyses, a series of ﬁnely dispersed Fe and Co species
with a range of valence states couple with the reactions between LiAlH4 and CoFe2O4 together play a synergisticrole in remarkably improving dehydrogenation properties of LiAlH4.
Keywords: Lithium aluminum hydride; Cobalt ferrite; Dehydrogenation performance; Kinetics desorption;
Dehydrogenation mechanism.

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NOVEL MG-IN-NI TERNARY ALLOYS FOR REVERSIBLE HYDROGEN
STORAGEY. S. Lu a,b, H. Wang a,b, J. W. Liu a,b, L. Z. Ouyang a,b and M. Zhu a,babSchool of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China
Key Laboratory of Advanced Energy Storage Materials of Guangdong Province

Abstract: Mg90In5Ni5 alloy was synthesized by ball-milling Mg(In) solid solution with Ni powders. Two new Mg-In-Ni
ternary phases X1 and X2 are respectively formed at the hydrogenation and dehydrogenation states of Mg90In5Ni5 alloy,
which have never been reported in the literature. The results indicate two dehydrogenation reaction characteristics of
Mg90In5Ni5 alloy, namely MgH2 + X1 ↔ X2 + H2 and MgH2 ↔ Mg + H2. The X2 phase has a stoichiometric composition of
Mg70In15Ni15 with tetragonal structure, a reversible hydrogen storage capacity of ca. 1.8 wt.% and desorption enthalpy of
71.29 kJ/molH are determined.

Introduction
Mg is considered to be a promising metallic hydrogenstorage material with high capacity, abundant resource
and inexpensive price. However, the over-high operating
temperature due to unfavourable thermodynamics ofmagnesium hydride (MgH2) hinders its practicalapplications. Composition and structure modification
have been proven to be effective in improving thehydrogen storage properties of MgH2. For example, we
found that Mg(In) and Mg(In,Al) solid solutions could bereversibly formed by dehydriding from their hydrogenatedproducts with lowered desorption enthalpy [1]. Herein we
investigate the reversible phase transformation of Mg-InNi ternary alloys during de-/hydrogenation cycles, andtheir de-/hydriding thermodynamic and kinetic properties.

enthalpy of 71.29 kJ/molH are determined according to
the PCI results in Fig.1 (b).

Results
The Mg90In5Ni5 alloy was milled from the Mg(In) solid
solution and Ni powders for a rather long time (170h), theelemental Ni is still present. Upon hydrogenation, the
Mg90In5Ni5 alloy transforms to MgH2 and a new Mg-In-Ni
ternary phase X1. After dehydrogenation, Mg andanother new Mg-In-Ni ternary phase X2 are formed. This
X1  X2 phase transition could be reproduced after
more than five de-/re-hydrogenation cycles. The milled
Mg90In5Ni5 alloy shows excellent hydrogen desorption
kinetics, and the PCI testing could be carried out at a lowtemperature of 230 °C (see Fig.1 (a)).
The X2 phase is deduced to have a stoichiometry of
Mg70In15Ni15 with tetragonal structure, a reversiblehydrogen storage capacity of ca. 1.8 wt.% and desorption

Fig.1 The PCI curves for the hydrogen desorption of
Mg90In5Ni5 (a) and Mg70In15Ni15 (b).

References[1] H.C. Zhong, H. Wang, J. W. Liu, D. L. Sun, M. Zhu,
Scripta Materialia, 2011, 65, 285-287.

Yanshan Lu was born on June 1990 in Jiangxi, China. He received his BSc degree in metallic
materials science and engineering in 2011 from South China University of Technology.
At present, he is a Ph.D. candidate at the Key Laboratory of Advanced Energy Storage Materials of
Guangdong Province.
His research area is focused on Mg-based hydrogen storage alloys.

Yanshan Lu
Corresponding author: Min Zhu, email: memzhu@scut.edu.cn, Tel.: +86-20-87113924.

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CARBON-SUPPORTED NI3B NANOPARTICLES AS CATALYSTS FOR
HYDROGEN GENERATION FROM HYDROLYSIS OF AMMONIA BORANE
Xiaoling Shan, Fangyi Cheng, Jing Liang, Zhanliang Tao, Jun Chen*
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry; Collaborative
Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, China
Abstract: We report the preparation of Ni3B and carbon-supported Ni3B (denoted as Ni3B/C) nanoparticles and theircatalytic performance from hydrolytic dehydrogenation of ammonia borane (NH 3BH3, AB). The as-obtained Ni3B catalysts
are in well-defined crystalline state and the carbon-supported Ni3B catalysts have a high dispersion in the carbon. The
hydrogen generation measurement shows that Ni3B/C presents enhanced catalyst activity during hydrolytic
dehydrogenation of AB. Among the nanoparticles, Ni 3B/C with 34.25 wt% Ni3B loading displays the highest catalytic-1 -1-1activity, with a high hydrogen release rate of 1168 mL min g and low activation energy of 46.27 kJ mol .

Introduction
Hydrogen has been considered as an attractive
alternative energy carrier because of its abundance,high-energy density, and environmental friendliness [1].
For the known hydrogen storage materials, ammonia
borane (NH3BH3, AB) complex has been identified as oneof the most compelling candidates for chemical hydrogenstorage owing to its high hydrogen content (19.6 wt%)
and high stability at room temperature [2]. So far, many
metal catalysts have been reported for hydrogengeneration from hydrolysis of AB [3,4]. Herein, we
prepared non-precious Ni3B nanoparticles and carbonsupported Ni3B (Ni3B/C) catalysts with different loading
contents as catalysts for hydrolysis of AB. The asprepared carbon-supported Ni3B catalysts exhibit higher
catalytic activities for the hydrolysis of AB. This result
sheds light on the development of cheap catalysts for thehydrolysis of AB.

Preparation, characterization and hydrogengeneration measurement of the catalysts
The catalysts were prepared by a direct solution
synthesis route. The chemical reagents include nickel
chloride, potassium borohydride, tetraethylene glycol andcarbon black. Small sized and well dispersed Ni3B
nanoparticles were obtained by adding the supporting
carbon. The structure, morphology, and chemicalcomposition of the obtained samples are characterizedby X-ray diffraction (XRD), scanning electron microscope(SEM) and transmission electron microscopy (TEM). A
series of experiments were carried out in order toinvestigate the catalytic activities of the as-synthesizedcatalysts for hydrogen generation of AB aqueous solution.
The effects of carbon content, reaction temperature,amount of catalyst and concentration of AB on thehydrolysis reaction were studied in detail.

Conclusion
In summary, Ni3B and Ni3B/C catalysts have beensynthesized in solution with a modified polyol process. As
the catalyst for hydrogen generation of AB hydrolysis, theas-prepared Ni3B/C composites show significantly
enhanced catalytic activity in comparison with pure Ni3B
catalyst due to the reduced particle size and the welldispersed structure. In the Ni3B/C series, Ni3B/C with34.25 wt% Ni3B loading shows the highest catalytic
activity, affording hydrogen release rate exceeding 1100
-1 -1
omL min g at 25 C and low activation energy of 46.27-1
kJ mol . The results indicate that carbon-supported Ni3B
has the potential to be used as a low-cost catalyst for thehydrolysis of AB.

References[1] Schlapbach, L.; Züttel, A. Nature 2001, 414, 353.
[2] Li, P.; Aijaz, A.; Xu, Q. Angew Chem Int Ed 2012, 51,
6753.
[3] Peng, B.; Chen, J. Energy Environ Sci 2008, 1, 479.
[4] Huang, Z.; Autrey, T. Energy Environ Sci 2012, 5,9257.

Jun Chen
Fangyi Cheng
Zhanliang Tao
Jing Liang
Corresponding author: Jun Chen, email: chenabc@nankai.edu.cn, Tel: +86-22-23506808

Xiaoling Shan

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A SYNERGETIC EFFECT OF NANO-CONFINEMENT AND NANOCATALYSIS FOR THE ENHANCED REVERSIBLE HYDROGEN STORAGE
OF LIBH4
Jie Shao, Xuezhang Xiao, Xiulin Fan, Liuting Zhang, Shouquan Li, Hongwei Ge, Qidong
Wang, Lixin Chen*
State Key Laboratory of Silicon Materials, Key Laboratory of Advanced Materials and Applications for Batteries ofZhejiang Province, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China
LiBH4 has been infiltrated into highly ordered mesoporous carbon scaffold containing dispersed NbF5 nanoparticles toinvestigate the possible synergetic effect of nano-confinement and nano-catalysis on the reversible hydrogen storage
performance of LiBH4. A systematic study shows that the onset desorption temperature for nano-confined LiBH4@MCNbF5 system is reduced to 150 °C, 225 °C lower than that of the bulk LiBH4. The activation energy of hydrogen
desorption is reduced from 189.4 kJ mol-1 for bulk LiBH4 to 97.8 kJ mol-1 for LiBH4@MC-NbF5 sample. Furthermore,rehydrogenation of LiBH4 is achieved under mild conditions (200 °C and 60 bar H2). These results are attributed to theactive Nb-containing species (NbHx and NbB2) and the function of F anions, as well as the nanosized pores and highspecific surface area of the MC scaffold, which facilitates the dissociation, diffusion and recombination of hydrogenmolecules on the surface and grain boundaries. The combination of nano-confinement and nano-catalysis may develop
to become an important strategy within the nanotechnology for improving reversible hydrogen storage properties ofvarious complex hydrides.

