th

11 $INTERNATIONAL$SYMPOSIUM$$
HYDROGEN$&$ENERGY$
Hydrogen$Production,$Hydrogen$Storage,$Hydrogen$Applications,$Theory$
and$Modelling,$Fuel$Cells,$Batteries,$Synthetic$Fuels,$Functional$Materials$
The$11th$symposium$“Hydrogen$&$Energy”$follows$the$10th$symposium$on$21.$–$
26. February$ 2016$ in$ Zao,$ Japan$ with$ more$ than$ 80$ participants.$ It$ serves$ as$ aninformation$ platform$ of$ the$ fundamental$ science$ and$ technology$ and$ the$frontiers$of$research$on$hydrogen$and$energy.$
The$symposium$consists$of$invited$keynote$lectures$reviewing$the$key$elements$
of$ the$ hydrogen$ cycle,$ i.e.$ the$ hydrogen$ production,$ hydrogen$ storage$ and$hydrogen$ combustion$ and$ fuel$ cells.$ Furthermore,$ contributions$ on$ the$conversion$ of$ renewable$ energy$ in$ general$ and$ energy$ carriers$ beside$ and$beyond$ hydrogen$ are$ very$ welcome.$ The$ world$ leading$ experts$ present$ the$current$ research$ challenges$ and$ most$ important$ results$ in$ invited$ and$contributing$talks.$Early$stage$and$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$ HILTON$ WAIKOLOA$ VILLAGE$ in$ the$beautiful$resort.$
The$number$of$participants$is$limited$to$80.$

February$26$to$March$3,$2017$
HILTON$WAIKOLOA$VILLAGE$
9`425$Waikoloa$Beach$Dr$
Waikoloa$Village$
HI$96738$
USA$$
URL:$hiltonwaikoloavillage.com)$

1

ACKNOWLEDGEMENT-2

OrganizersProfessor-Craig-M.-Jensen-and-Hope-T.-SartainUniversity-of-Hawai´i-at-MānoaDepartment-of-Chemistry2545-McCarthy-MallHonolulu,-HI-96822Email:-Jensen@hawaii.edu;-sartainh@hawaii.edu-

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11 !Int.!Symposium!Hydrogen!&!Energy!

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CONTENTS$
Timetable$
Abstracts$
Name!
Title!
SUNDAY'
15:00! 17:00! Registration!on!Kohala!promenade!

Page!

19:00! 21:00! Welcome!Reception!at!the!Lagoon!Lanai!
MONDAY'
08:00! 09:00! Breakfast)
Chair:)Craig)
JENSEN)
09:00! 10:00! Bjorn!C.!
HAUBACK!
10:00! 10:30! Vitalie!STAVILA!
10:30! 11:00! Coffee)break)
Chair:)Ping)CHEN)
11:00! 12:00! Tom!GENNETT!
12:00! 13:30! Lunch)
Chair:)Tom)GENNETT)
13:30! 14:30! Michael!
FELDERHOFF!

RareGearth!borohydrides!–!crystal!structures!and!thermal!properties!

12!

SIze!MATTERS:!NANOSCALE!METAL!HYDRIDES!AND!BEYOND!

13!

Hydrogen!Storage!Characterization!and!Optimization!research!effort!

14!

Metal!hydrides!for!heat!storage!G!an!integral!part!of!a!hydrogen!economy!

15!

!LITHIUM!IMIDE/!AMIDE:!A!VERSATILE!ENERGY!STORAGE!SYSTEM!

16!

15:00! 15:30! Mariana!
Electrochemical!CO2!reduction!
SPODARYK!
15:30! 16:00! Coffee)break)
Chair:)Michael)FELDERHOFF)
16:00! 17:00! Yumiko!
STRUCTURAL!STUDIES!ON!METAL!HYDRIDES!USING!INGSITU!XGRAY!
NAKAMURA!
DIFFRACTION!AND!THE!PDF!METHOD!

17!

17:00! 17:30! Mattia!
GABOARDI!
17:30! 18:00! Noris!
GALLANDAT!

SODIUM!SUBSTITUTION!EFFECT!IN!LITHIUM!INTERCALATED!FULLERIDES!

19!

Conversion!of!Renewable!Energy!to!Synthetic!Hydrocarbons!

20!

14:30! 15:00! Bill!DAVID!

18!

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11 !Int.!Symposium!Hydrogen!&!Energy!

19:00!G!
21:00!

Waikoloa!Village,!Hawaii,!USA!2017!

Poster'session'
Chair:)Michael)HIRSCHER)
Marina!CHONG! A!NEW!ROLE!FOR!SOLVENTS:!FROM!UNDESIRABLE!RESIDUE!TO!USEFUL!
ADDITIVE!
Andreas!ZÜTTEL! HYDROGEN!STORAGE!OPTIONS!
Kun!ZHAO!
CO2!adsorption!reaction!on!Ni!and!Cu!powder!surface!
Mirjana!
Neutron!scattering!studies!of!hydrogenous!materials!for!nextGgeneration!
DIMITRIEVSKA!
energy!storage!
Heena!YANG!
!ADSORPTION!BEHAVIOR!OF!BORON!DOPED!GRAPHENE!OXIDE!FOR!
AMMONIA!!
Jacob!TARVER!
USING!NEUTRONS!TO!PROBE!HYDROGEN!STORAGE!IN!METALORGANIC!
FRAMEWORKS!
TsanGYao!CHEN! CRYSTAL!SHAPE!CONTROLLED!H2!STORAGE!RATE!IN!NANOPOROUS!CARBON!
COMPOSITE!WITH!ULTRAGFINE!PT!NANOPARTICLE!
HsinGYi!CHEN!
Hydrogen!adsorption,!dissociation!and!spillover!on!metal!clusters!supported!
on!TiO2!and!carbonGbased!surfaces!
Katherine!HURST! A!MULTIGLABORATORY!COMPARISON!STUDY!OF!VOLUMETRIC!CAPACITY!
MEASUREMENTS!ON!HYDROGENGSORPTION!MATERIALS!
ShinGichi!ORIMO! Advanced!Hydride!Research!for!AllGSolidGState!Energy!Storage!Devices!
Noris!
GRZ!Technologies!SA!
GALLANDAT!
Noris!
Small!Scale!Demonstrator!for!Sion!
GALLANDAT!
Xin!JU!
PressureGinduced!phase!transitions!in!LiBH4!and!synergistic!effect!of!LiGTi!and!
KGTi!coGdoping!on!NaAlH4:!firstGprinciples!study!
Yijing!WANG!
Porous!nickelGand!cobaltGbased!oxides!nanorods!catalytic!effects!on!improving!
LiBH4!dehydrogenation!properties!

TUESDAY'
08:00! 09:00! Breakfast)! Chair:)Yumiko)NAKAMURA)
09:00! 09:30! Katie!RANDOLPH! Accelerating!Advanced!Water!Splitting!and!Hydrogen!Storage!Materials!
Development!
09:30! 10:00! Craig!BUCKLEY!
High!Temperature!Hydrides!for!Concentrated!Solar!Thermal!Storage!
10:00! 10:30! Young!Whan!
Complex!metal!hydrides!for!stationary!hydrogen!storage!and!rechargeable!
CHO!
batteries!
10:30! 11:00! Coffee)break)
Chair:)Katie)
RANDOLPH)
11:00! 12:00! Joseph!
Hydrogen!storage,!ion!transport!phenomena,!and!photoluminescence!of!
TEPROVICH!
composite!hydride!materials!

4 !
4 !
!
5 !
5 !
5 !
5 !
5 !
5 !
5 !
0!
0!
5 !
5 !

21!
22!
23!

24!

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12:00! 13:30! Lunch!
Chair:)Joseph)TEPROVICH)
13:30! 14:30! Tom!AUTREY!
HYDROGEN!STORAGE!CHARACTERIZATION!AND!OPTIMIZATION!RESEARCH!
EFFORT!
14:30! 15:00! Matthew!
THE!DEVELOPMENT!OF!MODEL!FOR!EVALUATING!THE!PERFORMANCE!OF!
THORNTON!
MATERIALSGBASED!HYDROGEN!STORAGE!SYSTEMS!AND!THE!SCREENING!OF!
HYDROGEN!STORAGE!MATERIALS!

25!
26!

15:00! 15:30! Robert!C.!
BOWMAN!

STATUS!OF!HIGHGPRESSURE!METAL!HYDRIDE!COMPRESSORS!FOR!
APPLICATIONS!EXCEEDING!700!BAR!

27!

15:30! 16:00! Coffee)break)
Chair:)Tom)AUTREY)
16:00! 16:30! Dhanesh!
CHANDRA!

Dynamic!XGRay!Photon!Correlation!Spectroscopy,!NVS!and!other!Studies!on!
(Ni0.60Nb0.4)100GxZrx!(x=0!to!30)!Amorphous!Alloy!Membranes!

28!

16:30! 17:00! Florian!MERTENS! THE!HYDROGENATION!OF!LITHIUM!SILICIDES!AN!OLD!STORY!CONTINUED!IN!A!
NEW!CONTEXT!

29!

17:00! 17:30! HaiGWen!LI!

METAL!BORANES!FOR!HIGH!DENSITY!HYDROGEN!STORAGE!AND!FAST!IONIC!
CONDUCTIVITY!
EFFECT!OF!PRESSURE!ON!TUNNELING!AND!VIBRATIONAL!SPECTRUM!OF!
HYDROGEN!IN!ALPHA!MANGANEZE!

30!

A!NEW!ROLE!FOR!SOLVENTS:!FROM!UNDESIRABLE!RESIDUE!TO!USEFUL!
ADDITIVE!

4 !

Andreas!ZÜTTEL!
Kun!ZHAO!

HYDROGEN!STORAGE!OPTIONS!
CO2!adsorption!reaction!on!Ni!and!Cu!powder!surface!

4 !
!

Mirjana!
DIMITRIEVSKA!

Neutron!scattering!studies!of!hydrogenous!materials!for!nextGgeneration!
energy!storage!

5 !

Heena!YANG!

!ADSORPTION!BEHAVIOR!OF!BORON!DOPED!GRAPHENE!OXIDE!FOR!
AMMONIA!!

5 !

Jacob!TARVER!

USING!NEUTRONS!TO!PROBE!HYDROGEN!STORAGE!IN!METALORGANIC!
FRAMEWORKS!

5 !

TsanGYao!CHEN!

CRYSTAL!SHAPE!CONTROLLED!H2!STORAGE!RATE!IN!NANOPOROUS!CARBON!
COMPOSITE!WITH!ULTRAGFINE!PT!NANOPARTICLE!

5 !

HsinGYi!CHEN!

Hydrogen!adsorption,!dissociation!and!spillover!on!metal!clusters!supported!
on!TiO2!and!carbonGbased!surfaces!

5 !

17:30! 18:00! Alexander!
KOLESNIKOV!
19:00!G!
21:00!

31!

Poster'session'
Chair:)Andreas)ZÜTTEL)
Marina!CHONG!

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11 !Int.!Symposium!Hydrogen!&!Energy!

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Katherine!HURST! A!MULTIGLABORATORY!COMPARISON!STUDY!OF!VOLUMETRIC!CAPACITY!
MEASUREMENTS!ON!HYDROGENGSORPTION!MATERIALS!
ShinGichi!ORIMO! Advanced!Hydride!Research!for!AllGSolidGState!Energy!Storage!Devices!
Noris!
GALLANDAT!
Noris!
GALLANDAT!
Xin!JU!
Yijing!WANG!

5 !
5 !

GRZ!Technologies!SA!
Small!Scale!Demonstrator!for!Sion!

0!

PressureGinduced!phase!transitions!in!LiBH4!and!synergistic!effect!of!LiGTi!and!
KGTi!coGdoping!on!NaAlH4:!firstGprinciples!study!
Porous!nickelGand!cobaltGbased!oxides!nanorods!catalytic!effects!on!improving!
LiBH4!dehydrogenation!properties!

5 !
5 !

WEDNESDAY'
Chair:)Bjorn)C.)HAUBACK)
09:00! 10:00! Ping!CHEN!
LIGNGH!MEDIATED!NH3!SYNTHESIS!AND!DECOMPOSITION!
32!
10:00! 10:30! Martin!
DEVELOPMENT!AND!PERSPECTIVES!OF!METAL!HYDRIDES!AND!METAL!HYDRIDE! 33!
DORNHEIM!
BASED!SYSTEMS!FOR!HYDROGEN!STORAGE!
11:00! 21:00! Excursion!
Exclusive!Volcano!Special!Tour:!City!of!Hilo!!!!!!
Liliuokalani!Park!!!!!
Rainbow!Falls!!!
Hawaii!Volcanoes!National!Park!(admission!included)!!!
(visitor!center,!steaming!bluff,!Kilauea!overlook,!Jaggar!Museum!and!Observatory,!
Halemaumau!crater,!Thurston!lave!tube,!Kilauea!Iki!overlook)!
Lunch!(on!own)!location!to!be!advised!!!

THURSDAY'
Chair:)Bill)DAVID)
09:00! 10:00! Guanqiaog!LI!
Hydrogen!Storage!Properties!of!Composite!Materials!between!BoronG!and!
Transition!MetalGBased!Complex!Hydrides!

34!

10:00! 10:30! Torben!R!JENSEN! MULTIGFUNCTIONAL!ENERGY!STORAGE!MATERIALS!
10:30! 11:00! Coffee)break)
Chair:)Guanqiaog)
LI)
11:00! 12:00! Daiju!
TimeGresolved!XGray!absorption!fine!structure!for!hydrogen!storage!materials!
MATSUMURA!
12:00! 13:30! Lunch)
Chair:)Daiju)MATSUMURA)
13:30! 14:30! Ragaiy!ZIDAN!
ADVANCE!IN!THE!FORMATION!AND!REGENERATION!OF!ALANE!FOR!
HYDROGEN!STORAGE!

35!