Introduction
Intensive interest has arisen on complex hydrides,
especially for LiBH4, owing to its high gravimetric andvolumetric hydrogen capacities. Unfortunately, highthermostability, sluggish kinetics and undesirable
rehydrogenation conditions limit its practical application
as a hydrogen storage medium. Herein, we report aneffective strategy to modify both kinetics andthermodynamics of LiBH4 by combining nanoconfinement and NbF5 nano-catalysis, which shows afavorable synergetic effect on the reversible hydrogenstorage of LiBH4.

between nano-confinement and NbF5 addition. The
combination of nano-confinement and functionalized
nanoporous scaffolds may develop to become an
important strategy within the nanotechnology for
improving properties of variety complex hydrides.

Results
The results show that the onset desorption temperaturefor nano-confined LiBH4@MC-NbF5 system reduces to
150 °C, 225 °C lower than that of the bulk LiBH4. More
importantly, rehydrogenation of LiBH4 is achieved at
200 °C and 60 bar H2, which are the lowest conditions
reported to date. The activation energy of hydrogen-1
desorption is reduced from 189.4 kJ mol for bulk LiBH4-1
to 97.8 kJ mol for LiBH4@MC-NbF5 sample, indicating a
reduced kinetic barrier. All these have been
demonstrated that there is a favorable synergetic effect

References[1] J. Shao, X. Z. Xiao, L. X. Chen, X. L. Fan, S. Q. Li, H.
W. Ge and Q. D. Wang, J Mater Chem, 2012, 22,20764-20772.
[2] T. K. Nielsen, M. Polanski, D. Zasada, P. Javadian, F.
Besenbacher, J. Bystrzycki, J. Skibsted and T. R.
Jensen, Acs Nano, 2011, 5, 4056-4064.

Jie Shao is currently pursuing his
Ph.D. in Department of Materials
Science and Engineering at theZhejiang
University
under
the
supervision of Prof. Lixin Chen. His
current research interests are thebasic researches and applications on
renewable energy storage materials.
Jie Shao

Lixin Chen received his Ph.D. in
Department of Materials Science andEngineering from Zhejiang University in
2000. He joined Zhejiang University as alecturer in 1992 and became a Professor
in 2005. His research is focused onenergy materials for hydrogen storage
and hydrogen energy technologies.
Lixin Chen

Corresponding author: Lixin Chen, lxchen@zju.edu.cn, 86-0571-87951152.

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Effect of the LaFeO3 on the hydrogenation/dehydrogenation propertiesof MgH2
Ying Chengb, Yuan Li b, Wei Zhang b, Zhibin Wangb, Shumin Han a, b, *abState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, P. R. China
Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao 066004, P. R. China

Abstract: In order to improve hydrogen properties of magnesium hydride, the novel additive LaFeO3 was used to forming
MgH2 +20 wt.% LaFeO3 composite by mechanically milling method. P-C-T tests indicated the MgH2+20 wt.% LaFeO3
composite could absorb 3.417 wt.% of hydrogen at 423 K within 21 min while the MgH2 is only 0.977 wt.% under thesame condition. The MgH2+20 wt.% LaFeO3 also presented excellent dehydrogenation properties with 3.894 wt.% ofhydrogen released at 623 K, which was almost twice than the MgH2. The TPD measurement showed that the onset
dissociation temperature of the MgH2+20 wt.% LaFeO3 composite was 570 K, which was decreased 80 K with respect tothe MgH2. From the Kissinger plot analysis of the MgH2 +20 wt.% LaFeO3 composite, the activation energy Edes forhydrogen desorption process was estimated to be 86.69 kJ/mol, which was 36 kJ/mol lower than that of MgH2. The newadditive LaFeO3 was not only beneficial to the reduction of the particle size but also acted as an inhibitor to keep theparticles from clustering during the ball-milled process, which was responsible for the improved hydrogenationdehydrogenation properties of MgH2 +20 wt.% LaFeO3 system [1-2].

0.0

423K MgH2+20 wt.% LaFeO3
423K MgH2

3.5

(b)

(a)

-1.0

2.5

Hydrogen content/wt.%

Hydrogen content/wt.%

623K MgH2 +20 wt.% LaFeO3
623K MgH2

-0.5

3.0

2.0
1.5
1.0

-1.5
-2.0

(b)

-2.5
-3.0
-3.5

0.5

-4.0

0.0
0

200

400

600

800

1000

1200

1400

0

200

400

600

800

1000

1200

t/s

t/s

Fig.1 Hydrogen curves of MgH2+20 wt.%
LaFeO3 composite and MgH2 at 423 K

Fig.2 Dehydrogenation curves of the
MgH2+20 wt.% LaFeO3 composite andMgH2 at 623 K

1400

References[1] Jia, YH, Han, SM., Zhang, W., Zhao, X., Sun, P., Liu,Y., Shi, H., and Wang, JS. Hydrogen absorption anddesorption kinetics of MgH2 catalyzed by MoS2 andMoO2, International Journal of Hydrogen Energy,
38(5), 2013 2352-2356.

[2] Wei Zhang, Ying Cheng, Shumin Han , Xin Zhao,
Ziyang Zhao, Dan Liang, Yaru Pei, Na Shen. Effect of
the LaFeO3 on the hydrogenation/dehydrogenation
properties of MgH2 International Journal of Hydrogen
Energy.

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials,
and rare earth chemistry.
In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogenstorage alloys, light weight hydrogen strorage materials and rare earth–Mg–Ni-based electrodematerials.
Shumin Han
Corresponding author: Shumin Han, Email: hanshm@ysu.edu.cn

Tel./fax: +86-335-8074648

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Structural Characteristics and Hydrogen Storage Properties of Sm2Co7
ZJ. Caoa,b, LZ. Ouyanga,b*, H. Wanga,b, JW. Liua,b, M. Zhua,baSchool of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, Chinab

Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou, 510641, China

Abstract: The Structural characteristics and hydrogen storage properties of Sm2Co7 alloy were investigated by X-ray
diffraction and PCI measurement. Two plateaus were clearly observed in the PCI curves where the first and second
plateaus corresponded to Sm2Co7H2.9 and Sm2Co7H6.4, respectively, and their desorption enthalpy changes were 42.0
and 48.5 kJ/mol H2, respectively. Sm2Co7 showed an excellent cycle stability without obvious capacity loss after 50thhydrogenation and dehydrogenation cycles. Sm2Co7 displayed very quick hydrogenation kinetics at ambient temperature,and the hydrogenation process followed a three-dimensional interface controlled reaction.

Introduction
Among the family of intermettallics, R2Co7 (R= rare earth
element) have attracted interest due to their applications
as permanent magnets. Apostolov et al. [1] ever reported
the magnetic properties of the compounds R2Co7 (R = Pr,
Sm, Ho and Tb), but they only paid attention to themagnetic properties of the hydrides with hydrogenconcentration corresponding to β and γ phases. Sm2Co7
was also found to be able to act as hydrogen acceptors
in the dehydrogenation of methanol [2]. In this study, we
attempted to synthesize Sm2Co7 and study its structuralcharacteristics and hydrogen storage properties.

the PCI curves where the first and second plateauscorresponded
to
Sm2Co7H2.9
and
Sm2Co7H6.4,
respectively, and their desorption enthalpy changes were42.0 and 48.5 kJ/mol H2, respectively. Sm2Co7 showed
an excellent cycle stability without obvious capacity loss
after 50th hydrogenation and dehydrogenation cycles.
This alloy also displayed very quick hydrogenation
kinetics at ambient temperature, and the hydrogenation
process followed a three-dimensional interface controlled
reaction.

Experimental details
The Sm2Co7 alloy was prepared by arc-melting Sm(99.9%) with Co (99.9%) under a high under an
atmosphere of high-purity argon (99.999%). The crystal
structures of these samples were determined by X-ray
diffraction (XRD) analysis using a Philips X’pert-MPD
instrument
equipped
with
Cu-Kα
radiation.The
thermodynamics of Sm2Co7 determined by the P-C
isotherms and its kinetic curves were evaluated on an
Advanced Materials Corporation (AMC) gas reaction.

Fig. 1. (a) Rietveld refinement of the observed XRD
pattern for the as-prepared Sm2Co7 alloy, (b)Pressurecomposition isotherm curves for the Sm2Co7-H
system at the temperatures between 348 K and 453 K.

Conclusions

References

The as-melted alloy was composed of Sm2Co7 phase,and a small amount of SmCo5 phase. The Sm2Co7 alloy
consisted of double layers of hexagonal structural blocks
for CaCu5-type SmCo5 alternating with double layers of
MgCu2-type cubic blocks SmCo2 along the common
hexagonal axis. Two plateaus were clearly observed in[1] Apostolovlb A, Stanev, Mydlafcz T. J Magn Magn
Mater. 1990;83:286-8.
[2] Imamura H, Takada T, Kasahara S, Tsuchiya S. Appl
Catal. 1990;58:165-73.

Born 13.9.1989 in jiangxi, China. In 2011 he received BSc degree in Materials Science andEngineering from Beifang University of Nationalities. Since 2012 he is a Ph.D. candidate inMaterials Processing from the South China University of Technology under Liu Zhang Ouyang.
His research is focused on the hydrogen storage materials with high dissociation pressure in the
Key Laboratory of Advanced Energy Storage Materials of Guangdong Province.

Zhijie Cao
Corresponding author: Liu Zhang Ouyang, email: meouyang@scut.edu.cn, Tel. : +86 2087114253.

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Investigation of the Thermodynamic and Kinetic Properties of La-Fe-B System
Hydrogen-storage Alloys
W. Xiong a, b, B. Q. Li a, b, L. Wang a, b, J. Li a, b, F. Q. Kong a, b, H. Z. Yan a, b,
aBaotou Research Institute of Rare Earths, Baotou 014030, PR China;b

National Engineering Research Center of Rare Earth Metallurgy and Functional Materials, Baotou
014030, PR China

Abstract : Alloys of three different chemical compositions obtained by the partial
replacement of iron and boron in La8Fe27B24, La15Fe77B8 and La17Fe76B7 by nickel,
manganese and aluminium were investigated in this work: La8Fe1.5Ni42B1.5Mn5Al,
La15Fe2Ni72Mn7B2Al2 and La17Fe3Ni73B2Mn3Al2. Based on their La content, the three alloys
were denoted L8, L15 and L17, respectively. La-Fe-B hydrogen-storage alloys wereprepared using a vacuum induction-quenching furnace with a rotating copper wheel. The
thermodynamic and kinetic properties of the La-Fe-B hydrogen-storage alloys were
investigated in this work. The P–C–I curves of the La-Fe-B alloys were measured over a
H2 pressure range of 10−3 MPa to 2.0 MPa at temperatures of 313, 328, 343 and 353 K.
The P–C–I curves revealed that the maximum hydrogen-storage capacity of the alloys
exceeded 1.23 wt% at a pressure of approximately 1.0 MPa and temperature of 313 K.
The standard enthalpy of formation ΔH and standard entropy of formation ΔS for thealloys’ hydrides, obtained according to the van′t Hoff equation, were consistent with theirapplication as anode materials in alkaline media. The alloys also exhibited goodabsorption/desorption kinetics at room temperature.
Table
Thermodynamic parameters of the three La-Fe-B hydrogen storage alloys.
Alloys

La/Fe+B-1
ΔH/kJ·mol H2-1-1
ΔS/J·K ·mol H2-1
ΔG/kJ·mol H2 (298 K)

Absorption

Desorption

Absorption

Desorption

Absorption

Desorption

L8

0.08

-37.8738.54-98.45

97.29

-8.52

9.53

L15

0.18

-39.5438.62-98.1392.96-10.28

10.90

L17

0.20

-36.72

40.23-89.3898.72-10.0710.80

Corresponding author. Tel.: +86-472-5179370; Fax: +86-472-5179370;

E-mail: yhzmail@126.com (H. Z. Yan)
Postal address: Baotou Research Institute of Rare Earths, No. 36, Huanghe
Street, Rare Earth Development Zone, Baotou 014030, P.R. China

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THEORETICAL INVESTIGATIONS ON THE STRUCTURAL STABILITIESOF MAGNESIUM NANOSTRUCTURES AND THE APPLICATIONS FOR
HYDROGEN STORAGE
Xiao-Bao Yang, Jia-Jun Tang and Yu-Jun Zhao
Department of Physics, South China University of Technology, Guangzhou 510640, P. R. China
Key Laboratory of Clean Energy Materials of Guangdong Higher Education Institute, South China University ofTechnology, Guangzhou 510640, P. R. China

Abstract Magnesium (Mg), which is fairly accessible at low cost, is a promising hydrogen carrying medium for the
onboard applications due to the high gravimetric hydrogen content, high volumetric density, and the highest energy
density. However, there are two main hurdles for MgH2 for practical usage: (i) slow kinetics in the reaction ofhydrogenation, which may account for surface oxidation of magnesium, low dissociation rate of H2 on magnesium
surface, and hydrogen penetration blocking induced by a surface magnesium hydride layer; (ii) a high temperature of
350−400 °C and a high hydrogen pressure of more than 3 MPa are required for the hydrogenation and dehydrogenation
reactions, which is ascribed to its high thermodynamic stability.Both theoretical [1] and experimental [2] investigations
showed that nanostructuring of magnesium materials provides rapid storage kinetics, especially in the hydrogen
desorption process, since it lowered the activation energies of hydrogenation and dehydrogenation.
In our recent study [3], we have studied hydrogen adsorption on the Mg(0001) surface under biaxial strain, using densityfunctional theory calculations. A phase diagram is obtained for an intuitive sense of how the strain and hydrogenchemical potential affect the structural stabilities of Mg−H system. It is found that the compressive (negative) strains
facilitate the formation of the H−Mg−H tri-layers, a precursor of the transition to magnesium hydride, due to the fact thatthe lattice constant of H−Mg−H tri-layer is shorter than that of pure Mg.
Besides the thin film and surface of Mg, we use the bond energy model to estimate the structural stabilities of Mg nanoclusters. According to the Generalized Wulff Construction [4], the stabilities of clusters depend on the contributions of
inner atoms, surface atoms and the edges. We describe the cluster with the number of various kinds of bonds andsearch the possible structures through the Wang-Landau method. We will finally determine the stable Mg clusters withvarious size and investigate the hydrogen storage in these stable clusters.

References[1] Rudy W. P. Wagemans, Joop H. van Lenthe, Petra E. de Jongh, A. Jos van Dillen, and Krijn P. de Jong, Hydrogen
Storage in Magnesium Clusters: Quantum Chemical Study, J. AM. CHEM. SOC. 2005, 127, 16675[2] Jeon, K. J.; Moon, H. R.; Ruminski, A. M.; Jiang, B.; Kisielowski, C.; Bardhan, R.; Urban, J. J. Air-stable magnesium
nanocomposites provide rapid and high-capacity hydrogen storage without using heavy-metal catalysts, Nat. Mater.
2011, 10, 286[3] Jia-Jun Tang, Xiao-Bao Yang, Ming Chen, Min Zhu, and Yu-Jun Zhao, First-Principles Study of Biaxial Strain Effecton Hydrogen Adsorbed Mg (0001) Surface, J. Phys. Chem. C.2012, 116, 14943[4] S. F. Li, X. J. Zhao, X. S. Xu, Y. F. Gao, and Zhenyu Zhang, Stacking Principles and Magic Sizes of Transition Metal
Nanoclusters Based on Generalized Wulff Construction, Phys. Rev. Lett. 2013, 111, 115501

1999.9-2003.7 B. Sc., Department of Physics, Tsinghua University
2003.9-2008.1 Ph. D., Department of Physics, Tsinghua University
2008.1-2010.6 Postdoc., City University of Hong Kong
2010.7-2012.7 Associate Prof. Department of Physics, South China University of Technology
2012.8-present Prof. Department of Physics, South China University of Technology
Xiao-Bao Yang
Corresponding author: Xiao-Bao Yang, scxbyang@scut.edu.cn, 020-87110427.

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Increased air stability and decreased dehydrogenation temperature of
LiBH4 via modification within poly(methylmethacrylate)
Jianmei Huang, Yurong Yan, Liuzhang Ouyang*, Hui Wang, Jiangwen Liu, Min Zhu
School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, People’s
Republic of China;
Abstract: An air-stable LiBH4 polymeric composite was successfully prepared by modifying LiBH4 with a gas-barrier
polymer matrix--Poly (methylmethacrylate) (PMMA). The nanoconfinement of LiBH4 in the PMMA network pore structure
leaded to fast H2 release from LiBH4 molecules at low temperature. Meanwhile, PMMA can not only protect LiBH4 fromwater and oxygen but also let hydrogen get in and out freely. LiBH4@PMMA composite show the good hydrogenoodesorption property, which started to dehydrogenate at 53 C and released 5.2 wt.% of hydrogen at 162 C within 1 h. It
could be concluded that PMMA can increase the stability of LiBH4 in the atmosphere and reduce the dehydrogenation
temperatureof
LiBH4.

Introduction
Nanoengineering had been demonstrated to be a useful
methodtoreducethedehydriding/rehydriding
temperature of LiBH4. Nanoscale LiBH4 is too reactive,
so it is necessary to stabilize it for commercial utilization.
PMMA had the better gas selectivity than othercommonly polymer, with a high permeability ratio of[1]
H2/O2 . Hence, it was used in hydrogen storage to keepaway the water and oxygen but let the hydrogen get in orout freely. In this work, LiBH4 was nanoconfined by
PMMA with fine network pore structure for the first time,
which protected from the water and oxygen anddecreased the dehydrogenation temperature significantly(scheme1).

weaker and completely disappeared in the end. The firstpeak could be contributed to decomposing behavior of
the LiBH4 nanoconfined by the PMMA network pore
structure, and the second peak was corresponding to theunconfined LiBH4 outside the PMMA network pore
structure. The above results confirmed that PMMA canprotect LiBH4 from the water and air but let the hydrogen
get out freely, and significantly lower the stability of LiBH4.
Morever, comparing with that the pure LiBH4 onlyoreleased 0.6 wt.% of H2 within 4 h at 260 C,
LiBH4@PMMA composites could release 5.2 wt.% ofhydrogen in 1 h and 5.6 wt.% of hydrogen in 4 h at 162oC, respectively.

Figure 1. MS hydrogensignals of the LiBH4@PMMA
composite(c) and after
exposure the LiBH4@PMMA
composite to air for 1h (d),4h (e), 8h (f). compared withthe pure PMMA (a) and
LiBH4(b).