36!

37!

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11 !Int.!Symposium!Hydrogen!&!Energy!

Waikoloa!Village,!Hawaii,!USA!2017!

14:30! 15:00! Yinzhe!LIU!

STUDY!OF!THE!DECOMPOSITION!OF!A!EUTECTIC!LITHIUM!AND!SODIUM!
BOROHYDRIDE!MIXTURE!WITH!NANOGSIZED!NI!

38!

15:00! 15:30! Mathias!
JØRGENSEN!
15:30! 16:00! Coffee)break)
Chair:)Ragaiy)
ZIDAN)
16:00! 16:30! Ankur!JAIN!

Halogenated!sodiumGclosoGdodecaboranes!as!solidGstate!ion!conductors!

39!

ALTERATION!IN!SODIUM!AMIDE!DECOMPOSITION!BY!THE!ADDITION!OF!
METAL!HYDRIDES!

40!

16:30! 17:00! Tessui!
NAKAGAWA!
17:00! 17:30! Mark!BOWDEN!

Room!temperature!dehydrogenation!of!Ammonia!borane!

41!

SOLVENTGCOORDINATED!COMPOUNDS!FORMED!FROM!MAGNESIUM!
HYDROBORATES!AND!TETRAHYDROFURAN!

42!

17:30! 18:00! ShinYoung!KANG! BEYONDGIDEAL!MODELING!OF!(DE)HYDROGENATION!IN!COMPLEX!METAL!
HYDRIDES!
19:00! 21:00!

43!

Conference!dinner!at!the!grand!staircase!at!the!Hilton!

FRIDAY'
Chair:)Martin)DORNHEIM)
09:00! 10:00! Mark!
ENABLING!REVERSIBILITY!IN!COMPLEX!METAL!HYDRIDES!
ALLENDORF!
10:00! 10:30! Sanjay!KUMAR!
Cyclic!hydrogen!storage!performance!of!MgH2!with!VGbased!additives!

44!

10:30! 11:00! Coffee)break)! Chair:)Mark)ALLENDORF)
11:00! 11:30! Michael!
SEPARATION!OF!HYDROGEN!ISOTOPES!IN!POROUS!MATERIALS!
HIRSCHER!
11:30! 12:00! Craig!JENSEN!
Closing remarks!

46!

SCIENCE$OF$HYDROGEN$&$ENERGY$AWARD$

60$

List$of$Participants$

92

Information$

100$

Notes$

109$

45!

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ABSTRACTS$
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12

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11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

RARE-EARTH BOROHYDRIDES – CRYSTAL STRUCTURES AND
THERMAL PROPERTIES
Bjørn C. Hauback, Michael Heere, Jørn Eirik Olsen, Christoph Frommen, Magnus, H.
Sørby
Physics Department, Institute for Energy Technology (IFE), P.O. Box 40, NO-2027 Kjeller, Norway
This work presents detailed studies of the crystal structures and thermal properties of rare-earth (RE) borohydrides. The
compounds show a big structural variety with anion substation, polymorphism, difference in coordination numbers andmultiple oxidation states. The thermal decomposition of the mixtures has been studied by in situ synchrotron radiation
powder X-ray diffraction. Composites with RE-borohydrides and LiBH4/LiH could be cycled at relatively mild conditions.

Introduction
Metal borohydrides have been extensively investigatedover the last years as potential hydrogen storage
materials due to their high volumetric and gravimetrichydrogen capacities. Because of the high Li-conduction
in for example hexagonal LiBH4 and also recently foundin other mixed metal borohydrides, these compounds are
possible candidates as solid state electrolytes in Li-ion
batteries. During the last years our interest has been
directed to the synthesis and properties of transition
metal- and rare-earth (RE) borohydrides with different
metal atoms and in some cases with anion substitution.
This work presents studies of RE-based borohydrides
with a focus on crystal structures and thermal properties.

Results and discussion
Mixtures of RECl3 and LiBH4 have been synthesized byball milling with RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Er, Tm, Yb and Lu [1-3]. The crystal structures have been
investigated by synchrotron radiation powder X-ray
diffraction (SR-PXD) at SNBL, ESRF and powder neutron
diffraction at the JEEP II reactor at IFE. The compounds
show a big structural variety with: (i) anion substitution;(ii) polymorphism; (iii) different coordination numbers; and(iv) multiple oxidation states of the RE. An overall trend is
that: (i) the early RE: La, Ce, Pr, Nd, Sm and Gd form
LiRE(BH4)3Cl in space group I-43m; (ii) the later RE: Sm,
Gd, Tb, Dy, Er, Tm and Yb form D-RE(BH4)3 in Pa-3,
while for Sm, Er and Yb a second polymorph named ERE(BH4)3 is formed in the higher-symmetry space groupPm-3m/Fm-3c; (iii) the smallest RE: Yb and Lu form
LiRE(BH4)4, space group P-42c; (iv) upon heating
Sm(BH)2 and Eu(BH4)2 (space group Pbcn) and two

B.C. Hauback

modifications of Yb(BH4)2-xClx (P-4 and Pbca) are
observed. The thermal decomposition of the mixtures has
been investigated by in situ SR-PXD, thermogravimetricanalysis / differential scanning calorimetry andtemperature programmed desorption. Furthermore wehave studied how composites with different ratios
between RECl3 and LiH/LiBH4 improve the reversiblehydrogen storage capacities [4-5]. The 3LiBH4+Er(BH4)3+
3LiH composite showed a reversible hydrogen storage
capacity of 3.7 wt% after 3 cycles.

Acknowledgements
The Research Council of Norway and the EU FP7 Marie
Curie ITN ECOSTORE project are acknowledged forfinancial support.

References[1] C. Frommen, M.H. Sørby, P. Ravindran, P.
Vajeeston, H. Fjellvåg, B.C. Hauback, J. Phys. Chem.
C 115 (2011) 23591.
[2] J.E. Olsen, C. Frommen, M.H. Sørby, B.C. Hauback,
RSC Adv. 3 (2013) 10764.
[3] J.E. Olsen, C. Frommen, T.R. Jensen, M.D. Riktor,
M.H. Sørby, B.C. Hauback, RSC Adv. 4 (2014) 1570.
[4] C. Frommen, M. Heere, M.D. Riktor, M.H. Sørby, B.C.
Hauback, J. Alloys Comp. 645 (2015) S155.
[5] M. Heere, S.H. Payandeh GharibDoust, C. Frommen,
T.D. Humphries, M.D. Ley, M.H. Sørby, T.R. Jensen,
B.C. Hauback, Phys. Chem. Chem. Phys. 18 (2016).
24387.

Bjørn C. Hauback is Department Head and Chief Scientist of the Physics Department, Institute forEnergy Technology (IFE) and adjunct professor of Physics at the University of Oslo in Norway. He
has a PhD in physics from Norwegian Institute of Technology from 1989. His main interests are
structure-property relationships of hydrogen storage materials and neutron diffraction. Hauback is
co-author of 285 peer-reviewed articles and he has 85 invited talks. He is a member of Norwegian
Academy of Technological Sciences. Hauback led the Task 22 on hydrogen storage materials of the
IEA Hydrogen Implementation Agreement in 2006-2012, and he was the co-chair of the Gordon
Research Conference Hydrogen-Metal Systems in July 2015.

Corresponding author: Bjørn C. Hauback, bjorn.hauback@ife.no, tel: +47 97 40 88 44.

13

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11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

SIZE MATTERS: NANOSCALE METAL HYDRIDES AND BEYOND
Vitalie Stavila,1,* Brandon Wood,2 Keith Ray,2 Tae-Wook Heo,2 Jonathan R. I. Lee,2 James L.
White,1 Josh D. Sugar,1 Lennie L. Klebanoff,1 Terrence J. Udovic,3 Mark D. Allendorf1
1
Sandia National Laboratories, Livermore, CA, 94551, USA
2
Lawrence Livermore National Laboratory, Livermore, CA, 94551, USA
3
National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA
We demonstrate that nanoconfinement and nanostructuring of complex metal hydrides can fundamentally alter both the(de)hydrogenation reaction pathways due to altered surface energies of nanoparticles, or as a direct consequence ofsolid-solid nanointerfaces within the material. This dramatically improves the kinetics and lowers the thermodynamic
requirements in the Li3N/LiNH2+2LiH, LiAlH4 and NaAlH4 complex hydride systems to achieve improved reversibility.

Introduction
Nanostructured metal hydrides have been considered todate as potential candidates for hydrogen storage
applications because of the improved reversibility andkinetics of hydrogen release and absorption. Reducing
the dimensionality of metal hydride particles exploits theshort diffusion distances and constrained environmentthat exist in nanoscale materials, which lowers theenergy requirements for H2 cycling.

shows an EELS/TEM image of the nanoconfined Li3N (Lired) inside the carbon host (C-green); the figure on theright shows the predicted mole fraction of relevant
phases in the Li-N-H system in bulk and at 2 nm.

Results
In this study, we show that not only the kinetics of thehydrogen storage reactions can be tuned at nanoscale,but also the enthalpy (ΔH) and entropy (ΔS). Our
calculations
andexperiments
indicatethatnanostructured LiAlH4, NaAlH4 and LiNH2/2LiH undergo
one step thermal decomposition when the particle size isless than 10 nm. In contrast, dehydrogenation of bulk
NaAlH4 and LiNH2/2LiH occurs via two-step reactions
with intermediate Na3AlH6 [1] and Li2NH [2] species being
formed. To probe the size effects in metal hydrides,
functionalyzed mesoporous carbons with average poresizes between 2 and 10 nm were infiltrated with metal
hydrides by solution and solid-state approaches. Typicalhydride loadings were between 8 to 30 wt%; the highest
loading of 41 wt% was achieved for the
LiNH2/2LiH@3nm-Carbon system. The nano-Li3N/o
LiNH2+2LiH system reversibly cycles hydrogen at 240 C
in a single step. Our theory modeling suggests that thesingle-step decomposition pathway in LiNH2/2LiH@3nmCarbon results directly from the presence of solid-solid
nanointerfaces within the hydride particles, which arise
because of the coexistence of multiple phases during(de)hydrogenation. The left size of the figure below

Vitalie Stavila

Conclusions
In conclusion, we demonstrate that size matters innanoscale LiAlH4, NaAlH4 and LiNH2/2LiH with respect tohydrogen storage properties; in addition to improved
kinetics, nanostructuring alters both the hydrogenationand dehydrogenation reactions. Not only does
nanoconfinement change the reaction pathway in thesematerials, but it also dramatically lowers the pressure andtemperature required to achieve full reversibility.

References[1] Bogdanović, B., et al., Metal-doped sodium aluminium
hydrides as potential new hydrogen storage
materials. J. Alloys Comp., 2000, 302, 36-58.
[2] Chen, P., et al., Interaction of hydrogen with metal
nitrides and imides. Nature, 2002, 420, 302-304.

Dr. Vitalie Stavila holds a PhD in chemistry (2002) and has extensive expertise in synthesis andcharacterization of inorganic compounds and nanostructured materials. He is currently a Principal
Member of Technical Staff at Sandia National Laboratories where he is working on several projects
focussed on materials for energy storage. His projects in the area of hydrogen storage focus on thedevelopment of sorbents and metal hydrides with improved thermodynamics and kinetics ofhydrogen release and absorption. A central theme in Dr. Stavila’s research is the rational design of
new materials by changing the chemical composition, the arrangement of the atoms or molecules insolids, and the size, shape, and orientation of nanoparticles, crystals or other macroscopic units.

Corresponding author: Vitalie Stavila, Email: vnstavi@sandia.gov, Tel. 925.294.3059

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Waikoloa$,$Hawaii$2017$$

HYDROGEN) STORAGE) CHARACTERIZATION) AND) OPTIMIZATION)RESEARCH)EFFORT)Thomas$Gennett,$Ph.D.$
National$Renwable$Energy$Laboratory$$

Summary)
The$ HySCORE$ collaboration$ is$ a$ DOEKFCTO$ funded$
initiative$ that$ brings$ together$ internationally$ recognized$
leaders$ in$ hydrogen$ storage$ materials$ characterization$
and$ development$ from$ NREL,$ LBNL,$ PNNL$ and$ NIST.$
This$collaboration$is$predicated$on$a$synergistic$approach$
to$further$develop$the$key$coreKcapabilities$necessary$for$
accurate$ evaluation$ of$ hydrogen$ storage$ materials$
capacity,$ kinetics,$ and$ sorption/desorption$ physioK
chemical$ processes.$ Furthermore,$ these$ experts$ also$
conduct$ a$ parallel$ experimentalKmodeling$ collaborative$
approach$ to$ utilize$ the$ coreKcapabilities$ developed$ in$order$ to$ rapidly$ define,$ model,$ synthesize$ and$characterize$ the$ appropriate$ materials$ necessary$ for$achieving$ the$ 2020$ Hydrogen$ Storage$ goals$ set$ forth$ by$
DOE.$ The$ approach$ is$ multifaceted$ to$ mitigate$ risk$ and$ensure$ success$ as$ we$ bridge$ the$ gap$ between$
physisorption$ and$ chemisorption$ to$ provide$ the$ basis$ for$a$ new$ generation$ of$ hydrogen$ storage$ materials$
technologies.$ Our$ focus$ is$ to$ Develop$ and$ Enhance$hydrogen$ storage$ core$ capabilities$ and$ to$ Validate$$$claims,$ concepts,$ and$ theories$ of$ hydrogen$ storage$
materials.$The$overarching$goal$is$to$ascertain$pathways$
and/or$ new$ materials$ that$ have$ the$ possibility$ to$volumetric$capacities$of$greater$than$45$g/L$and$isosteric$heats$ of$ hydrogen$ adsorption$ in$ the$ range$ of$ 15K20$
kJ/mol$ with$ the$ additional$ caveats$ of$ acceptable$
gravimetric$ capacities$ and$ the$ ability$ to$ deliver$ onK
demand$H2$at$an$appropriate$rate$and$pressure.$In$order$
to$ capture$ the$ benefits$ of$ reduced$ system$ cost$ and$
forecourt$ compression$ energetics,$ the$ maximum$
overpressure$ would$ be$ <100$ bar$ of$ hydrogen,$ with$ a$delivery$temperature$of$greater$than$150$K$and$as$close$
to$ambient$temperature$as$possible.$$This$ talk$ will$ outline$ the$ advanced$ characterization$techniques,$ standardized$ benchmarking/protocols$ and$capabilities.$ We$ will$ also$ highlight$ several$ new$ materials$
sets,$ the$ impact$ of$ the$ new$ characterization$ tools$ and$
how$ this$ has$ acceleratd$ advances$ in$ hydrogen$ storage$
materials$development.))$