Scheme 1. Schematic
illustration of LiBH4
protected from oxygen
and water by PMMA

Result
The LiBH4 particles had a diameter distribution of 19-73
nm in the crosslinked network pore structure of PMMA,and showed an amorphous structure. The resuts
indicated that the particle size of LiBH4 was significantly
refined by modifying with PMMA. The LiBH4@PMMAocomposite presents a lower onset temperature of 53 C,
and with two mian dehydrogenation peaks (figure 1). As
the exposure time extending, the intensity of peak at 360o
C became

References[1] K. J. Jeon, H. R. Moon, A. M. Ruminski, B. Jiang, C.
Kisielowski, R. Bardhan and J. J. Urban, Nat. Mater.,
2011, 10, 286.

Jianmei Huang is a PhD candidate in Materials Processing from the South China University ofTechnology. Her current research interests are focused on the metal borohydrides for hydrogenstorage.

Jianmei Huang
Corresponding author: Liuzhang Ouyang, meouyang@scut.edu.cn, +86 2087114253

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TOWARDS EASY AND FULLY REVERSIBLE DEHYDROGENATION OF
LIBH4 BY CATALYZING OF HIERARCHIC NANOSTRUCTURED COB
Weitong
Cai1,2,
Hui
Wang1,2,
Wang3,*,LiuzhangOuyang1,2, Min Zhu1,2,*

Jiangwen

Liu1,2,Lifang

Jiao3,

Yijing1 School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P.R.China
2 Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou 510640, P. R. China
3 Institute of New Material Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai
University, Tianjin 300071, P. R. China
Abstract: LiBH4 is one of the most promising hydrogen storage materials due to its high gravimetric hydrogen density
3(18.5wt.%) and volumetric density (121kg/m )[1,2]. However, LiBH4 suffers from high thermodynamic stability, kinetics
barriers and the resultant poor irreversibility which hinder its practical utilization. In this work, hierarchic nanostructured
rod-like, flake-like, chain-like, waxberry-like and mulberry-like CoB catalyst was synthesised and doped into LiBH4 by ball
milling. It was revealed that CoB possessed extraordinary catalytic effect, dependent on its morphology, to improve thehydrogen storage properties of LiBH4. Its dehydrogenation was dramatically facilitated under lower temperature, and therehydrogenation was easily realized under mild conditions. Almost full reversibility was achieved with the assistance ofmulberry-like CoB.

Hydrogen storage properties of LiBH4-CoB
systemNanostructured CoB with different morphology of rodlike, flake-like, chain-like, waxberry-like and mulberry-like,
was synthesized by controlling chemical reduction
method[3], and then was mechanically milled with LiBH4
in a weight ratio of 1:1. Figure 1 shows thedehydrogenation kinetics of LiBH4-CoB system. It was
found that CoB played as a pure catalyst facilitating thedehydrogenation of LiBH4, and its morphology influenced
greatly catalytic activity. The catalytic effect of those CoB
is approximately in the order of mulberry-like > waxberrylike > chain-like > flake-like > rod-like, which is inaccordance with their specific surface area from high tolow. This led to the different dehydrogenation
performance of those CoB doped LiBH4 at 350°C. Among
those nanostructured CoB, mulberry-like CoB showed
the best catalytic effect. With its catalyzing, 10.4wt.%
hydrogen was liberated from LiBH4 with 1 h, which was
faster than that of pristine LiBH4 (Figure 1 left). By tuning
the rehydrogenation conditions of hydrogen pressure andtemperature, a almost full reversibility was achieved
under 400°C and 10MPa, remaining stable 9.6wt.%
hydrogen capacity at the fourth cycle (Figure 1 right).
Conclusively, almost fully reversible dehydrogenation of

LiBH4 has been realized under rather mild condition byusing nanostructured CoB catalyst.

Figure 1 Dehydrogenation kinetics of LiBH4-CoB systemwith different morphology (left), cyclic dehydrogenation ofmulberry-like CoB doped LiBH4 (right). Hydrogencapacity was calculated with respect to LiBH4.

References[1] L. Schlapbach, A. Züttel. Nature, 2001, 414, 353-358.
[2] P. Chen, M.Zhu. Materials today, 2008, 11, 36-43.
[3] Q. H. Wang, L. F. Jiao, H. M. Du, D. W. Song, W. X.
Peng, Y. C. Si, Y. J. Wang, H. T. Yuan.
Electrochimica Acta, 2010, 55, 7199-70203.

WeitongCai was born on 20 Nov. 1986 in Guangdong, P. R. China. 2005 Bachelor in School ofMaterials Science and Engineering, South China University of Technology, Guangzhou 510640,
P.R.China.
At present, he is a Ph.D. candidate at the Key Laboratory of Advanced Energy Storage Materials of
Guangdong Province, Guangzhou 510640, P. R. China.
His research field is complex hydrides (LiBH4).
WeitongCai
Corresponding authors: Min Zhu, memzhu@scut.edu.cn, +86-20-87113924; Yijing Wang, wangyj@scut.edu.cn, +86-2223503639.

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

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

Ronald Griessen has investigated the thermodynamics of palladium films and theisotope effect on the electronic structure of hydrides. Furthermore, the effect ofanharmonicity and Debye-Waller factor on superconductivity of PdHx and PdDx havebeen studied by Ronald before he developed a semi-empirical model for the heat ofsolution of hydrogen in transition metals. He also studied the trapping energy forhydrogen on lattice defects as well as the heat of solution of disordered transition
metals. The volume expansion upon hydrogen absorption, the Gorsky-effect, thediffusion, 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 under high hydrogen pressure in a diamond anvil cell, Ronald has discovered
the switchable optical properties of yttrium and lanthanum hydride films. This has thenstimulated Ronald to investigate thin films with optical methods and to develop new
methods for the combinatorial search of new hydride phases as well as for thedetermination of the thermodynamic parameters e.g. stability and kinetics of thehydrides. Furthermore, new applications for hydrides as hydrogen detectors and opticalfilters have been developed in his group.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2008
Louis Schlapbach, born March 4, 1944 in Belp Switzerland. He
graduated from the Swiss Federal Institute of Technology Zurich(ETHZ) in Experimental Physics and got his PhD in Solid State
Physics – Magnetism also at ETHZ. As a postdoc at a CNRS
laboratory in Paris, he studied hydrogen storage in intermetallic
compounds. Back at ETHZ, he developed the surface science
aspects of the hydrogen interaction with metals and alloys. From1988 till 2001, Louis Schlapbach was Full Professor for Physics
at the University of Fribourg. As such he built up a research teamof 20-25 people working on the topic „New Materials and theirSurfaces“ resulting in about 40 PhD, 200 scientific papers andsome patents. A strong collaboration with industry wasestablished. In spring 2001, he has been appointed CEO of
Empa, the materials science and technology institution of theProf. Dr. Louis Schlapbach ETH domain with 750 coworkers in Dübendorf, St. Gallen and
Thun.

Louis Schlapbach started his scientific work in 1970, 38 years ago, with theinvestigation of the Hall effect, electrical transport and magnetic susceptibility of liquid
rear earth elements like Cerium. 30 years ago in 1970 he was coauthor with Busch andWaldirich on a paper about the hydrides of La-Ni compounds. LaNi5 was subsequently
investigated in view of the structure, surface segregations, hydrogen occupation ofinterstitial sites and as electrode material.LaNi5 is still the base material for most of theelectrochemical applications of metal hydrides today. The work on LaNi 5 wascomplemented by the research on FeTi. Louis Schlapbach realized the importance ofthe surface composition for the hydrogen sorption process and he was able to describe
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 theformation of metallic clusters as superparamagnetic particles acting as the active sites
in hydrogen dissociation and recombination. The investigation of the surface of metal
hydrides was further intensified by means of X-ray photoelectron spectroscopy. Louis
Schlapbach was the first scientist correctly describing the activation process of a metal
hydride and, furthermore, to model the chemical composition and states of theelements in a surface profile. He also succeeded to analyze the electronic structure ofraere earth elements and their hydrides by means 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 and Development
Center, Suffern, NY. From 1983-1991 he was Vice President andDirector of Technology at Ergenics, Inc., Ringwood, NJ. From
1992-1993 Gary Sandrock was visiting professor at the Kogakuin
University, Hachioji, Tokyo, Japan where he developed a newchemical surface treatment and investigated the activation
characteristics of chemical treated AB5 alloys. Gary then became
the president of SunaTech, Inc., Ringwood, NJ, where hedeveloped reversible hydrogen storage systems. At the sametime Gary Operating Agent, International Energy Agency
Hydrogen Implementing agreement Tasks 12 & 17 (Hydrogen
Storage Materials) and worked as a consultant for the US DOE
via Sandia National Laboratories, Livermore, CA.

In 1995 Gary Sandrock started to creat and mainten Hydride Databases of
IEA(HIA)/DOE/SNL (http://hydpark.ca.sandia.gov) and he is author of several bookchapters 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 most recently Gary investigated thehydrogen desorption behavior of AlH3 and explaned the mechanism 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 ina controlled 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 the hydride 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 and wasaffiliated with Nordita, (Nordic Institute for Theoretical Physics) in
Copenhagen before he became a member of the scientific staff ofHaldor Topsøe A/S, Lyngby in 1981. He continued theinvestigation of gas molecules at the surface of metals anddeveloped a picture of adsorption and desorption of hydrogenemerging from self-consistent model calculations. In 1992 he wasappointed as a professor of theoretical physics in the departmentof physics at the Technical University of Denmark, Lyngby andbecame the director of the Center for Atomic-scale Materials
Physics (CAMP), Department of Physics, Technical University ofDenmark, Lyngby.