Dr.$ Thomas$ Gennett$ is$ currently$ a$ Principle$ Scientist$ at$ NREL$ and$ holds$ Professor' Emeritus' of$Chemistry$ and$ Materials$ Science$ status$ with$ the$ Rochester$ Institute$ of$ Technology.$ $ At$ NREL,$ Dr.$
Gennett$ leads$ three$ distinct$ projects]$ one$ focuses$ on$ the$ mechanism$ of$ hydrogen$ adsorption$ for$sorbents,$the$second$on$the$development$of$advanced$materials$for$nonKPGM$fuel$cell$catalysts$and$finally$development$of$next$generation$organic$based$flow$batteries.$$Previously,$while$a$Professor$at$
RIT$he$was$coKfounder$and$director$(2001K03)$of$the$Institute$NanoPower$Research$Laboratory.$$Dr.$
Gennett$ has$ had$ a$ strong$ collaboration$ with$ Nanostructured$ Materials$ and$ NCPV$ groups$ at$ NREL$
since$1998,$coming$to$NREL$on$sabbatical$in$1998$and$2005.$$$$His$previous$research$with$NREL$
focused$ on$ the$ use$ of$ pulsed$ laser$ vaporization$ to$ produce$ high$ purity$ single$ wall$ nanotubes,$quantum$ dots,$ and$ other$ nanoscale$ materials.$ $ This$ work$ has$ made$ significant$ advances$ in$ the$purification$ and$ derivatization$ of$ the$ carbon$ based$ nanostructured$ materials$ for$ hydrogen$ storage,$battery$anodes/cathodes,$gas$separations$and$catalysts$applications.$$In$2001,$Thomas$joined$NREL$
in$ 2008$ as$ a$ DOE$ Hydrogen$ Sorption$ Center$ of$ Excellence$ as$ the$ Hydrogen$ Spillover$ Research$
Cluster$lead.$$Dr.$Gennett$received$his$B.A.$in$Chemistry$from$the$State$University$College$of$New$
York$ at$ Potsdam$ and$ his$ Ph.D.$ in$ Analytical$ Chemistry,$ University$ of$ Vermont,$ Burlington,$ VT$ and$
conducted$his$postdoctoral$studies$at$Purdue$University.$$$$Corresponding$author:$Tom$Gennett,$Thomas.gennett@nrel.gov,$303K384K6628$

$

$$

$

15

METAL HYDRIDES FOR HEAT STORAGE – AN INTEGRAL PART FOR A
HYDROGEN ECONOMY
Michael Felderhoff
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr
Abstract: For the storage of heat at different temperature levels metal hydrides offer high heat storage capacities.
Hydrides are in principle low-cost materials with excellent cycling stability. These heat storage materials possess highgravimetric and volumetric heat storage densities. Due to the separation of the reaction products and their storage in
different locations heat losses can be avoided.

Hydrogen Economy and Metal hydrides
The hydrogen economy is a proposed system ofdelivering energy using hydrogen as secondary energy
carrier. Proponents of a hydrogen economy advocatehydrogen as a potential fuel for automotive (alsoincluding boats) and on-board auxiliary power, stationary
power generation (for the energy needs of buildings), andas an energy storage medium (for interconversion fromexcess electric power). Molecular hydrogen does notoccur naturally in convenient reservoirs; nonetheless it
must be generated by steam reforming of hydrocarbons,water electrolysis or by other methods. Hydrogen used inany kind of burning process for the production ofelectricity and/or heat produces only water as waste
component.
Additionally, hydrogen can be used in reversible
thermochemical heat storage applications withoutburning of hydrogen. In this case, hydrogen is used only
as working medium and is not irreversibly consumed in areaction with oxygen gas.

Metal hydrides for heat storage
Metal hydrides for heat storage can link the electricity
and heat production with excess energy storage anddistribution of hydrogen in future energy systems.

In the heat storage application, the heat of reaction
liberated during the hydride formation process serves asuseful heat. Thereby hydrogen is confined in a closed
system and is preserved during a great number of heatstorage cycles. The high heat amount and the stability
over thousands of cycles (closed systems) turn metal
hydrides into ideal candidates for different heat storage
applications, depending on the thermodynamic propertiesof the metal hydride system and the temperature of the
proposed application. Some possible areas ofapplications for heat storage with metal hydrides are
domestic heating (up to 150 °C), processing industries(200 °C–1200 °C) or solar power plants (400 °C–800 °C).

References[1] Michael Felderhoff and Borislav Bogdanović, High
Temperature Metal Hydrides as Heat Storage
Materials for Solar and Related Applications, Int. J.
Mol. Sci. 2009, 10(1), 325-344.
[2] Ewa C. E. Rönnebro, Greg Whyatt, Michael Powell,Matthew Westman,Feng (Richard) Zheng andZhigang Zak Fang, Metal Hydrides for HighTemperature Power Generation, Energies 2015, 8(8),8406-8430.

since 1999 senior scientist MPI für Kohlenforschung, Department of Heterogeneous Catalysis
1997–1998 scientific co-worker University of Osnabrück
1996–1997 scientific co-worker Eberhard Karls University of Tübingen
1993–1996 scientific co-worker University of Essen
1993 PhD University of Essen
M. Felderhoff
Corresponding author: Michael Felderhoff, felderhoff@mpi-muelheim.mpg.de, Tel. +49 (0)208 306 2368

16

th

11 Int. Symposium "Hydrogen & Energy"

Waikoloa , Hawaii 2017LITHIUM IMIDE/ AMIDE: A VERSATILE ENERGY STORAGE SYSTEMW I F David1,2, J W Makepeace2, T J Wood1, H M A Hunter1, M O Jones1
1 ISIS, Rutherford Appleton Laboratory, Harwell Campus, OX11 0QX, UK, 2 Inorganic Chemistry Laboratory, South
Parks Road, University of Oxford, Oxford, OX1 3QR, UK.
Abstract
The lithium imide/ amide system is not only attractive as a reversible lightweight hydrogen store but is also an effective
catalyst in the decomposition of ammonia. This presentation focuses on the use of isotopically enriched materials in bothpowder diffraction and mass spectrometry studies to elucidate the mechanisms of both reversible hydrogen storage andammonia cracking.

Introduction
The lithium imide and amide system is fascinating bothfrom a fundamental viewpoint and also as a key player inboth hydrogen storage and ammonia utilisation as anenergy vector.
Lithium amide may be regarded as an ordered variant of
the anti-fluorite-related lithium imide structure and thisclose relationship facilitates the bulk reversibility oflithium imide to lithium amide which results in facilehydrogenation mild conditions. In-situ X-ray powder
diffraction measurements have provided detailed
understanding of both the kinetics and thermodynamics
of this highly reversible lightweight hydrogen storage
system. Non-stoichiometric lithium imide is also an
excellent catalyst for the efficient cracking of ammonia. In
situ neutron scattering experiments coupled with mass
spectrometry measurements using isotopically enriched
2
15
H and
N materials have provided a detailed
mechanistic understanding of the effectiveness of lithium
imide as an ammonia cracking catalyst.

Experimental
X-ray diffraction experiments were performed at the I11
diffractometer at the Diamond Light Facility, UK. Time-offlight neutron powder diffraction measurements werecollected on the POLARIS diffractometer at the ISIS
Facility, UK. A deuterated sample of lithium imide wasprepared for these neutron experiments to optimise thecoherent neutron scattering from the sample. Deuterated
lithium amide (LiND2) was prepared by the reaction of
deuterated ammonia (ND3) with lithium nitride (Li3N).

The decomposition of lithium amide under ammonia wasmonitored using the Intelligent Gravimetric Analysis for
Neutrons apparatus (IGAn, Hiden Isochema). A sampleof lithium amide (390 mg) was loaded into a stainlesssteel bucket and attached to the IGAn balance in an
argon-filled glove box. The apparatus was sealed andevacuated, then refilled with 1100 mbar of ammonia. Theoosample was then heated to 450 C at 1 C/min, with themass and temperature of the sample recorded
simultaneously.

Results and Discussion
In-situ X-ray diffraction studies of hydrogenation anddehydrogenation of the lithium amide/amide system
highlight non-stoichiometry effects with both kinetic and[1]thermo-dynamic behaviour . Neutron powder diffraction
measurements show that hydrogen from the ammonia is
exchanged with, and incorporated into, the bulk catalystmaterial, in a significant departure from existing ammonia[2]
decomposition catalysts . This is confirmed by mass215
spectrometry analysis of isotopically labelled H and N[3]compounds .

References[1] J. W. Makepeace, M. O. Jones, S. K. Callear, P. P.
Edwards and W. I. F. David, Phys. Chem. Chem. Phys.,
16, 4061 (2014)[2] J. W. Makepeace, T. J. Wood, H. M. A. Hunter, M. O.
Jones and W. I. F. David, Chem. Sci., 6, 3805 (2015).
[2] T. J. Wood, J. W. Makepeace and W. I. F. David (inpreparation

Bill David is STFC Senior Fellow at the ISIS Neutron Source, Oxfordshire, UK, Professor ofMaterials Chemistry in the Inorganic Chemistry Laboratory, University of Oxford, and Fellow in
Physics at St. Catherine’s College, Oxford. He is a Fellow of the Royal Society, a Fellow of theInstitute of Physics, a Fellow of the Royal Society of Chemistry and an Honorary Life Member of the
British Crystallography Association.
Bill’s research is focused on the discovery and characterisation of novel energy storage systems
and, in particular, lightweight hydrogen store and the development of ammonia as an energy vector.
Bill David
Corresponding author: W I F David, bill.david@stfc.ac.uk +44 1235 445179 / +44 1865 272689

17

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11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa$,$Hawaii$2017$

ELECTROCHEMICAL+CO2+REDUCTION+
Mariana$Spodaryk,$Andreas$Züttel$
Laboratory$of$Materials$for$Renewable$Energy$(LMER),$Institute$of$Chemical$Sciences$and$Engineering$(ISIC)$
Basic$Science$Faculty$(SB),$École$polytechnique$fédérale$de$Lausanne$(EPFL)$Valais/Wallis,$Energypolis,$
Rue$de$l’Industrie$17,$CP$440,$CHV1951$Sion,$Switzerland$
The$simultaneous$electrochemical$reduction$of$CO2$and$H2O$allows$the$direct$production$of$hydrocarbons,$which$have$the$same$energy$density$as$fossil$fuels,$from$electricity.$Among$the$other$imposrtant$factors,$the$key$factor$in$determining$the$ product$ distribution$ in$ electrochemical$ CO2$ reduction$ is$ the$ cathode$ material.$ Our$ study$ is$ focused$ in$ direct$
electrochemical$CO2$reduction$on$new$catalytic$copperVcontaining$surfaces.$
Carbon$ dioxide$ concentration$ in$ the$ atmosphere$ is$12
continuously$increasing$and$corresponds$to$750×10 $kg$
C.$However,$most$of$the$CO2$on$the$Earth$is$stored$in$the$12
ocean$ (41’031×10 $ kg$ C).$ CO2$ reduction$ to$ specific$hydrocarbon$ after$ its$ extraction$ from$ the$ air$ is$ of$ great$
importance$ for$ the$ future$ energy$ economy$ based$ on$
renewable$ energy,$ however$ the$ direct$ electrochemical$
CO2$ reduction$ from$ the$ seawater$ would$ be$ even$ more$
attractive$and$efficient.$

Since$ all$ the$ listed$ above$ products$ are$ formed$ under$
potentials$ lower$ than$ hydrogen$ evolution$ reaction$ (HER)$○(starts$at$V0.414V$vs.$SHE$at$25 C$and$pH$7$according$to$
Pourbaix$ diagram)$ the$ main$ byproduct$ of$ CO2$ reduction$
on$copper$oxide$electrodes$is$hydrogen.$Suppressing$the$
HER$ and$ therefore,$ increasing$ the$ faradaic$ efficiency$ of$the$ formation$ of$ hydrocarbons$ is$ challenging$ and$ a$
crucial$ task,$ which$ is$ of$ our$ interest$ for$ further$investigation$of$these$materials.$

Among$ the$ others,$ the$ key$ factor$ in$ determining$ the$product$ distribution$ in$ CO2$ reduction$ is$ the$ cathode$material.$ Copper$ is$ a$ unique$ electrode,$ which$ can$electroVcatalytically$ convert$ CO2$ and$ water$ into$hydrocarbons$ and$ alcohols$ at$ atmospheric$ temperature$
and$pressure$[1].$$
Our$ study$ is$ focused$ in$ direct$ electrochemical$ CO2$
reduction$ on$ new$ catalytic$ copperVcontaining$ surfaces,$
which$ are$ electrode$ and$ catalyst,$ such$ as$ copper$
nanoclusters,$ high$ surface$ area$ copper$ oxides$ and$ in$
case$ of$ copperVcontaining$ metal$ hydrides$ is$ also$ an$ HVdonor$for$creating$hydrocarbons.$
The$ electrochemical$ CO2$ reduction$ is$ carried$ out$ in$ the$three$electrode$electrochemical$cell$$(CE$–$Au$foil,$RE$–$
Ag/AgCl$ in$ 3M$ KCl$ solution)$ using$ saturated$ with$ CO2$
0.1M$ KHCO3$ electrolyte$ (Sigma$ Aldrich,$ 99.995%,$ pH$
6.65V6.8)$ with$ continuous$ supplying$ CO2$ gas$ during$experiment.$ As$ example,$ here$ we$ present$ the$ results$ of$reaction$ on$ electrochemically$ oxidised$ Cu$ foil$ (Good$2
fellow,$99.9$%,$thickness$of$0.125$mm)$electrode$(5$cm ).$Electrochemical$ reduction$ of$ CO2$ resulted$ in$ following$products:$ CO$ (2252.3$ ppm),$ CH4$ (8.2$ ppm),$ C2H4$ (160$ppm),$ C2H6,$ (10.4$ ppm)$ which$ were$ detected$ by$ FIDV
methanizer$ detector$ (Fig.1)$ and$ confirmed$ by$ mass$
spectrometryj$ hydrogen$ was$ detected$ by$ TCD$ detector$(Gas$chromatograph$8610C,$SRI).$

Fig.1.$ Hydrocarbons$ obtained$ during$ electrochemical$
CO2$reduction$in$three$electrode$cell$(upper$right$corner)$
at$V1.38$V$vs.$SHE$on$oxidised$copper$foil$(FID$detector).$

References+[1]$ Y.$Hori,$Modern$Aspects$of$Electrochemistry,$42,$ch.$
3,$89–189,$Springer,$New$York$(2008)

Short$CV$of$Mariana$Spodaryk$th
Born$17 $of$October$1988$in$IvanoVFrankivsk,$Ukraine$
2011$ Master$ Degree$ in$ Technical$ Electrochemistry$ in$ Kyiv$ National$ University$ of$ Technology$ and$
Design,$Ukraine$
2011$V$14$PhD$student,$Ukraine$National$Academy$of$Science$in$Kyiv,$Ukraine$
2013$V$14$Guest$Scientist$at$EMPA$Materials$Science$&$Technology,$Dübendorf,$Switzerland$
June$2015$PhD$degree$in$Physical$Chemistry,$Ukraine$National$Academy$of$Science,$Ukraine$
October$2015$Post$Doc$Researcher$at$EPFL,$Valais$SB$ISIC$V$LMER$in$Sion,$Switzerland$
Mariana$Spodaryk$
Corresponding$author:$Mariana$Spodaryk,$email:$mariana.spodaryk@epfl.ch,$Tel.$+41$21$69$58213$

18

STRUCTURAL STUDIES ON METAL HYDRIDES USING IN-SITU X-RAY
DIFFRACTION AND THE PDF METHOD
Yumiko Nakamura, Kouji Sakaki, Hyunjeong Kim, Kohta Asano
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan
Our recent studies on metal hydrides using advanced in-situ X-ray diffraction (XRD) and Pair Distribution Function (PDF)
methods are reported. In-situ time-resolved XRD set up using synchrotron radiation X-ray was developed to follow phasetransformation and structural changes of materials during hydrogen absorption and desorption. Upgrading the set up, thecurrent system can collect in-situ XRD data for the PDF method, also, which enables to analyze local structure andnanostructure changes.

Introduction

Results

Metal hydrides can store hydrogen safely and reversibly
in a limited space. They are promising for effectivehydrogen storage for CO 2-free hydrogen society in future.
We have been doing research on metal hydrides
focusing on their hydrogenation and structural properties.
Since hydrogen absorption is accompanied by structuralchanges, structural properties are closely related to thehydrogenation properties. In this study, our recent results
accompanied by developing new set up for in-situ timeresolved and PDF methods [1] will be presented.

Time-resolved measurements were conducted for LaNi5based LaNi2Co3 alloy. When 1 MPa of hydrogen was
loaded, alpha phase transformed to an intermediatephase, which was not observed in an equilibrium state,
and then continuously changed into gamma phase. In
contrast, when 0.2 MPa of hydrogen was loaded, alphaphase transformed to beta, and finally to gamma phasewith passing two phase regions, as seen in equilibrium
measurements. From these results, this method enables
to find a reaction pass and structural changes in nonequilibrium reaction.

Experimental
In-situ XRD measurements were conducted at BL22XU(high-energy beam line) at SPring-8. Angular-dispersive
XRD data were collected in transmission geometry on aflat panel detector using monochromatic X-rays (E ~ 35
keV or 70 keV). Powder or pieces of sample was sealed
into a sample holder made of kapton capillary and fitting
connection, which was connected to a Sieverts
apparatus. Hydrogen gas was supplied to the capillary inabsorption measurements, and the capillary wasevacuated in desorption measurements. Rotating
mechanism was attached to the sample holder to reduce
effects of preferred orientation.
For time-resolved XRD measurements, data wascollected every second. For PDF measurements, data
was collected for around 1 to 300 seconds for each state
depending on the intensity of the sample and the rate ofobserved reaction. The data was integrated andconverted each for the Rietveld method for crystal
structure analysis or the PDF method for local/nano
structure analysis.

The PDF method was applied to Ti-Cr-V solid solution
alloys and their hydrides. During absorption/desorption
cycles, r-dependent peak broadening in PDF significantly
increased. This is attributed to disordering induced bydislocations in the metal lattice, and related todegradation [2]. In another trial, nanostructure in Mgbased thin film and their structural change uponhydrogenation was successfully detected.

References[1] Th. Proffen, S. J. L. Billinge, T. Egami and D. Louca,
Z. Kristallogr. 218 (2003) 132–143[2] H. Kim, K. Sakaki, H. Ogawa, Y. Nakamura, J.
Nakamura, E. Akiba, A. Machida, T. Watanuki, Th.
Proffen, J. Phys. Chem. C, 117 (2013) 26543−26550
Acknowledgement This work has been conductedunder collaboration with Dr. Machida (QST) and Prof.
Dam (TU Delft), supported by Photon and Quantum
Basic Research Coordinated Development Program(MEXT, Japan).

Yumiko Nakamura is a Principal Research Manager of Research Institute of Energy Frontier,
National Institute of Advanced Industrial Science and Technology (AIST). She joined AIST in 1998
after research experiences at SANYO Electric Co. Ltd., and RITE. She received a doctoral degree at
Kyoto University in 2002. She studied at Institute for Energy Technology (IFE), Norway in 20052006.

Yumiko Nakamura

Her main research interest has been hydrogen storage using metal hydrides, focusing on relation
between structural properties and hydrogenation properties. For this purpose, she has beendeveloping in-situ setup in X-ray diffraction, neutron diffraction/scattering, and other in-situ
characterization methods with her group members and collaborators.

Corresponding author: Yumiko Nakamura, yumiko.nakamura@aist.go.jp, +81-29-861-9309

19

SODIUM SUBS ITUTIONFULLERIDESEFFECTIN

LITHIUM INTERCALATED

M. Gaboardi,1 C. Milanese,2 G. Magnani,3 N. Sarzi-Amadé,4 M. Riccò,3 S. Sanna,4 D.
Pontiroli,3 and F. Fernandez-Alonso.1,5
1 - ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire (UK). 2 - Department of Chemistry, Universityof Pavia (Italy). 3 - Department of Physics and Earth Sciences, University of Parma (Italy). 4 - Dipartimento di Fisica,
Università di Pavia, Pavia, (Italy). 5 - Department of Physics and Astronomy, University College London, London (UK).
Abstract: We report here a thorough study of NaxLi6-xC60 and NaxLi12-xC60 alkali cluster-intercalated fullerides as optimized
materials for hydrogen storage. In these materials, hydrogen is chemisorbed by the C60n- anion, through the formation of
C60Hy (y=10-48). The destabilizing effect of Na reflects on a 70 °C lower absorption temperature, 14 kJ/mol H2 lower
desorption enthalpy, 67% improved absorption kinetics, and an optimized absorption of about 5 wt% H2 at 280 °C (100 bar
H2).

Methods
NaxLiy-xC60 phases were synthesized via solid state
reaction of Na, Li, and C60. Sodium and lithium azides canalso be exploited in the synthesis. Several days of
annealing and regrind were found to improve thecrystallinity. Kinetic absorption measurements werecarried out at 5 °C/min up to 350 °C and desorptions up to
400 °C. Samples were investigated by XRD and in situ
neutron diffraction upon D2 absorption.[1] Raman
spectroscopy was carried out by using a 532 nm
wavelength laser in order to study the state of charge of
C60 and, indirectly, the residual charge on intercalated
metals. Nuclear magnetic resonance (NMR) was carriedout on NaxLi6-xC60 fullerides in order to study the alkali
cluster structural transitions.[2,3].

Discussion
The substitution of Li by small amounts of Na (x=0.5-2)
significantly improves all the H2 sorption parameters(Ton(des), Ton(des), ΔHdes, ab/de-sorption kinetics, andmaximum absorption).[4] On the other hand, an increasing
amount of Na improves the crystallinity at the expense of
the sorption properties. All these materials presented fullreversibility and the crystallinity was found to improveupon cycling. In contrast to what expected, the second
cycle displays improved kinetics, suggesting easy
diffusion of H2 in the large interstitial voids of the C60nstructure. NaxLi12-xC60 fullerides were also investigated
and they showed improved crystallinity. In particular, NMR
and muon spin relaxation spectroscopies evidenced theformation of Li-H covalent species, thought to trigger thehydrogenation process and stable even after the complete
H2 absorption. [5]Mattia Gaboardi

Fig. 1: Hydrogen absorption (left) and desorption (right)
kinetics of NaxLi6-xC60 fullerides.

References[1] Gaboardi M, Duyker S, et al. JPCC, 2015;
119:19715–21.
[2] Amadè NS, Gaboardi M, et al. Submitted, 2016.
[3] Maidich L, Gaboardi M, et al. Carbon N Y, 2016;
96:276–84. doi:10.1016/j.carbon.2015.09.064.
[4] Gaboardi M, Milanese C, et al. arXiv: 1611.06512,
2016.
[5] Gaboardi M, Cavallari C, et al. Carbon N Y,
2015;90:130–7.

Short CV: I have recently been appointed to a Marie-Curie fellowship and I’m developing my researchat the Rutherford Laboratories, as Post Doc in the Molecular Spectroscopy group. I have been working
at the Carbon Nanostructures Laboratory at the Physical Department of Parma’s University until 2016.
I have a M.Sc. in Materials Science and a PhD in Physics. My main research activity is focused on
the synthesis of metal decorated and intercalated carbon nanostructures for energy storage and theirspectroscopic, structural, and physical study.

Corresponding author: Mattia Gaboardi, mattia.gaboardi@stfc.ac.uk, Tel. +44 (01235) 445492

20

th

11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa,$Hawaii$2017$

CONVERSION)OF)RENEWABLE)ENERGY)TO)SYNTHETIC)HYDROCARBONS)
Noris$Gallandat,$Jérémie$Bérard,$Andreas$Züttel$
Institute$ of$ Chemical$ Sciences$ and$ Engineering$ (ISIC),$ Basic$ Science$ Faculty$ (SB),$ École$ polytechnique$ fédérale$ de$
Lausanne$(EPFL)$Valais/Wallis,$Energypolis,$Rue$de$l’Industrie$17,$CP$440,$CHW1951$Sion,$Switzerland$
The$design$and$build$of$a$pilot$plant$for$the$demonstration$of$the$conversion$of$solar$energy$to$synthetic$hydrocarbons$is$presented.$ The$ average$ power$ of$ the$ installation$ is$ set$ to$ 2kW,$ which$ corresponds$ to$ the$ world$ average$ energy$
consumption$ of$ a$ single$ person.$ The$ installation$ allows$ studying$ the$ energy$ flows$ and$ reservoirs$ and$ the$ interaction$
between$different$components,$comparing$the$performance$of$competing$technologies$and$establishing$an$energetic$and$
economic$database$from$the$real$world.$Further,$the$operating$parameters$such$as$pressure,$temperatures$and$energy$
flows$ are$ recorded$ at$ different$ locations$ to$ enable$ for$ system$ modeling$ and$ advanced$ optimization$ techniques$ to$ be$applied$ on$ real$ data.$ Last,$ the$ degradation$ of$ the$ various$ components$ will$ be$ investigated$ under$ actual$ working$conditions.$

Introduction)
The$ increasing$ share$ of$ renewable$ electricity$ sources$
brings$ about$ a$ challenge$ in$ terms$ of$ energy$
management:$ typical$ renewable$ electricity$ sources$ such$as$ wind$ and$ solar$ undergo$ daily$ and$ seasonal$ cycles.$Hence,$there$is$a$critical$need$for$the$conversion$and$the$storage$ of$ renewable$ energy.$ The$ technical$ solution$ to$this$ problem$ that$ is$ now$ emerging$ makes$ use$ of$ CO2$
capture$ technology$ combined$ with$ hydrogen$ produced$
from$ renewable$ energy$ to$ produce$ synthetic$
hydrocarbons$[1].$Small?Scale)Demonstrator)in)Sion)(SSDS))
In$ spite$ of$ the$ fact$ that$ most$ of$ the$ individual$ processes$
depicted$in$Figure$1$have$been$known$for$a$long$time,$the$integration$ of$ the$ full$ cycle$ is$ an$ engineering$ challenge$
and$detailed$ investigations$of$the$relevant$parameters$ at$a$ practical$ scale$ are$ missing.$ The$ build$ of$ the$ Smale&
Scale( Demonstrator( in( Sion( (SSDS)$ will$ exhibit$ the$feasibility$ of$ the$ overall$ process$ from$ solar$ to$ synthetic$
fuels.$ Furthermore,$ this$ unique$ system$ will$ deliver$performance$ data$ on$ real$ conditions$ and$ represent$ an$experimental$ platform$ where$ new$ components$ can$ be$easily$ integrated$ and$ existing$ materials$ can$ be$exchanged$by$new$ones$of$a$later$generation.$
The$ main$ components$ are$ the$ solar$ cells,$ batteries$ for$electricity$ storage,$ the$ electrolyser,$ the$ metal$ hydride$storage$ unit,$ the$ metal$ hydride$ compressor,$ the$ CO2$
absorber$ and$ the$ chemical$ reactors.$ The$ energy$ is$handled$ in$ 4$ sectors:$ (1)$ solar$ energy$ converted$ by$
photovoltaics$ to$ electricity,$ (2)$ Electricity$ converted$(DC/DC$and$DC/AC)$and$stored$in$two$types$of$batteries$(leadWacid$and$NickelWmetal$hydride$with$a$capacity$of$72$
kWh$ each),$ (3)$ Hydrogen$ produced$ by$ mean$ of$ water$electrolysis$ and$ stored$ in$ a$ metal$ hydride$ storage$ with$ a$capacity$ of$ 2.05$ kg$ corresponding$ to$ 80.8$ kWh,$ and$ (4)$Methane$ and$ methanol$ formed$ from$ the$ hydrogen$ and$
CO2.$