Recent research of the group of Jens Norskov covers several of the most relevant
topics: 1) The development of theoretical methods e.g. “Scaling Properties of
Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces”;
2) Theoretical surface science e.g. “Role of strain and ligand effects in the modificationof the electronic and chemical properties of bimetallic surfaces”; 3) Nanostructures andmaterials properties e.g. Atomic-scale imaging of carbon nanofiber growth”; 4)
Heterogeneous catalysis e.g. “Ammonia synthesis from first 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 fuel cell 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 the understanding 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
Rüdiger Bormann was born September, 14 1952 in Germany. He
received 1977 his diploma in physics (Metalphysics), from the
University Göttingen and 1979 his Dr. rer. nat. from the University
Göttingen. From 1981 to 1982 he was visiting scientist in theDept. of Applied Physics at Stanford University, U.S.A. From1982 to 1988 he was Assistant Professor (Hochschulassistent) at
the University Göttingen where he received the Habilitation
University Göttingen, venia legendi in 1988. From 1989 to 1997
he was Professor of Metalphysics (GKSS Research Centre,
Geesthacht and Hamburg University of Technology) and from1996 to 2009 he was director of the Institute for Materials
Research, GKSS Research Centre, Geesthacht and since 2009
he is Professor of Applied Materials Physics and President of theProf. Dr. Rüdiger Bormann University of Bayreuth. Rüdiger Bormann died on 13. January
2013 in an accident in Cologne, Germany.

Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses,
metastable crystalline and amorphous alloys as well as the thermodynamics andkinetics of the amorphous 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 a great step forward in the development ofhydrogen storage materials. Furthermore, very important was also the interpretation of
the role of the grain boundaries for the diffusion of hydrogen 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 of materials design forhydrogen storage. Therefore, we aword Prof. Rüdiger Bormann with the Science ofHydrogen & 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 director of
the Institute for Energy Research and Policy. Since 2008
he is Honorary Professor of Materials Science of the School ofMetallurgy and Materials at the University of Birmingham.

Prof. Dr. Ivor Rex Harris

For around 40 years, Rex Harris was leader of the Applied Alloy Chemistry Group(AACG) in Metallurgy and Materials. During this time he maintained a long-standing
research interest in 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 and application of the Hydrogen Decrepitation (HD) process tothe manufacture of NdFeB magnets. The HD process resulted in up to a 25% saving in
production cost and is now used world-wide in the fabrication of NdFeB sinteredmagnets. These materials are playing a vital role in the production of energy efficientelectric 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 researchalso made a very significant contribution to the development and understanding of theHydrogenation, Disproportionation, Desorption and Recombination (HDDR) process
which enabled 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 anumber of books. During these years he has successfully supervised around 120
postgraduate students, many of whom are still working in applied materials science andoccupy senior positions in industry, government and academia throughout the world.
Since stepping down as group leader and head of school he has focused his activities
on the application of NdFeB magnets and hydrogen storage materials to practicaldemonstrators such as the Ross Barlow hybrid canal boat. This zero- carbon emission
craft is serving to highlight the huge potential of magnets and hydrogen in 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 ofclimate change and resource depletion. He continues to be very active in this campaign
which he considers 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
Rainer Kirchheim was born May 24, 1943 in Halle/Saale,
Germany. He studied Physics at the University of Stuttgart from
1966-1971 and received the diploma for the work
“Electrochemical studies of oxygen solid solutions in high melting
metals” at the Max-Planck-Institut für Metallforschung/Universityof Stuttgart. He received his Ph.D. for the thesis entitled “Thermoand electrotransport of oxygen and nitrogen in Va metals “ fromthe
UniversityofStuttgart,
Max-Planck-Institut
fürMetallforschung in 1973. In 1988 he received the Habilitation“Measurements and modelling of hydrogen solubility anddiffusivity in disordered metal lattices“ from the University of
Stuttgart, Faculty of Chemistry Metallurgy.
Since 1993 he is Full Professor (Gustav Tamman Chair)Prof. Dr. Rainer Kirchheim University of Göttingen Göttingen Germany and Director GeorgAugust-Universitaet Goettingen, Institut für Materialphysik
Göttingen Germany .

Prof. Rainer Kirchheim has investigated 30 years ago oxygen in metals, especiallydiffusion, thermo-transport and thermo-power of oxygen in transition metals and alloys.
In 1980 he started to study diffusion of hydrogen in dillute alloys of copper and niobiumin palladium. He developed an electrochemical method for the measurement of thehydrogen diffusion in palladium and palladium alloys and performed fundamental
studies on the diffusion mechanism of interstitial species. The interaction of hydrogenwith dislocations in palladium and the interpretation with a model based on the FermiDirac distribution are of great importance for the understanding of the interstitial site
occupation of hydrogen in alloys and amorphous metals.
For the enormous contributions on the hydrogen dynamics and thermodynamics inmetals as well as the hydrogen interaction with dislocations, grain bounderies andinterfaces we award Prof. Rainer Kirchheim with the Science of Hydrogen & Energy
prize 2010.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2011
Koji Hashimoto was born October 23, 1935 in Japan. He received
the M. Sc. In Chemistry from the Faculty of Science of the Tohoku
University, Sendai, Japan. In 1966 he received the Doctor degreein sciences from the Tohoku University and in the same year hebecame an associate professor in the Institute for Materials
Research (IMR) of the Tohoku University. From 1967 to 1969 he
was a Post Doctorate Fellow in the Division of Applied Chemistryof the National Research Council in Canada.
From 1987 to 1999 he was a Professor in the Institute forMaterials Research (IMR) of the Tohoku University and from 1999
to 2006 he was Professor at the Tohoku Institute of Technology.

Prof. Dr. Koji Hashimoto

Prof. emeritus Koji Hashimoto has published over 520 papers in scientific journals in
addition to review articles and book chapters. He has worked on corrosion-resistantalloys, electrolysis, especially he pioneered the electrolysis of seawater. He tailored thecatalysts for carbon dioxide methanation, in particular, he has built a prototype plant for
global CO2 recycling in 1995 on the roof top of the Institute for Materials Research,
Tohoku University. The plant consists of power generation by photovoltaic cells,
hydrogen production by seawater electrolysis and methane formation by the reaction ofcarbon dioxide with hydrogen, carbon dioxide recovery at an energy consuming district,and transportation of carbon dioxide. The plant uses tailored key materials with highperformance and durability, that is, cathodes for hydrogen production, anodes for only
oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for
rapid and selective production of methane by the reaction of carbon dioxide withhydrogen. The performance of the plant has substantiated that global CO2 recycling
can supply abundant energy generated from solar energy on deserts in the form of
methane and can really prevent global warming induced by carbon dioxide emissions.
In 2003, he has built a pilot plant of global CO2 recycling at Tohoku Institute ofTechnology which is the minimum unit of industrial scale for seawater electrolysis andcarbon dioxide methanation.
He is in the Editorial Board of "Corrosion Science", a Member of NACE International,
the Electrochemical Society and the International Society of Electrochemistry. Memberof Japan Society of Corrosion Engineering, the Japan Institute of Metals, the Surface
Finishing Society of Japan, the Iron and Steel Institute of Japan, the Electrochemical
Society of Japan, the Society of Chemical Engineers, Japan, the Chemical Society ofJapan, and other scientific societies in Japan.
He received many awards among those also The Electrochemical Society Fellow
Award in 1997 in recognition of contribution to the advancement of science andtechnology, for leadership in electrochemical and solid state science and technology
and for active participation in the affairs of the Electrochemical Society, Inc.
We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogenand the use of hydrogen for the reduction of CO2 with the Science of Hydrogen &Energy prize 2011.
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SCIENCE OF HYDROGEN & ENERGY AWARD 2012
Mogens Mogenson is research professor in the fuel cells andsolid state chemistry division, Risø National Laboratory for
Sustainable Energy, Technical University of Denmark (DTU).
He has spent 37 years in electrochemistry. He received his
MSc in 1973 and PhD in 1976 from the Department ofMetallurgy, DTU. After a postdoctoral period at the
Department of Chemistry A, DTU, and a short period in thebattery industry (Hellesens A/S), he was employed at Risø
National Laboratory in 1980. He was manager for numerous
projects and programs (mainly within R&D of practicalelectrochemical cells such as solid oxide fuel cells) and now
the Strategic Electrochemistry Research Center (SERC). He
has coauthored more than 250 scientific papers and reports,and has 16 patents/patent applications.
Prof. Dr. Mogens MOGENSON
Prof. Mogens Mogensen from the Risø National Laboratory for sustainable Energy made anenormous contribution in the development for electrochemical systems like SOFCs (High
Temperature Solid Oxide Fuel cells), SOEC (Solid Oxide Electrolyser Cells) as well as oxygen
separation membranes over the last 20 years. His topics in this field include the material
development for electrodes, electrolytes as well as interconnects, coatings and sealing’s.
Mogens is known for his broad knowledge and understanding of the total systems andespecially the deep knowledge of the thermodynamics and electrochemical behavior of the cells.
The driving force behind his research activities are the principle understanding of the aging
mechanisms in SOEC and SOFC systems, the electrochemical behavior, but also thedevelopment of new materials for better performance and competitive prices. In the field ofadvanced materials he was very active and successful in the development of catalytic metaloxides with fluorite and perovskite related structures. These compounds are extremely flexible
with respect to substitution of host cations and non-stoichiometry. By this purpose he has done“material engineering” by tailoring the basic materials properties for aspects like high electronic
and ionic conductivity, matching thermal expansion coefficient, stability in hydrogen and/or
oxygen atmosphere, etc. The development of novel materials was leading to the “world record”
in power density for electrochemical cells, accompanied by a low aging- and degradation rate(>1%/1000h) and an outstanding mechanical strength and flexibility. Mogensen was also very
active in cells and stack development with high electrical efficiency and fuel flexibility including
natural gas, biogas, diesel, LPG, methanol, DME and ethanol.
Recently his topic and interest are the synthetic fuels derived from water and CO2. This isinteresting as the produced syngas (H2 + CO) can react to form methane, which is a moresuitable energy carrier. In this process, the catalytic process is taking place inside the cell, so
the reaction heat can be utilized.
We award Prof. Mogens Mogenson for his outstanding work on the electrochemistry ofelectrolysers and fuel cells with the Science of Hydrogen & Energy prize 2012.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2013
Graduated Nagoya University with Msc applied physics and
Bsc in physics..
Joined Toyota Motor Corporation in 1981, then working as
engineer in production engines and advanced engine
systems. Later working as Toyota Engine representative at
Toyota Europe in Brussels. Involved for first hybrid (Prius)development as manager for emission and fuel economy. In
later years working as a planner for world hybrid deployment.
From 2004 fuel cell development manager.
Currently project general manager at R&D management
division and Energy Affairs department.