References)[1]$ A.$ Züttel,$ P.$ Mauron,$ S.$ Kato,$ E.$ Callini,$ M.$ Holzer,$and$ J.$ Huang,$ “Storage$ of$ Renewable$ Energy$ by$
Reduction$ of$ CO2$ with$ Hydrogen,”$ Chim.( Int.( J.(
Chem.,$vol.$69,$no.$5,$pp.$264–268,$May$2015.$

Figure$1:$ Representation$ of$the$ main$ components$ of$ the$ Small$ Scale$ Demonstrator$ Sion$ (SSDS)$ and$ key$figures$ of$
the$installation.$$
Noris$Gallandat$

Born$ in$ 1990$ in$ YverdonWlesWBains,$ Switzerland,$ Noris$ Gallandat$ graduated$ with$ a$ BSc$ in$
Mechanical$ Engineering$ from$ the$ Swiss$ Federal$ Institute$ of$ Technology$ Zurich$ (ETHZ)$ in$ 2012.$
During$this$time,$he$worked$as$an$undergraduate$research$assistant$in$the$field$of$hydrogen$storage$
and$CO2$methanation$at$EMPA.$He$then$went$on$to$pursue$graduate$studies$as$a$Fulbright$Scholar$
at$ the$ Georgia$ Institute$ of$ Technology,$ where$ he$ obtained$ his$ PhD$ degree$ in$ 2015.$ His$ doctoral$
thesis$ focused$ on$ the$ enhancement$ of$ ambient$ heat$ rejection$ in$ passive$ thermal$ management$
systems.$$
noris.gallandat@epfl.ch,$Phone:$+41$21$695$8213$
21

ACCELERATING ADVANCED WATER SPLITTING AND HYDROGEN
STORAGE MATERIALS DEVELOPMENT
Katie Randolph, Ned T. Stetson, and Eric Miller
U.S. Department of Energy
Accelerating the discovery and deployment of novel materials is essential for the U.S. to compete globally in manufacturingin the 21st century. In support of the DOE’s materials innovation and advanced manufacturing priorities, EERE launched
the Energy Materials Network (EMN)1 in 2016. The EMN is a network of national lab-led consortia aimed at accelerating
the development and commercial deployment of novel materials by enhancing the accessibility of unique material researchresources at the national laboratories to external stakeholders, such as academia and industry. EMN’s have been
established under the Hydrogen Production and Hydrogen Storage programs to accelerate materials development and tohelp meet the Programs’ targets that will enable widespread commercialization of hydrogen and fuel cell technologies.

Overview

HyMARCThe US Department of Energy’s (DOE) Fuel Cell
Technologies Office (FCTO) has made significant
progress in advancing and reducing costs of hydrogen andfuel cell technologies. With rollouts of fuel cell electricvehicles (FCEVs) underway, enabling technologies for thewidespread production of affordable, sustainablehydrogen becomes increasingly important as does
providing materials based options for on-board hydrogenstorage that can meet consumer demands of range andprice. The FCTO has launched several EMN consortia tohelp accelerate materials discovery and development.
This presentation provides an overview of the FCTO’s
Hydrogen Production and Storage Programs anddiscusses the role their associated EMN consortia,
HydroGEN for Advanced Water-Splitting (AWS) Materials2and HyMARC3 (Hydrogen Materials – Advanced ResearchConsortium), will play in supporting the FCTO’s mission.

The DOE Hydrogen Storage Program supports RD&D foradvanced hydrogen storage technologies that meet the
on-board storage demands of light duty vehicles.
Commercial FCEVs being released today use highpressure 700 bar hydrogen storage onboard, and thehydrogen fueling infrastructure is being installed to support
fast fueling of 700 bar hydrogen. High-pressure tanks are
significantly more expensive, larger and heavier thanconventional gasoline or diesel fuel tanks and fuelingrequirements add significant costs to the fuel and create
reliability issues at the station. Materials storage offers an
opportunity to enable storage at high density in a compact
container at lower pressures, providing the potential todecrease the cost of the hydrogen storage system andfueling infrastructure.
HyMARC is tasked with carrying out foundational research
to understand the interaction of hydrogen with materials in
relation to the formation and release from storage
materials. This effort includes the development ofcomputational material design tools, synthetic andcharacterization methodologies, and online databases ofhydrogen storage materials properties and computational
data that will accelerate materials discovery anddevelopment.

HydroGENThe DOE Hydrogen Production & Delivery Programsupports research, development and demonstration(RD&D) efforts to address critical challenges and barriers
for sustainable, large-scale hydrogen production
technologies. AWS pathways (including electrolysis,
photoelectrochemical and solar thermochemical routes)
are some of the more versatile pathways and can play asignificant role in terms of long-term, clean, high volume,
sustainable production.
The HydroGEN Consortium aims to accelerate the RD&D
of AWS technologies with a long-term cost goal of <$2/kgH2 by making available the consortium’s extensive
collection of materials research capabilities to address
RD&D challenges in efficiency, durability and cost.

KatieRandolph

References[1] EMN website: http://energy.gov/eere/energy-materialsnetwork/energy-materials-network[2] HydroGEN website: https://www.h2awsm.org/[3] HyMARC website: https://hymarc.org/

Katie has been a Technology Manager at DOE’s Fuel Cell Technologies Office for over eight years managing awide range of hydrogen production, delivery and storage research and development projects. In addition to project
management, her role includes managing the HydroGEN consortium and serving as the DOE co-chair for the U.S.
DRIVE’s HPTT. She received her bachelor’s degree in Chemical Engineering at University of Colorado, Boulder
and did her Ph.D. work at Colorado School of Mines focusing on in-depth experimental and modeling studies on
the high temperature pyrolysis of C6 hydrocarbons to evaluate the effects of temperature and fuel structure on
conversion, hydrogen production, reactivity, and deposit formation under SOFC operating conditions. Prior tojoining the DOE, Katie worked for Shell Exploration and Production Co. as a petrophysical engineer on amultidisciplinary team in the continued development of a mature Deep Sea Gulf of Mexico oil fields. Corresponding
author: Katie Randolph, Katie.randolph@ee.doe.gov, 240-562-1759

22

High Temperature Hydrides for Concentrated Solar Thermal Storage
Craig Buckley, Drew Sheppard, Terry Humphries, Dehua Dong
Department of Physics and Astronomy, Fuels and Energy Technology Institute, Curtin University, GPO Box U1987, Perth
6845, WA, Australia

Solar energy is the most abundant renewable energy resource that is available and therefore logically represents the mostimportant renewable energy resource to focus our attention upon. The International Energy Agency roadmap for solar
energy set a target of approximately 22% of global electricity production from solar energy by 2050, with 50% being
produced from concentrating solar thermal power systems. Achieving this target will be possible only if the costs ofproducing electricity from solar energy are significantly reduced and cost effective energy storage technologies can be
developed.
Energy storage is required to overcome the problems created by the fact that solar energy, like wind energy, is unevenly
distributed geographically, seasonally variable, intermittent and unpredictable due to weather conditions. A major challenge
is to achieve continuous, low-variability power generation from renewable energy sources, for stand-alone applications orfor integration with domestic power grids. Solar mirror collection fields can collect thermal energy during the day and run aheat engine to convert it into electricity, but cannot provide power at night unless integrated with an energy storage system.
At the present time Concentrated Solar Thermal (CST) systems with heat storage use the heat capacity (sensible heat) ofbinary liquid molten salt mixtures (40% NaNO3; 60% KNO3) to produce electricity during non-sun hours. A fundamental
problem is the large quantity, volume and cost of the molten salts required to store sufficient heat to operate the plant forseveral hours during periods when the sun does not shine. The cost of solar thermal heat storage is a critical factor in its
future deployment and there are two strategies for reducing its cost: 1) utilizing higher energy density storage materials to
reduce the volume and mass of material required and; 2) utilizing higher energy storage temperatures to increase overallsolar to electricity conversion efficiencies.
Reversible thermochemical reactions have the potential for substantially higher heat storage capacities than sensible heator phase change materials. In a CST system paired with a reversible thermochemical reaction, heat energy is primarily
used to operate the heat engine (i.e. steam turbine) to generate electricity. Excess heat energy can be stored chemicallyby allowing this heat to drive an endothermic chemical reaction. The beauty of the storage system lies in its reversibility,
allowing heat to be generated on demand by allowing the chemical reaction to proceed in reverse, exothermically. Thus a
CST system coupled with an optimised storage system allows for continuous electricity generation (day and night) fromsolar energy. By combining a high temperature metal hydride with a low temperature metal hydride a coupled pair
reversible metal hydride thermochemical solar energy storage system is created [1].
I will discuss the use of CST worldwide and will present some results on the properties of metal hydrides that are suitablefor CST applications, focussing on high temperature hydrides [2 – 10].

References[1] D.N. Harries, M. Paskevicius, D.A. Sheppard, T.E.C. Price, C.E. Buckley. Proc. of the IEEE, 100 (2012) 539-549.
[2] M. Fellet, Feature Editors: C.E. Buckley, M. Paskevicius, D.A. Sheppard. MRS Bulletin 38 (2013) 1012-1013.
[3] D.A. Sheppard, T.D. Humphries, C.E. Buckley. Materials Today 18 (2015) 414-415.
[4] M. Paskevicius, D.A. Sheppard, K. Williamson, C.E. Buckley. Energy, 88 (2015) 469-477.
[5] Q. Lai, M. Paskevicius, D.A. Sheppard, C.E. Buckley, K.F Aguey-Zinsou et al. ChemSusChem, 8 (2015) 2789-2825.
[6] D.A. Sheppard, , C. Corgnale, T. Motyka, R. Zidan, C.E. Buckley et al. RSC Advances, 4 (2014) 26552-26562.
[7] D.A. Sheppard, M. Paskevicius, T.D. Humphries, M. Felderhoff, M. Dornheim, T. Klassen, P.A. Ward, J.A. TeprovichJr., C. Corgnale, R. Zidan, D.M. Grant, C.E. Buckley et al. Applied Physics A, 122:395 (2016) 1-15.
[8] D.A. Sheppard*, T.D. Humphries, C.E. Buckley. Applied Physics A, 122:406 (2016) 1-13.
[9] P.A. Ward , C. Corgnale, J.A. Teprovich Jr., T. Motyka, B. Hardy, D.A. Sheppard , C.E. Buckley, R. Zidan. Applied
Physics A, 122:462 (2016) 1-10.
[10] T.D. Humphries, D.A. Sheppard, M.R. Rowles, M.V. Sofianos, C.E. Buckley. J Materials Chemistry A, 4 (2016)
12170-12178.

Professor Craig Buckley is Dean of Research in The Faculty of Science andEngineering, Professor of Physics, Head of the Hydrogen Storage ResearchGroup and Deputy Director of the Fuels & Energy Technology Institute at Curtin
University, Australia. Since being awarded his Ph.D. in 1994 from Griffith
University he has held various research positions in the U.K, USA and Australia
prior to being awarded tenure at Curtin University. His research is focussed onhydrogen storage materials and the investigation of the structural properties ofa wide range of materials. Craig has published 127 scientific papers in peer
reviewed journals.
Professor Craig Buckley

Corresponding author: Professor Craig Buckley, c.buckley@curtin.edu.au, +61401103602

23

th

11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

COMPLEX METAL HYDRIDES FOR STATIONARY HYDROGEN STORAGE
AND RECHARGEABLE BATTERIES
Julien O. Fadonougbo, Jee-Yun Chung, Yong-Seok Choi, Young-Su Lee, Jin-Yoo Suh,
Young Whan Cho*
High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, South Korea
Abstract
Some complex metal hydrides have high volumetric capacity suitable for massive scale stationary hydrogen storage
system and can also be tailored to have high ionic conductivity at moderate temperatures for rechargeable battery
applications. In this presentation, we will present our recent work on the process development for the production of Mg/Fe
nanocomposite powders which can be hydrogenated under relatively mild condition. Characteristics of the solid state Liion conductors based on LiBH4-oxide nanocomposites will also be discussed including preliminary results on theelectrochemical cell tests both at room temperature and at elevated temperatures.

Mg2FeH6 for stationary hydrogen storage
Mg2FeH6 has gravimetric and volumetric capacity of 5.5
3wt.% and 150 kg/m , respectively and excellent
reversibility over 500 cycles above 723K and below 100
bar [1]. However, the reaction kinetics becomes too slow
below 673K which is the practical upper limit temperatureof the storage system combined with a thermal
management unit based on commercially available heattransfer fluid. We have been studying two competing orcomplement milling processes which can be developed
eventually for large scale production of highly active
nanocomposite powders starting from Mg and Fe powders
together with process control agents (PCAs). The PCAs
help to process the powders in air. So far, lab-scale but
mass scalable tumbling ball milling and vertical roll milling(fig. 1) have been successfully tested in our laboratory
using low cost commercial Mg and Fe powders with anorganic additive as a PCA. The final product is
nanocrystalline powders with a particle size distribution
suitable for safe handling in air.

capacity in 2 hours and 80% in 24 hours at 673K under 60
bar H2.

LiBH4-oxide composite solid electrolytes
We have developed a fast solid state Li ion conductor
composed of LiBH4 and SiO2 by means of interface
engineering [2]. A composite of LiBH4–SiO2 was simply
synthesized by high energy ball-milling, and two types of
SiO2 (MCM-41 and fumed silica) having different specificsurface areas were used to evaluate the effect of the
LiBH4/SiO2 interface on the ionic conductivity
enhancement. The ionic conductivity of the ball-milled
LiBH4–MCM-41 and LiBH4–fumed silica mixture is as high
−5
−1
−4
−1
as 10 S cm and 10 S cm at room temperature,
respectively. In particular, the conductivity of the latter iscomparable to the LiBH4 melt-infiltrated into MCM-41. The
conductivities of the LiBH4–fumed silica mixtures atdifferent mixing ratios were analyzed employing acontinuum percolation model, and the conductivity of the5
LiBH4/SiO2 interface layer is estimated to be 10 times
higher than that of pure bulk LiBH4. The result highlights
the importance of the interface and indicates thatsignificant enhancement in ionic conductivity can beachieved via interface engineering.

References[1] B. Bogdanovic, A. Reiser, K. Schlichte, B. Spliethoff,
B. Tesche, J. Alloys Comp. 345 (2002) 77-89.
Fig 1. Tumbling ball mill (left) and vertical roll mill (right)
Moreover, this nanocrystalline powder could behydrogenated more than 60-70% of the theoretical

Y. W. Cho[2] Y.-S. Choi, Y.-S. Lee, K.-H. Oh, Y. W. Cho, Phys.
Chem. Chem. Phys., 18 (2016), 22540-22547.

Dr. Young Whan Cho has been working on hydrogen storage materials since 2002 and is the authorof more than 150 scientific publications and 20 patents. Following a PhD in Materials Science andMetallurgy of Cambridge University in 1990, he took up a position as senior researcher with Korea
Institute of Science and Technology where he is now a principal researcher. Dr. Cho is also chairprofessor of Nanomaterials Science and Engineering of University of Science and Technology. Since
2007, he has been one of the expert members of IEA-HIA Task 22 and 32 and working with many
international institutes including Aarhus University, Birmingham University, Caltech, EMPA, HZG, andKIT.
Corresponding author: Young Whan Cho, oze@kist.re.kr, +82-2-958-5465

24

th

11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa$,$Hawaii$2017$

HYDROGEN) STORAGE,) ION) TRANSPORT) PHENOMENA,) AND) PHOTOLUMINESCENCE) OF)
COMPOSITE)HYDRIDE)MATERIALS)
Joseph$ A.$ Teprovich$ Jr.,$ Patrick$ Ward,$ ThanhFTam$ Truong,$ Josef$ Velten,$ Jonathan$ Christian,$ Jason$ Weeks,$ Hope$ Hartman,$
Jefferson$Dixon,$Brent$Peters,$Hector$R.$ColonFMercado,$Aaron$Washington,$Jay$Gaillard,$Scott$Greenway,$Ragaiy$Zidan$
Savannah$River$National$Laboratory,$USA,$Aiken,$SC$29803$
Abstract:$This$talk$will$cover$recent$and$ongoing$work$supported$by$the$Materials$Science$and$Engineering$Division$of$the$Office$of$
Basic$ Energy$ Sciences$ at$ our$ laboratory.$ The$ goal$ of$ this$ project$ is$ to$ achieve$ a$ basic$ understanding$ of$ the$ formation$ and$ the$physicochemical$properties$of$composite$hydride$materials,$formed$by$the$interaction$of$carbon$nanomaterials$with$hydrides$and/or$hydrogen$ gas.$ $ The$ purpose$ of$ our$ investigation$ is$ to$ understand$ hydrogen$ interaction$ with$ a$ novel$ class$ of$ materials$ and$ to$develop$ control$ over$ a$ material’s$ properties$ at$ the$ electronic,$ molecular,$ and$ atomic$ level,$ which$ will$ serve$ as$ the$ foundation$ for$discovering$unique$materials$for$new$energy$technologies$and$can$support$other$aspects$of$DOE$missions.$With$this$foundation,$we$
will$ be$ able$ to$ design,$ synthesize,$ and$ characterize$ new$ materials$ for$ various$ energy$ storage$ applications$ through$ a$ synergistic$
theoretical$ and$ experimental$ approach.$ $ The$ main$ focus$ of$ this$ research$ is$ for$ hydrogen$ storage^$ however,$ we$ discovered$ that$
many$of$these$materials$are$multiFmodal$and$possess$many$of$the$properties$desired$for$the$next$generation$of$energy$storage$and$conversion$devices.$

Hydrogen)Storage)
The$ ability$ of$ metalFdoped$ carbon$ nanocomposites$ systems$(MxFC60FHy,$M=Li,$Na)$to$reversibly$interact$with$hydrogen$has$
been$wellFestablished$in$the$literature.$The$metal$intercalation$
is$ found$ to$ alter$ the$ electronic$ structures,$ allowing$ CFH$bonds$
to$ form$ and$ dissociate$ at$ milder$ condition$ than$ pure$ C60.$ $ For$
example,$ a$ LixC60Hy$ material$ demonstrated$ a$ reversible$hydrogen$storage$capacity$of$5$wt%$in$which$a$rarely$observed$
reversible$ fcc$ to$ bcc$ phase$ change$ occurring$ at$ mild$[1]
conditions. $$Hydrogen$is$stored$via$the$formation$of$covalent$
CFH$ bonds$ to$ form$ a$ hydrogenated$ fullerene$ (fullerane).$Interestingly,$ NMR$ experiments$ and$ theoretical$ modelling$suggests$ the$ formation$ of$ a$ Li$ atom$ inside$ the$ C60$
(endohedral^$ Li@C60)$ during$ hydrogenation.$ $ In$ the$ Na$intercalated$ system,$ we$ observed$ the$ formation$ of$ C60H60$[2]through$a$series$of$LDIFTOFFMS$experiments. $$$It$ was$ also$ found$ that$ C60$ could$ act$ as$ a$ catalyst$ for$ the$desorption$ of$ hydrogen$ from$ LiBH4$ and$ decrease$ the$[3]
desorption$temperature$by$~150°C. $$$We$also$demonstrated$
that$ LiBH4$ can$ be$ reversibly$ regenerated$ in$ the$ presence$ of$
C60$ at$ temperatures$ and$ pressures$ much$ lower$ than$ that$ of$
pure$LiBH4.$$Ion)Transport)Phenomena)
Through$ solid$ state$ NMR$ work$ we$ discovered$ that$ a$ highly$+[4]mobile$ Li $ species$ is$ formed$ in$ a$ LiBH4:C60$ nanocomposite. $$Further$ electrochemical$ experiments$ confirmed$ this$observation$and$it$was$demonstrated$that$the$material$can$be$[5]
used$ as$ a$ solidFstate$ electrolyte$ in$ a$ lithium$ halfFcell. $$Theoretical$work$suggested$that$the$observed$high$lithium$ion$+
Fmobility$is$due$to$a$nanoionic$mechanism$in$which$the$Li /BH4 $ion$ pair$ is$ destabilized$ in$ the$ presence$ of$ C60$ leading$ to$ the$+high$Li $mobility.$

Recent$ work$ demonstrated$ that$ milling$ Li2B12H12$ produced$ a$material$that$has$fast$lithium$ion$conduction.$$This$material$can$achieve$ a$ lithium$ ion$ conductivity$ >1$ mS/cm$ at$ temperatures$[6]
above$ 55°C. $ $ Further$ experimental$ work$ demonstrated$ that$
this$material$can$be$used$as$a$solid$state$electrolyte$in$half$and$
full$ lithium$ ion$ battery$ cells$ with$ good$ cycle$ stability$ at$ room$
temperature.$$$$$$$

Photoluminescent)Properties)
During$our$work$with$the$MxC60Hy$ systems$we$observed$that$a$
color$ change$ would$ occur$ when$ the$ material$ was$hydrogenated.$$This$suggested$that$it$may$be$possible$to$fineF
tune$ the$ photoluminescent$ properties$ of$ these$ materials$
through$ the$ formation$ of$ CFH$ bonds$ on$ C60.$ $ To$ isolate$ the$effect$ of$ H$ chemisorption$ on$ the$ photoluminescent$ properties$
of$C60,$we$prepared$a$series$of$fulleranes$(C60Hx)$with$different$[7]levels$ of$ hydrogen$ content. $ $ It$ was$ found$ that$ C60H18$ and$C60H36$ are$ formed$ during$ hydrogenation$ with$ emission$
occurring$at$550$and$435$nm$respectively.$$Recent$work$on$the$Na$and$Li$intercalated$fullerane$systems$demonstrated$that$the$emission$spectrum$can$be$further$shifted$to$the$blue$portion$of$
the$ visible$ spectrum$ through$ the$ formation$ of$ fulleranes$ with$>36$ hydrogen$ atoms$ per$ C60.$ $ It$ was$ also$ found$ that$ these$materials$can$be$incorporated$into$polymers$with$potential$use$
in$luminescent$down$shifting$applications.$

References)[1]$ Nano%Letters,$2012,$12,$582F589.$[2]$$Nanotechnology,$2013,$24,$455601.$[3]$$J.%Phys%Chem.%C,)2013,$117,$22569F22575.$[4]$ J.%Phys.%Chem.%C.,)2010,$114,$19862F79866.$[5]$$J.%Phys.%Chem.%C,)2014,$118,$21755F21761.$[6]$$J.%Mater.%Chem.%A,$2015,%3,$22853F22859.$[7]$$Nanoscale,$2016,$8,$18760F18770.$

Joseph$received$his$Ph.D$in$chemistry$from$Lehigh$University$in$2008.$He$worked$as$a$postFdoctoral$
research$ scientist$ at$ the$ Savannah$ River$ National$ Laboratory$ (SRNL)$ from$ 2009$ to$ 2011.$ In$ 2011,$
he$ became$ a$ full$ time$ staff$ member$ at$ SRNL$ and$ is$ currently$ a$ principal$ scientist$ in$ the$ Clean$
Energy$directorate.$He$has$published$23$peerFreviewed$articles$on$the$use$of$hydrides$in$a$variety$of$energy$ storage$ and$ conversion$ applications$ and$ presented$ this$ research$ at$ multiple$ national$ and$international$ conferences.$ This$ includes$ the$ synthesis$ of$ alane$ (AlH3)$ for$ portable$ power$ systems,$
boron$based$hydrides$for$solid$ionic$conductors,$alanates$for$use$as$highFcapacity$anode$materials,$
metal$ intercalated$ carbon$ nanocomposites$ for$ hydrogen$ storage,$ and$ metal$ hydride$ based$ thermal$energy$storage$systems$for$concentrating$solar$power.$He$also$serves$as$an$adjunct$professor$in$the$$general$chemistry$sequence$at$the$University$of$South$Carolina$–$Aiken$campus.$
Joseph$A.$
Teprovich$Jr$
Corresponding$author:$Joseph$A.$Teprovich$Jr.^$joseph.teprovich@srs.gov^$570F578F7842$

25

HYDROGEN STORAGERESEARCH EFFORTCHARACTERIZATIONAND

OPTIMIZATION

Iffat Nayyar, Marina Chong, Adrian Houghton, Abhi Karkamkar, Mark Bowden, Bojana
Ginovska, Phuong Nguyen, Craig Jensen and Tom Autrey.
Pacific Northwest National Laboratory, Richland, WA 99352, USA
Pacific Northwest National Laboratory, in collaboration with the National Renewable Energy Laboratory, Lawrence
Berkeley National Laboratory, and the National Institute Standards and Technology, is developing advanced
characterization capabilities to validate theories and test concepts proposed in the development of new hydrogen storage
materials. Specifically, in-situ multi-nuclear solid state variable pressure (VP) Magic Angle Spinning NMR, to 200 bar,temperature to 473 K, to identify key intermediates in the release and uptake of hydrogen in complex metal hydrides.
This work is focused on understanding how additives control selectivity and enhance reversibility; Low temperature (to 5K) solid state 1H NMR to measure dynamics and thermodynamics of adsorption of H2 to high surface area storage
materials; multi-nuclear liquids NMR, variable pressure 1 – 100 bar, variable temperature (250 – 350 K) to measure key
intermediates, kinetics and thermodynamics of hydrogen release and uptake in liquid carriers and variable pressure (120 bar) variable temperature (298 – 353 K) reaction calorimetry to measure kinetics and enthalpies of H 2 uptake in liquidand solid stores to benchmark and validate computational predictions of binding enthalpies in liquid carriers.

Introduction
PNNL is developing new capabilities to validate theories andtest novel concepts proposed by the research community toassist in the design and discovery of novel approaches andnew materials for the storage and delivery of hydrogen forfuel cell power applications. A parallel research effort onmaterials evaluation compliments the characterization
capability development. Examples of current study are solid
stores, specifically to understand how additives control thereactivity and selectivity of reversible pathways in Mg(BH 4)2;
liquid stores, to validate and benchmark the enthalpies of H2
release and uptake by liquid N-heterocycle carriers andphysi-sorption of H2 to high surface area carbons doped withelectron rich and electron deficient defects.
The materials evaluation effort provides the benefit of
testing, demonstrating and improving the value of thecharacterization methods and to provide experimental data
to enable the benchmarking of computation methods used to
predict the thermodynamic properties of hydrogen storage
materials. Properly calibrated computational methods havethe promise to ‘narrow the field’ and accelerate the progress
towards the development of new hydrogen storage
materials. However, there are inconsistencies between somecomputational predictions and even between different levelsof theory. The research efforts underway are to understandthese discrepancies to provide a rational approach to
improving theory to fulfill its promise to accelerate progress.