Mr. Katsuhiko HIROSE

Katsuhiko HIROSE has a very important role in the development of hydrogen formobility by building the bridge between industry (Toyota) and academia as well as thebridge between Asia and Europe.
He initiate the hydrogen's economical value assessments. Hydrogen fuel is valuable forthe economy as well as for the environment. The value-chain analysis of Fuel Cellvehicles and Hydrogen Energy analysis identifies the big economical value of the useof hydrogen as a fuel. This analysis has re-ignited many activities on hydrogen all over
the world
He also initiated the H2Mobility activities and brought many OEM and stakeholder into
these activities. Resulting in the German H2mobility report. A portfolio of power-trains
for Europe: a fact-based analysis, which stimulated the hydrogen activities world wide
again.
The large number of key-note speeches in both engineering conference and academic
conference stand for his continuous efforts as an interpreter between the industries andacademic scientists.
He is responsable for the world leading research in hydrogen storage by means ofhybrid tank systems, i.e. the combination of pressurized hydrogen gas and metal
hydrides, which leads to a hydrogen storage with greater gravimetric and volumetrichydrogen density as compared to the individual system. Furthermore, he also
developed a Cryo-adsortion tank system.
We award Mr. Katsuhiko HIROSE for his outstanding work on the implementation ofhydrogen for mobility and for linking the key people worldwide together with the
Science of Hydrogen & Energy prize 2013.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2013
Hans Geerlings studied experimental physics in Amsterdam,
where he received his PhD degree in 1987. In that year hemoved to Shell, where he worked in research on a number of
topics including synthesis gas conversion, hydrogen storage
and CO2 capture and storage. In 2007 he was appointed asa part time professor at the Delft University of Technology.
His current research interests are in the area of ‘Solar Fuelsynthesis’ and ‘Mineralization of CO2’.

Prof. Dr. Hans GEERLINGS
Hans Geerlings has worked on complex hydrides, i.e. alanates, especially on the synthesis andthe characterization of MgAlH4 and CaAlH4, before he focused on the CO2 capture andmineralization. Recently, he published a paper in Environmental Science entitled “Efficient
Production of Solar Fuel Using Existing Large Scale Production Technologies” in which theefficient production of solar fuels today using existing technologies is described. The feasibilityof liquid hydrocarbon fuels production from CO2 and water with efficiencies approaching 10%
from solar energy is demonstrated, this is about an order of magnitude higher than alternativetechnologies currently under development. The reduction of CO2 with hydrogen for the
production of synthetic fuels is a new challenging research branch with an enormous potential
for the future energy economy.
We award Prof. Hans Geerlings for his outstanding work on the hydrogen production andstorage as well as his effort to open new fields in a world leading oil producing company with
the Science of Hydrogen & Energy prize 2013.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2014

Prof. Dr. Andreas ZÜTTEL

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering
Degree in Chemistry, Burgdorf, Switzerland. 1990 Diploma in
Physics from the Unversity of Fribourg (UniFR), Switzerland.
1993 Dr. rer. nat. from the science faculty UniFR. 1994 SNF
Post doc with AT&T Bell Labs in Murray Hill, New Jersey,
USA. 1997 Lecturer at the Physics Department UniFR. 2003
External professor at the Vrije Universiteit Amsterdam,
Netherlands. 2004 Habilitation in experimental physics at thescience faculty UniFR. President of the Swiss Hydrogen
Association „HYDROPOLE“. 2006 Head of the section“Hydrogen & Energy” at EMPA. Prof. tit. in the Physics
department UniFR. 2009 Guest Professor at IMR, Tohoku
University in Sendai, Japan. 2012 Visiting Professor at Delft
Technical University, The Netherlands

Andreas Züttel has worked on metal hydride electrodes and developed new overstoichiometric
AB2 Laves-phase alloys wher the B atoms partially occupy A-sites. He developed amathematical model for the capacity of a metal hydride electrode. With the discovery of carbon
nanotubes and first reports about the great hydrogen storage capacity of single wall carbon
nanotubes he started to investigated the interaction of hydrogen with nanostructures by meansof electrochemical sorption measurements and described the relationship between thehydrogen density and the materials surface area of nanostructures. Furthermore, the size
dependent hydrogen sorption properties of monodisperse Palladium clusters as small as 55
atoms were investigated electrochemically and modeled by A. Züttel. He intitiated the researchon borohydrides for hydrogen storage 10 years ago and published together with S.I. Orimo
important papers on the properties of borohydrides e.g. a model for the stability and thehydrogen sorption mechanism. Recently his activities have expanded to the reduction of CO2
with hydrogen for the production of synthetic hydrocarbons as fuels. This is the basis to closethe materials cycle for hydrocarbons as energy carriers.
We award Prof. Andreas Züttel for his outstanding work in the science on the interaction ofhydrogen with solids e.g. intermetallic compounds, nanostructures and complex hydrides with
the Science of Hydrogen & Energy prize 2014.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2014
Qidong Wang is a professor of Department of Materials Science andEngineering, Zhejiang University. He was born in 1921, and obtained
his BSc degree in 1943 from Zhejiang University of China, MSc degreein 1948 from Stanford University and PhD in 1951 in the University of
Iowa of USA, majoring in the heat power of mechanical engineering. He
returned China in January of 1951 to teach and do research in Zhejiang
University until he retired in 2011. His main research work focuses onhydrogen storage materials and their actual applications. Besides theresearching tasks and teaching, he has also done many administrativeand social services.

Prof. Qidong Wang
Prof. Qidong Wang from the Department of Materials Science and Engineering of Zhejiang
University was involved in the fields of mechanical engineering, metallurgical engineering andfunctional materials in his 60 years’ research career. He has made many outstanding
contributions in the topics such as process intensification of melting procedure in cupola,
precision casting of high speed steel cutting tools and developments of new hydrogen storage
materials and systems. In particular, he is well known as a pioneer in the development andapplications of hydrogen storage alloys in China. He has done a lot of excellent work in the
research fields of rare earth based hydrogen storage materials and new metal-hydride systems.
His research interests also focus on the purification and transportation of hydrogen as well as
Ni-MH batteries.
Since 1978 he devoted himself into the research on hydrogen storage alloys and compounds
and their applications for storing and transporting hydrogen and the use of hydrogen as
supplementary fuel for internal combustion engines. He firstly used lanthanum-rich mischmetal,
which has almost the same hydrogen storage capability but the cost of the alloy lowers by one
third, to replace the pure lanthanum. Moreover he firstly employed mechanical milling method toprepare mischmetal cathode materials for hydrogen storage batteries, which hereafter were
widely accepted by peers. He has contributed with his coworkers more than 500 scientificpapers and reports and he has 18 patents and more than 20 awards on his contributions inscientific researches, teaching and social contributions. So far, his scientific papers have been
cited more than 5000 times and his H-index reached as high as 33.
Even though at an advanced age, he is still concerning on the development of hydrogen
economy. His endurance and diligence are the merits we scientific workers should learn from.
We award Prof. Qidong Wang for his outstanding work on hydrogen storage materials andtheir applications with the Science of Hydrogen & Energy prize 2014.

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Zhaoqing, P.R. China 2014BEST POSTER AWARD 2011
Ms. Alondra TORRES TRUEBA“Hydrogen Storage in Structure II
Clathrate Hydrates with Various
Promoters”
Department of Process & Energy,
Delft University of Technology,
Delft, Netherlands

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

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

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Zhaoqing, P.R. China 2014BEST POSTER AWARD 2012
Mr. Andreas BLIERSBACH“How to Watch Hydrogen Diffuse in
any Absorbing Material”
Department of Physics andAstronomy, Materials Physics
Division, Uppsala University,
Sweden.
Born 1986 in Cologne, Germany.
2011 Diploma in physics at the
RheinischeFriedrich-Wilhelms
University Bonn, Germany. 2008 –2009 studies and research, as
exchange student, at Uppsala
University, Sweden. 2010 – 2011
research on hydrogen diffusion innano sized materials by direct
imaging at Uppsala University,
Sweden. Since December 2011
PhD student at EMPA, D bendorf,
Switzerland and involved in smart
carbon based hydrogen storage
materials.