Results
Our experimental studies on variable loading of solvates toMg(BH4)2 show that THF adducts yield the release of H 2 attemperatures below 200 °C forming Mg(B10H10) as the major
dehydrogenation adduct. The results of our in-situ solid state
MAS 11B NMR, to gain insight into the initial stages ofdecomposition of Mg(BH 4)2*nTHF solvates as well as thehydrogenation of Mg(B3H8)2*yTHF, will be discussed. We
are developing a library of chemical shifts of potential
intermediates consisting of the 11B NMR spectra of authentic
intermediate borane anions, e.g., B 3H8, B9H14 and B11H14, in
addition to the calculate solid state 11B NMR spectra ofpotential intermediates where no experimental data isavailable.
The reported Td for H2 release from perhydro-1,3,5 triazine(C3N3H9 Ù C3N3H3 + 3 H2, ca. 6.9 wt% H2) is ca. 60 °C.
However, the parent triazine is a solid at room temperature.
Alternatively, 2,4,6 trimethyl – 1,3,5 – triazine (C6N3H15),
density 1.044 g/cc, is a liquid at room temperature. This
LOHC provides ca. 48 g H 2/L. Methyl-triazine can provide
ca. 54 g H2/L whereas fuel blends of triazine and methyl
triazine can provide LOHCs between 48 - 54 g H2/L. These
liquid blend carriers are made from inexpensive starting
materials and stable to air. We will measure the temperature
range to preserve liquid fuel composites and use the unique
PNNL characterization capabilities in calorimetry to
determine an experimental value of ΔHd for H2 release tocompare with the computational predictions provided in the
Air Products final report. The experimental work will be used
to benchmark computational approaches developed to
predict thermodynamics in condensed phase materials.
Acknowledgements. Support for this research is provides by
The Fuel Cell Technology Office, in the US Department ofEnergy’s Office of Energy Efficiency and Renewable Energy
is gratefully acknowledged. Pacific Northwest National
Laboratory is operated by Battelle for the U.S. Department ofEnergy. The authors acknowledge helpful discussion withTom Gennett, Gary Edvenson, Mira Dimitrievska, Terry
Udovic, Craig Brown, Matt Kapelewski and Jeff Long.

Tom Autrey is Staff Scientist in the Physical and Computational Science Directorate at the PacificNorthwest National Laboratory. Dr. Autrey’s current research interests are focused on small molecule
activation in catalysis and approaches to energy storage for fuel cell power applications. NMR methods,
Reaction Calorimetry are used to identify key intermediates and measure thermodynamic properties ofreactions involving the activation of hydrogen in condensed phase materials.
Corresponding author: Tom Autrey, tom.autrey@pnnl.gov, +1 (509) 375-3792

26

THE
DEVELOPMENT
OF
MODEL
FOR
EVALUATINGTHEPERFORMANCE OF MATERIALS-BASED HYDROGEN STORAGE
SYSTEMS AND THE SCREENING OF HYDROGEN STORAGE
MATERIALS
Matthew Thornton (NREL), Davis Tamburello (SRNL) and Kriston Brooks (PNNL)One of the most critical elements in engineering a hydrogen fuel cell vehicle is the design of the on-board hydrogenstorage system. Because the current compressed-gas hydrogen storage technology has several key challenges,
including cost, volume and capacity, materials-based storage technologies are being evaluated as an alternative
approach. These materials-based hydrogen storage technologies include metal hydrides, chemical hydrides, andadsorbent materials, all of which have drawbacks of their own. To optimize the engineering of storage systems based onthese materials, it is critical to understand the impacts these systems will have on the overall vehicle system performanceand what trade-offs between the hydrogen storage systems and the vehicle systems might exist that allow thesealternative storage approaches to be viable.
To gain a better understanding of the interactions that exist between various materials-based hydrogen storage systems
and the vehicle system and to understand the performance and viability of various material candidates, the National
Renewable Energy Laboratory (NREL), Savanna River National Laboratory (SRNL) and the Pacific Northwest National
Laboratory (PNNL) developed a vehicle-level model designed to be sensitive to these issues. This model was developed
under the Hydrogen Storage Engineering Center of Excellence (HSECoE) as a specialized tool that could be used toassist in the design and engineering of materials-based hydrogen storage systems being considered by the HSECoE.
This tool is designed to not only allow for understanding key trade-offs, but also to have a seamless integration with the
HSECoE fuel cell and detailed hydrogen storage system models and to evaluate progress towards the U.S. Departmentof Energy's hydrogen storage technical targets. This model has been integrated with a fuel cell model developed by Ford
Motor Company in a HSECoE common modeling framework.
This paper will focus on the development, structure, and validation of the modeling framework and demonstrate its
application to material screening and hydrogen storage system engineering. This includes hydrogen storage sizing
analyses, mass compounding analyses, range versus volume studies, and vehicle and component performance
analyses, such as acceleration rates and fuel cell and energy storage interactions.

Matthew Thornton manages NRELs Fuels Performance Group, which includes the Advanced
Biofuels and Advanced Combustion and Fuels teams. Research in this group focuses on theperformance and utilization of advanced fuels and high efficiency combustion strategies. He also is
the NREL lead for DOE's Hydrogen Storage Engineering Center of Excellence, advancing materialsbased hydrogen storage systems for fuel cell vehicles. Previously, he served as task leader for
NREL’s ReFUEL laboratory and Systems Analysis Team, overseeing engine and vehicle fueleconomy testing, and modeling and simulation research. He holds a PhD in civil and environmental
engineering from the Georgia Institute of Technology and master’s degrees in civil engineering andurban and regional planning from Michigan State University.
Matthew
Thornton
Corresponding author: Matthew Thornton, matthw.thornton@nrel.gov, 720-232-4285

27

STATUS OF HIGH-PRESSURE METAL HYDRIDE COMPRESSORS FORAPPLICATIONS EXCEEDING 700 BAR
Robert C. Bowman, Jr.1, Terry A. Johnson2, Craig M. Jensen3, D. Barton Smith1, &Lawrence M. Anovitz1
1. Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; 2. Sandia National Laboratories, Livermore CA 94551
USA; 3. Hawaii Hydrogen Carriers, LLC, Honolulu HI 96813 USA
Abstract: This presentation considers (a) fundamental aspects of materials development with a focus on structure andphase equilibrium of metal hydrogen systems for the hydrogen gas compression; and (b) detailed assessments from athermal management viewpoint on system design and performance trade-offs for these hydride compressors. The
various concepts for metal hydride compressors built for specialized applications over the past four decades arereviewed. The prospects for achieving efficient MH compression devices that can be integrated into the gaseoushydrogen refuelling stations that can refill the 700-bar gas tanks of fuel cell powered vehicles will be discussed.

Background & Performance Requirements
Metal hydride (MH) thermal compression is an efficientand reliable method for increasing hydrogen (H2) gas
pressures by ratios from one to three orders ofmagnitude [1,2]. The most important component of suchdevices is the metal hydride material itself, which should
possess several characteristics in order to achieve an
efficient performance. Beyond the common hydrogenstorage properties important for every solid H 2 storage
material (e.g. high gravimetric and volumetric efficiency of
H2 storage, sufficiently fast hydrogen sorption kinetics
and effective thermal conductivity), the thermodynamics
of the metal hydrogen systems determine thetemperature dependence of the absorption/desorption
pressures. Several factors govern the performance of the
MH-compressors including appropriate matching of theabsorption/desorption pressure plateaus for multi-stagecompressors, minimal sloping of the isotherms andhysteresis parameters, increase of cycling stability andlife time, along with challenges in system design due tovolume expansion of the metal matrix during thehydrogenation.

Prototype 875-bar Hydride Compressor
Our team has just initiated a project that is explicitly
investigating and will ultimately demonstrate on thelaboratory scale a two-stage metal hydride compressor
with a feed pressure of approximately 100 bar to deliver
high purity H2 gas at outlet pressures ≥ 875 bar with the

Bob Bowman

potential capability for an energy efficiency of < 2.0
kWh/kg when relying on process waste heat from colocated equipment at a refuelling station. Candidate
alloys are being assessed to identify compatible pairs forthe lower pressure and higher-pressure stages for moredetailed characterizations of both absorption/desorption
hysteresis and stability during extended cycling prior toconstructing and evaluating the prototype compressor.
Acknowledgments: Authors thank the Fuel Cell
Technology Office of the U.S. Department of Energy(DOE), Office of Energy Efficiency and Renewable
Energy for support of this work. The Oak Ridge National
Laboratory is operated by UT-Battelle, LLC, underContract No. DE-AC05-00OR22725 with the U.S. DOE.
Sandia National Laboratories is managed and operated
by Sandia Corporation, a subsidiary of Lockheed Martin
Corporation, for the DOE’s National Nuclear Security
Administration under contract DE-AC04-94AL85000.

References[1] M.V. Lototskyy, V.A. Yartys, B.G. Pollet, R.C.
Bowman Jr., Int. J. Hydrogen Energy 39 (2014) 58185851.
[2] V. A. Yartys, M. Lototskyy, V. Linkov, D. Grant, A.
Stuart, J. Eriksen, R. Denys, R. C. Bowman, Jr., Appl.
Phys. A 122 (2016) 415.

Robert C. Bowman, Jr. is a Distinguished Member of the Technical Staff at the Oak Ridge National
Laboratory. He was born in Dayton OH in 1945 and earned the following Chemistry degrees: B.S.
Miami University; M.S. Mass. Inst. Tech.; and Ph.D. from Cal. Inst. Tech. He has previously worked
as research scientist/engineer at the Mound Laboratory (OH), Aerospace Corporation (CA), Aerojet
ElectroSystems (CA), and the Jet Propulsion Laboratory (CA). He started his research studies onproperties of metal hydrogen systems in 1969 and currently has over 260 technical publications injournals, conference proceedings, and review chapters in books on these materials and theirapplications. He holds three patents on metal hydrides for electrochemical devices and hydrogenstorage. He has been a co-chairman of several metal hydrogen conferences. Among Dr. Bowman’sawards are the 2015 DOE Hydrogen and Fuel Cells Program R&D Award in Hydrogen Storage
materials.

Corresponding author: Robert C. Bowman, Jr. rcbjr1967@gmail.com, Tel. 1-937-903-4350

28

Dynamic X-Ray Photon Correlation Spectroscopy, NVS and other Studies on(Ni0.60Nb0.4)100-xZrx (x=0 to 30) Amorphous Alloy Membranes
D. Chandra 1*, S. Sarker1, N. Pal1, S-M Kim1, R.Shi1, T.J. Udovic2, B. Ruta3, D. Isheim4, W-M Chien1, M.S. Somayazulu.5,
M. Dolan6, D. Viano6, J.Wermer7 , A. Paolone8, O. Palumbo8 (Corrosponding author: D. Chandra)
1 Mat. Sci.& Engr., University of Nevada, Reno, MS 388, Reno NV 89557 2 NIST Center for Neutron Research, MS
6102, Gaithersburg, MD 20899-6102, 3 European Synchrotron Radiation Facility BP 220, F-38043, Grenoble France, 4Mat. Sci.& Engr., Northwestern University, 2220 Campus Dr, Evanston, IL 60208 5CSIRO, QCAT, Energy, 1 Technology
Court, Pullenvale QLD 4069 Australia , 6 CDAC-CIW, 5251 Broad Branch Rd. NW, Washington, DC 20015-1305 , 7 Los
Alamos National Laboratory, Los Alamos, NM 87545,8 Physics Department, Sapienza University of Rome, Italy
Abstract: Crystalline Pd/Pd-Ag membranes are generally used in hydrogen separation from CO2 and other gases in power
generation applications. Inexpensive amorphous Ni-based alloys are being developed as an alternative to expensive Pdalloys. Amorphous membrane ribbons of (Ni0.60Nb0.40)100-xZrx fabricated by melt-spinning method exhibit highpermeabilities of hydrogen between 200-400oC [1-5]. Atom probe tomography (APT) revealed Nb-rich and Zr-rich clusters
embedded in a Ni-rich matrix whose compositions that deviated from the nominal overall composition of the membrane.
Fukuhara et al. [6] reported icosahedral cluster arrangement of Ni-Nb-Zr atoms; we also found clusters based on APT andneutron SANS data which can be interpreted as icosahedral arrangement. Neutron vibrational spectroscopy of these alloyyielded possible positions of hydrogen. Atom dynamic studies by X-ray photon correlation spectroscopy (XPCS) revealed
a dramatic reversible acceleration of the atomic motion under hydrogen atmosphere at low temperatures; these effects areobserved by standard thermodynamic/kinetic measurements. Dynamic mechanical analyses (DMA) indicated amorphous
to amorphous phase transitions well below the recrystallization temperature, as well as the change elastic modulus as afunction of temperature. Devitrification kinetics of these amorphous ribbons by using the John-Mehl-Avrami method
showed Avrami exponents ranging from 1.92 to 2.47 indicating diffusion controlled 3-D growth mechanism. In an attempt
to develop new alloys we show liquidus profiles for the ternary system using CALPHAD methodology. Hydrogen
permeation, atom probe tomography, small angle neutron scattering, neutron vibrational spectroscopy, dynamic
mechanical analyses, XPCS and devitrification kinetic aspects of these membranes will be presented.
(This research is supported by US DOE-NNSA grant, DENA0002004 and DOE-NETL FE0000998).
X-Ray Photon Correlation Spectroscopy (XPCS):
XPCS is used to obtain aging properties of themembranes. Atom dynamics are obtained by analyzing
the temporal correlations among photons scattered by thestudiedmaterial.
Typically,aQranges between 103 A-1 to several A-1(107–103Hz)depending on thesample and theFig. 1.Speckle formation by F.van
der Veen and F. Pfeiffer, J. Phys.
scattering
Cond. Mat. (1198).
geometry. Coherent
scattering
gives
speckle patterns as shown in the Fig.1. Incoherent
scattering gives the expected hallow with no speckle
not shown here.