“HOW TO WATCH HYDROGEN DIFFUSE IN ANY ABSORBING MATERIAL”
The kinetics of interstitial hydrogen are of great interest and importance for many technologies.
In particular nano-sized materials motivate fascinating applications and scientific questions.
Even though diffusion is one of the most studied phenomena the complex combination ofquantum effects and dynamic interplay with the displacement of host atoms [1,4] is still only
partially understood. We present a method to quantify chemical diffusion of hydrogen in nanosized materials. The changes in the absorptance of a vanadium single crystal thin-film, inducedby hydrogen, are observed visually and in real-time as a function of position. Concentration
profiles and their evolution in time, during chemical diffusion, can be measured down to ahydrogen content corresponding to just a few effective monolayers, randomly distributed within
VHx.

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Zhaoqing, P.R. China 2014BEST POSTER AWARD 2013
Mr. Moreno DE RESPINIS“Optimization of Anneal Procedure in Metal Oxides: Case
Study of Nanostructured Tungsten Processed via Low-Energy
Helium-Ions”
Delft University of Technology, Faculty of Applied Siences,
Department of Chemical Engineering, Materials for Energy
Conversion and Storage; Julianalaan 136, 2628 BL Delft, The
Netherlands
Moreno de Respinis received his bachelor degree in physics at
the University of Milan in 2008, and earned his master degree
in sustainable energy with study line hydrogen and fuel cells at
the Technical University of Denmark (DTU) in 2011. He
concluded his master with a fellowship at the Lawrence
Berkeley National Laboratory with Dr. Heinz M. Frei’s group, in
which he performed mechanistic studies of water photooxidation by visible-light driven Co3O4 catalyst. He is currently
a Ph.D. student at Delft University of Technology where he isresearching on photoanodes for solar water splitting.

“Optimization of Anneal Procedure in Metal Oxides: Case Study of Nanostructured
Tungsten Processed via Low-Energy Helium-Ions”
One challenge in developing highly efficient nanostructured photoelectrodes is to control theirmorphology, crystal phase and stoichiometry. We present a novel physical processing route thatuses high-flux of low-energy helium- ion to generate porous structures on tungsten targets.
Optimal anneal condition to form WO3 photoanode is determined via in-situ XRD. SEM images
show mesoporous crystalline structure, and feature sizes depend on substrate temperature andcan be tuned between 30 nm and 1 μm. Our research shows that a two-step anneal procedureis optimal to oxidize surface nanostructures into crystalline WO3, preserving the bulk as metallic
W for good electrical contact. As a result, IPCE of 20% is obtained, resulting in an AM1.5
photocurrent of 0.75 mA/cm2 at 1.23 VRHE (compared to 0.15 mA/cm2 after standard thermaloxidative anneal). The excellent control over feature size offers an exciting new processing
route to nanostructure materials for e.g. solar water splitting.

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PARTICIPANTS

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Name

Address

Phone / Fax / emailpDr. Liu BAOZHONG

Yanshan University
Dept. of Materials Science&Technology
438 Hebei street
CN-Qinhuangdao GUANGZHOU

Fax: 15225817609
email:
b_z_liu@163.com

69

Weitong CAI

School of Materials Science andEngineering,

107

South China University ofTechnology,

Mobile:+86

137

6089

2214
Email:caiweitong1986@1
63.com381 Wushan Road, Tianhe District,
Guangzhou 510640,China

Dr. Elsa CALLINIProf. Jun CHEN

Empa
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Duebendorf Dübendorf
Nankai Univ
Physics
No.94 Weijin Road
DK-Tianjin Kongens Lyngby

email:
elsa.callini@empa.ch49

Tel: 86-22-23506808
Fax: 13821226868
email:
chenabc@nankai.edu.c
n

87

33
Prof. Dr. Ping CHEN

Dalian Institute of Chemical
Physics, Dalian, CHINA, 116023

Tel: 0411-84379905
Email:
pchen@dicp.ac.cn

Dr. Young Whan CHO

Korea Institute of Science andTechnology
iNANO, Chemistry Department
Hwarangno 14-gil 5, Seongbuk-gu
DK-Seoul 136-791 Aarhus

email: oze@kist.re.kr

1543
Mr. Hailiang CHU

Guilin University of Electronic
Technology
Science InstituteNo. 1 Jinji Road
IS-Guilin Reykjavik

email:
chuhailiang@guet.edu.cnMr. Moreno DE
RESPINISSUNUM
Julianalaan 136
TR-2628BL Istanbul

email:
m.derespinis@tudelft.nl

53

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Name

Address

Phone / Fax / emailpDr. Renaud DELMELLE

EMPA Materials Science &Technology
Physics
Ü berlandstrasse 129
NL-8600 Dübendorf Kortenhoef

Tel: +41 58 765 6541
email:
renaud.delmelle@empa.ch73

Mr. Fang FANG

Department of Chemical
Engineering
220 Handan Road, Shanghai
NL-Shanghai Delftemail:
f_fang@fudan.edu.cn

Prof Jin GUO

College of Physics Science andTechnology
Physics Department
Guangxi University, Nanning
530004, China
IT-530004,Nanning Parma

Fax: 13507713721
email:
guojin@gxu.edu.cn

Miss Sheng GUO

University of Birmingham
Department of physics andastronomy
Edgbaston
SE-Birmingham Uppsala

Fax: 447594622858
email:
sxg819@bham.ac.uk

Mr.Guotao WU

Dalian Institute of Chemical
Physics, Chinese Academy of
Sciences
457 Zhongshan Road
IT-Dalian 116023 Rome

Tel: -84379908
Fax: 13941120975
email: wgt@dicp.ac.cn

Prof. Shumin HAN

Yanshan University
438 Hebei street
NL-066004/Qinhuangdao Delft

Tel: -8074897
email:
hanshm@ysu.edu.cn

Asc. Prof. Teng HE

Dalian Institute of Chemical
Physics, Chinese Academy of
Sciences
Chemical Engineering
457#, Zhongshan Road, Dalian,
China
NL-116023 Delft

Tel: -84379908
Fax: -18642819956
email:
heteng@dicp.ac.cn

09

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Name

Address

Phone / Fax / emailpDr. Michael HIRSCHER

Max Planck Institute for Intelligent
Systems
Hydrogen & Energy
Heisenbergstr. 3
CH-70569 Stuttgart Dübendorf

Tel: 497116891808
email:
hirscher@is.mpg.de

17

Mrs. Fadime HOSOGLU

Empa
Institut Européen de Membranes
Uberlandstrasse 129
FR-Dubendorf Montpellier

Fax: 41763101185
email:
fadime.hosoglu@empa.
ch79

Dr. Cunke HUANG

College of Physics Science andTechnology
Department of Physics
College of Physics Science andTechnology, Guangxi University,
Nanning 530004, China
DK-530004,Nanning Kgs. Lyngby

Tel: 0771-3237386
Fax: 13647880085
email: hckcn@163.com

39

Prof. Huatang YUAN

Institute of New Energy Material
Chemistry,Nankai Uinversity
Institute of Materials Science ofSeville94 Weijing Road
ES-300071/Tianjin Sevilleemail:
yuanht@nankai.edu.cn

Dist. Prof. Puru JENA

Virginia Commonwealth University
Structural chemistry of solid body
Physics Department
UA-Richmond Kyiv

Tel: 8048288991
Fax: 8048188358
email: pjena@vcu.edu

Dr.Jianmei HUANG

School of Materials Science andEngineering, South China
University of Technology,
Guangzhou, 510641, People’s
Republic of China

Prof. Jiangwen LIU

Key Laboratory of Advanced
Energy Storage Materials of
Guangdong Province, South China
University of Technology,
Guangzhou 510640, China

61

21

Tel.: +86-20-87112830.
Email:

67

mejwliu@scut.edu.cn

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8th Int. Symposium Hydrogen & Energy

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Name

Address

Phone / Fax / emailpProf. Hannes JÓ NSSON

University of Iceland
Institute for Material Sciences ofSevilleFaculty of Physical Sciences, VR-III
ES-Reykjavik SevillaTel: 3545254643
Fax: 3548923560
email: hj@hi.is

45

Dr. Xiangdong KANG

Institute of Metal Research,
Chinese Academy of Sciences
Hydrogen & Energy
72 Wenhua Road, Shenhe District
CH-Shenyang Dübendorf

Tel: 86-24-8397 0722
Fax: 13898800081
email:
xdkang@imr.ac.cn

Ms. Guanqiao LI

Tohoku University
Hydrogen & Energy
Katahira 2-1-1, Aoba ku
CH-9808577 / Sendai Dübendorf

Tel: -2250
Fax: -6694
email:
likk@imr.tohoku.ac.jp

Prof. Liquan LI

Nanjing University of Technology
Inorganic Chemistry and Catalysis
5 Xinmofan Road
NL-210009/Nanjing Utrecht

Tel: 025-83587255
email: lilq@njut.edu.cn

Dr. Ping LI

University of Science andTechnology Beijing
SB ISICxueyuan road 30,haidian,beijing
CH-100081/Beijing Lausanneemail:
liping@ustb.edu.cn

Mr. Yongtao LI

Anhui University of Technology
Hydrogen & Energy
Hudong Road
CH-Manshan Dübendorf

email:
lyt2013@ahut.edu.cn

71

Dr. Yuan LI

Yanshan University
Physics
438 HEBEI STREET
IT-066004/Qinhuangdao Parma

email:
liyuan@ysu.edu.cn

57

Prof. Yongfeng LIU

Zhejiang University
Dept. Physics and Astronomy
Department of Materials Scienceand Engineering, Zhejiang
University
IT-Hangzhou Bologna

Tel: 8657187952615
Fax: 8657190000000
email:
mselyf@zju.edu.cn

11

65

85

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Name

Address

Phone / Fax / emailpProf. Dr. Liuzhang
OUYANGSouth China University ofTechnology Dept. of Materials
Science&Technology
Tianhe Zone,Wushan Street CN510640 Guangzhou

Tel:00862087114253
Fax:00862087111317
Email:meouyang@scut.
edu.cnMobile:13143778049

75

Prof. Shin-ichi ORIMO

WPI-AIMR / Institute for Materials
Research
Hydrogen & Energy
2-1-1 Katahira, Aoba-ku
CH-Sendai / 980-8577 Dübendorf

email:
orimo@imr.tohoku.ac.jp

77

Prof. Hongge PAN

Zhejiang University
Laboratoire d'Electrochimie
Physique et Analytique
Department of Materials Scienceand Engineering, Zhejiang
University
CH-Hangzhou LausanneTel: 8657187952615
Fax: 8657190000000
email:
hgpan@zju.edu.cn

Mr. Arndt REMHOF

Empa
Institute of Nanotechnology
Ü berlandstrasse 129
DE-8600 Dübendorf EggensteinLeopoldshafen

Tel: +41 58 765 4369
Fax: +41 77 4430720
email:
arndt.remhof@empa.ch

35

Ms. Cand. Xiaoling SHAN

Nankai University
Institute of Computational Physics
Nankai University, Tianjin
CH-Tianjin Winterthur

email:
lynnsxl@hotmail.com

93

Asc. Prof. Huaiyu SHAO

Kyushu University
Department of Chemistry
744 Motooka, Nishi-ku
US-Fukuoka 819-0395 Honolulu

Tel: -7546
email:
h.shao@i2cner.kyushuu.ac.jp

1395
PhD candidate Jie SHAO

Department of Materials Scienceand Engineering, Zhejiang
University
School of Science and Engineering
38#, Zhe Da Road HangZhou
ZheJiang China
GB-310027/Hangzhou
Middlesbroughemail:
shaojie35@aliyun.com

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Name

Address

Phone / Fax / email

Mrs. Yun SONG

Physics Department
220 Handan Road, Shanghai
IT-Shanghai Pavia

email:
songyun@fudan.edu.cn

PhD student Mariana
SPODARYK

Institute for Problems of Materials
Science Ukrainian National
Academy of Science
Materials for Energy Conversion
and Storage
Zabolotnogo 148A
NL-03179/ KIEV Delft

Tel: 380685417935
Fax: 380685000000
email:
poshtamary@ukr.net

59

Dr. Nicholas STADIE

Empa
Ü berlandstrasse 129
CH-8600 Dübendorf Bernemail:
nicholas.stadie@empa.ch25

Mr. Dalin SUN

Department of Physics and Earth
Sciences
Department of Materials Science,
Fudan University, 220 HandanRoad
IT-Shanghai Parma

email:
dlsun@fudan.edu.cn

Prof. Lixian SUN

Guilin University of Electronic
Technology
School of Materials andEngineering
No. 1 Jinji Road
CN-Guilin Chengdu

email:
sunlx@guet.edu.cn

Prof. Tejs VEGGETechnical University of Denmark
DTBH/LTH
Frederiksborgvej 399
FR-4000 Roskilde GRENOBLE Cedex
09
Empa, Swiss Federal Laboratories
for Materials Science andTechnology
Hydrogen & Energy
Ueberlandstrasse 129
CH-Duebendorf Dübendorf

Tel: (+45) 4677 5818
Fax: (+45) 5164 1787
email: teve@dtu.dk

31

Tel: 41587654160
email:
ulrich.vogt@empa.ch

23

PD Dr. Ulrich VOGTp

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Zhaoqing, P.R. China 2014

Name

Address

Phone / Fax / emailpMr. Hui WANG

School of Materials Science andEngineering, South China
University of Technology,
Guangzhou, 510641, China
Key Laboratory of Advanced Energy
Storage Materials of Guangdong
Province

Tel.: +86-20-39380578
email:
mehwang@scut.edu.cn
mobile:13726814939

81

Prof. Ping WANG

Institute of Metal Research,
Chinese Academy of Sciences
Nanotechnologie
72 Wenhua Road, Shenhe District
DE-Shenyang Geesthacht

Tel: 86-24-23971622
Fax: 13898130150
email:
pingwang@imr.ac.cn

Asc. Prof. Chaoling WU

College of Materials Science andEngineering, Sichuan University
Hydrogen & Energy
24#, South section 1, Yihuan Road
CH-610064/Chengdu Dübendorf

Tel: 86-28-85466916
Fax: 86-13981807020
email:
wuchaoling@scu.edu.cn

51

Mr. fangming XIAO

Chemistry and Bioengineering
NO.363 changxin lu
CH-510650/Guangzhou Zürich

email:
xfmworld@163.com

29

Mr. Gongbiao XIN

Peking University
Room A909, College of Chemistry
and Molecular Engineering, Peking
University, Beijing
IT-100871 Parma

Tel: 010-62753691
Fax: 15210626783
email:
xgb0212@163.com

Xingguo LI

The College of Chemistry andMolecular Engineering, Peking
University, 100871, Beijing, China

Tel: 86-10-6276 5930
email:xgli@pku.edu.cn

Prof. Fen XU

Guilin University of Electronic
Technology
Institute of Technical
Thermodynamics
No. 1 Jinji Road
DE-Guilin Stuttgart

email:
xufen@guet.edu.cn

Prof. Yu XUEBIN

Fudan University
Physics
Handan Road 220
DK-Shanghai Kongens Lyngby

Fax: 13918375176
05
email:
yuxuebin@fudan.edu.cn

47

PROCEEDINGS

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8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

Name

Address

Phone / Fax / email

Mr. Huizhong YAN

Baotou Research Institute of Rare
EarthsCompany Management
No. 36, Huanghe Street, RE
Development Zone, Baotou, Inner
Mongolia
DK-014030/Baotou Lyngby

Tel: 022-58910553
email:
yhzmail@126.com

p

Dr. Yigang YAN

EMPA
Physics
Ueberlandstrasse 129
NO-Duebendorf Kjeller

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

19

Prof. Dr. XiaoBao YANG

Department of Physics, South
China University of Technology
Institut für Kern- undEnergietechnik
Wushan RD.,Tianhe District
DE-Guangzhou Eggenstein
Leopoldshafen

email:
scxbyang@scut.edu.cn

103

Prof. Yijing WANG

Institute of New Energy Material
Chemistry, Nankai University
94 Weijin Road
CA-300071/Tianjin Trois-Rivières

email:
wangyj@nankai.edu.cn

43Prof. Yongmei WANG

Institute of New Energy Material
Chemistry, Nankai Uinversity
94Weijin Road
NL-300071/Tianjin Delftemail:
yuanht@nankai.edu.cn

Prof. Yunfeng ZHUNanjing University of Technology
Dept. 21
5 Xinmofan Road
DE-210009/Nanjing Dresden

Tel: 025-83587242
email:
yfzhu@njut.edu.cn

55

Mr. Yongjin ZOU

Guilin University of Electronic
Technology
Nanotechnology
Research&Application Center
1 Jinji Road
TR-Guilin 541004 Istanbul

Tel: 0773-2216607
Fax: 13635187300
email:
zouyongjing518@126.com

07

PROCEEDINGS

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8th Int. Symposium Hydrogen & Energy

Zhaoqing, P.R. China 2014

Name

Address

Phone / Fax / email

Shumao Wang

Department of Energy Materials
and Technology
General Research Institute for
Nonferrous Metals
2 Xinjiekou Wai Street, Beijing
100088, P.R. China

Tel:86 10 82241238
Fax:86 10 82241294
Mobile:86 13501285751

p03
Prof. Dr. AndreasZÜ TTELEMPA Materials Science &Technology
R&D management
Ü berlandstrasse 129
JP-8600 Dübendorf Aichi

Tel: +41 58 765 4038
Fax: +41 79 484 2553
email:
andreas.zuettel@empa.
chPROCEEDINGS

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Zhaoqing, P.R. China 2014

Information

PROCEEDINGS

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Zhaoqing, P.R. China 2014

Map from Guangzhou Baiyun International Airport to Zhaoqing

Map of OYC Hotel and DingHu Mountain(Social event) in Zhaoqing

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Zhaoqing, P.R. China 2014

EMERGENCY TELEPHONE NUMBERS
country code for China +86

POLICE

110

FIRE FIGHTERS

119

AMBULANCE120

OYC Hotel:
Add:Xinghu Dadao,Zhaoqing,Guangdong,China
Tel:(86-758)2888888
Website:http://www.oychotel.com

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Zhaoqing, P.R. China 2014

NOTES

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