(b)

W=1270s
(x)
W=25s

(c)

Selected XPCS Results Ni60Nb40 Alloy Ribbon: The
relaxation times of Ni and Zr W (no H2)=1270s decreases
to W =25s (with H2). Addition of Zr (30at.% to this to W =25s
(with H2). Addition of Zr (30at.% to this Ni60Nb40)
changes the W (no H2)=9800s, which drops to W=380s (with
H2), showing changes in the acceleration of dynamics(Fig. 2). The detector is set at the maxima of the XRD
broad peak of the hump; in this case the Q=2.7 (A-1) .
References
1. S. Sarker, D. Chandra, M. Hirscher, M. Dolan, D. Isheim, J.
Wermer, D. Viano, M. Baricco, D. Grant, O. Palumbo, A.
Paolone, R. Cantelli, Applied Physics A, A 122, 168 (2016).
2. S. Yamaura, Y. Shimpo, H. Okouchi, M. Nishida, O Kajita, H.
Kimura and A.Inoue, Materials Transactions, 44 (2003) 18851890

(a)

(d)

.Fig.2. (x) XPCS Auto correlation function plots,g2
ovs..time at 100 C and two time correlation function
maps: (a) with no H2 (b) with added H2 (c) desorptionof H2 (#1),(d) further desorption H2 (#2).
3. M.D. Dolan, N.C. Dave, A.Y. Ilyushechkin, L.D. Morpeth, K.G.
McLennan, J. Membr. Sci. 285 (2006) 30.
4. S.M Kim , D. Chandra et al, Journal of Non-Crystalline Solids,
358 (2012) 1165–1170.
5. S. Paglieri, N. Pal, D. Chandra, Journal of Membrane Science,
378 (2011) 42-50.
6. M. Fukuhara, N. Fujima, H. Oji, A. Inoue, S. Emura, JALCOM,
497 (2010)29

THE HYDROGENATION OF LITHIUM SILICIDES AN OLD STORYCONTINUED IN A NEW CONTEXTFranziska Biedermann, Daniel Thomas, Regina Hüttl, Jürgen Seidel, Florian Mertens
Technische Universität Bergakademie Freiberg, Freiberg, Germany
The use of silicon as an additive to destabilize metal hydrides was one of the first examples to tune the reversibility ofmetal hydride reactions. [1] Later the concept was expanded to metal hydride mixtures, which became a largely exploitedmethod to generate new hydrogen storage systems. [2] Originally the destabilization of lithium hydride by silicon assumed
the role of a demonstrator and was not used as a base for further investigations. However, recently lithium silicides haveattracted a lot of attention as potential energy storage materials in the context of lithium ion batteries. In contrast to thestandard anode material, lithiated graphite, with its capacity of 372 mAh/g, lithium silicides bear a theoretical potential ofa capacity of 4054 mAh/g. In the framework of the renewed interest in these materials, it was noticed that large
discrepancies in the description of the binary phase diagram exist and that thermodynamic data were only marginallyavailable and even worse, being contradictory. [3,4] Using a combination of direct calorimetric measurements to determine
absolute entropies and the determination of free reaction energies of sequence of hydrogenation reactions from thelithium richest phases to the ones that are very poor in respect to their lithium content, essentially all ambiguity regarding
the thermodynamic description of these phases was removed. [5,6] The high quality of some of the obtained data partly
depended on a turbo-pump modified Sieverts´ apparatus allowing hydrogenation experiments at very low pressure. The
implications of the gained thermodynamic description in respect to the cell potentials of corresponding lithium ion
batteries will be given.

References[1] J. J. Vajo, F. Mertens, C. C. Ahn, R. C. Bowman Jr., B. Fultz: “Altering Hydrogen Storage Properties by Hydride
Destabilization through Alloy Formation: LiH and MgH2 Destabilized with Si:” J. Phys. Chem. B 2003, 108, 13977.
[2] J. J. Vajo, S. L. Skeith, F. Mertens, “Reversible Storage of Hydrogen in Destabilized LiBH4”,
J. Phys. Chem. B 2005, 109(9), 3719.
[3] Peisheng Wang, Artem Kozlov, Daniel Thomas, Florian Mertens, Rainer Schmid-Fetzer “Thermodynamic Analysis of
the Li-Si Phase Equilibria from 0 K to Liquidus Temperatures” Intermetallics 2013, 42,137-145[4] Daniel Thomas, Michael Zeilinger, Daniel Gruner, Regina Hüttl, Jürgen Seidel, Anja U.B. Wolter, Bernd Büchner,
Thomas F. Fässler, Florian Mertens “The Heat Capacity and Entropy of the Lithium Silicides Li17Si4 and Li16.42Si4 in
the Temperature Range from 2 K to 873 K”, J. Chem, Thermodyn. 2015, 85, 178–190[5] Song-Mao-Liang, Franziska Biedermann, Artem Kozlov, Jürgen Seidel, Florian Mertens, Rainer Schmid-Fetzer„Thermodynamics of Li-Si and Li-Si-H Phase Diagrams Applied to Hydrogen Absorption and Lithium Ion Batteries”,
submitted to Intermetallics”, 2016[6] Daniel Thomas, Nadine Bette, Franziska Biedermann, Jürgen Seidel, Regina Hüttl, Florian Mertens “Experimental
Determination of the Enthalpies of Formation of the Lithium Silicides Li7Si3 and Li12Si7 Based on Hydrogen Sorption
Measurements”, submitted to Journal of Alloys and Compounds, 2016
Short CV
University Education
1985 – 1991
1991-1995

Studies of Physics, Johann Wolfgang Goethe Universität,
Frankfurt, Germany
Fritz Haber Institut der Max Planck Gesellschaft, Berlin, supervisor Prof.
G. Ertl, doctoral degree, Freie Universität Berlin, Germany

Professional Experience
1995 – 1998
University of Texas at Austin, Dept. of Physics and Center for
Nonlinear Dynamics, USA
Postdoctoral fellow and lecturer
1999 – 2003
Adam Opel AG, Global Alternative Propulsion Center,
Mainz-Kastel, Germany
Project leader for advanced hydrogen storage development
2003 – 2005
General Motors, R&D Center, Warren-Detroit, USA
Technical head of General Motors’ Hydrogen Storage Innovation
Program.
since 2005
Technische Universität Bergakademie Freiberg, Germany
Full Professor for Physical Chemistry and Head of Department
Corresponding author: Florian Mertens, florian.mertens@chemie.tu-freiberg.del, Tel. ++493731393737
Florian Mertens

30

METAL BORANES FOR HIGH DENSITY HYDROGEN STORAGE AND
FAST IONIC CONDUCTIVITY
Hai-Wen Li1,2, Liqing He3, Hironori Nakajima3, Yaroslav Filinchuk4, Son-Jong Hwang5,
Hans Hagemann6, Torben R. Jensen7, Etsuo Akiba1,2,3
1 International Research Center for Hydrogen Energy, Kyushu University, 2 International Institute for Carbon-Neutral
Energy Research (WPI-I2CNER), Kyushu University, 3 Department of Mechanical Engineering, Kyushu University,
4 Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, 5 Division of Chemistry andChemical Engineering, California Institute of Technology, 6 Département de Chimie Physique, Université de Genève,
CH1211 Geneva 4, Switzerland, 7 Center for Materials Crystallography, Interdisciplinary Nanoscience Center (iNANO)
and Department of Chemistry, University of Aarhus, DK-8000 Aarhus C, Denmark
Metal boranes M(BxHy)n have been attracting increasing interest especially for energy applications including high density
hydrogen storage and fast ionic conductivity. The metal closo-borane like M2(B12H12)n possessing a stable icosahedral
cage structure, has been widely regarded as the main barrier for rehydrogenation to M(BH4)n with gravimetric hydrogendensity of 10 mass%. The stable M2(B12H12)n, on the other hand, favors its potential application for fast ionic conductivity,e.g. ionic conductivity of LiNaB12H12 reaches 0.79 S/cm at 550 K.

M2(B12H12)n, a dehydrogenation intermediateof M(BH4)nImproved ionic conductivity of M(B12H12)nby cation substitution

Metal boranes, expressed as M(BxHy)n like M(BH4)n,M2(B12H12)n, etc., have been attracting increasing interestfor energy applications [1]. Lower metal boranes such as
metal tetrahydroborate M(BH4)n like LiBH4, Mg(BH4)2 andCa(BH4)2, with hydrogen gravimetric density higher than
10 mass%, have been extensively investigated for highdensity hydrogen storage. The dehydrogenationaccompanies with the formation of intermediates
2containing polyanions, like [B2H6] , [B3H8] and/or
22[B12H12] [2]. The [B12H12] intermediate, having strong
B-B bonds in a stable icosahedral boron cage, is as an
obstacle for the rehydrogenation to borohydrides [3].

M2(B12H12)n with a stable icosahedral cage structure,favors its potential application as superionic conductor.
Recently, we found that the ionic conductivity of abimetallic closo-borane LiNaB12H12 reaches 0.79 S/cm
at 550 K above its order-disorder phase transition. Thisvalue is 10 times higher than those of its single
counterpart of Li2B12H12 and Na2B12H12 at the same
temperature [7].

Synthesis and thermal decomposition ofanhydrous M2(B12H12)nAnhydrous M2(B12H12)n (M = Li, Na, K, Mg, Ca, LiNa)
have been successfully synthesized by sintering of
M1/nBH4 and B10H14 with the stoichiometric chemicalcompositions [4-6]. Thermal decomposition of anhydrous
M2(B12H12)n proceeds in two steps: (1) dehydrogenate toproduce H-deficient M2(B12H12-x)n keeping the icosahedral
B12 skeletons and (2) polymerization of M2(B12H12-x)n toform (M2BxHy)n polymers [7].

Hai-Wen LI

References[1] Hansen et al., Coord. Chem. Rev. 323, 60 (2016)[2] Yan et al., Mater. Trans. 52, 1443 (2011)[3] Li et al., J. Alloys Compd. 580, S292 (2013)[4] He et al., J. Phys. Chem. C 118, 6084 (2014)[5] He et al., Dalton. Trans. 44, 15882 (2015)[6] He et al., Chem. Mater. 27, 5483 (2015)[7] He et al., Energies 8, 12429 (2015)

Hai-Wen LI obtained his Ph. D. degree in 2005 from Kitami Institute of Technology (Japan), under
the supervision of Prof. Kiyoshi Aoki. In 2005, he started to work as a postdoctoral researcher with
Prof. Shin-ichi Orimo at Institute for Materials Research, Tohoku University. From 2006-2008, hebecame a JSPS (Japan Society for the Promotion of Science) Research Fellow. In 2008, he was
assigned as an assistant professor at Institute for Materials Research, Tohoku University. Since
2011, he works as an associate professor at International Research Center for Hydrogen Energy
and International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University.
His research interests focus on investigating fundamental, physical and chemical properties ofinterstitial and non-interstitial hydrides, aiming at developing advanced materials for high-density
hydrogen storage and advanced electrochemical applications.

Corresponding author: Hai-Wen Li, Email: li.haiwen.305@m.kyushu-u.ac.jp, Tel. (+81) (92) 802 3226

31

11th Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

EFFECT OF PRESSURE ON TUNNELING AND VIBRATIONAL
SPECTRUM OF HYDROGEN IN ALPHA MANGANEZE
A.I. Kolesnikov,1 A. Podlesnyak,1 R.A. Sadykov,2,3 V.E. Antonov,4 M.A. Kuzovnikov,4,5 G.
Ehlers,1 G.E. Granroth1
1
Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA, 2Institute for High Pressure Physics, RAS,
Moscow, Troitsk, Russia, 3Institute for Nuclear Research, RAS, Moscow, Russia, 4Institute of Solid State Physics, RAS,
5
Chernogolovka, Moscow Region, Russia, Institute of Physical Chemistry, PAS, Warsaw, Poland

The pressure effect on the tunneling mode and vibrational spectra of hydrogen in α-MnH0.07 has been studied by inelastic
neutron scattering. Applying hydrostatic pressure of up to 30 kbar is shown to shift both the hydrogen optical modes andthe tunneling peak to higher energies. First-principles calculations show that the potential for hydrogen in α-Mn becomesoverall steeper with increasing pressure. At the same time, the barrier height and its extent in the direction of tunnelingdecrease and the calculations predict significant changes of the dynamics of hydrogen in α-Mn at 100 kbar, when theestimated tunneling splitting of the hydrogen ground state exceeds the barrier height.

16 kbar

S(Q,E) (arb. units)

0

30 kbar0.00060.00040.0002

0.494

0.496

0.498

0.0000

0.500

0.504

0.506

c (un

it

cell)

50
0.5

0.502

00
0.5

Alexander
Kolesnikov

10

25
0.5

The measured INS spectra of α-MnH0.07 showed that thehydrogen optical modes and tunneling mode
progressively shift to higher energies with increasing

1 bar
22 kbar20

5

Results and discussions

0.000830

0.47

The INS measurements were performed using SEQUOIAand CNCS spectrometers at SNS, ORNL, and we used aclamp piston-cylinder Ni-Cr-Al pressure cell with effective
sample volume ∼0.3 cm3. First-principles calculations
were performed using the Vienna ab initio simulation
package (VASP).

0.001040

00.45

Experiment and calculations

50

x (unit cel )Inelastic neutron scattering (INS) studies revealed a giant
tunneling effect of hydrogen in α-Mn, where H atoms
occupy positions arranged in dumbbells of 0.68 Å long[1,2]. The study showed that the peak in the INS spectra
at 6.3 meV originated from transitions between thevibrational ground states, which are split due to thetunneling of H atom inside the dumbbells. The pressure
effect on H tunneling in α-Mn was earlier studied by INS[3], and it was shown that nonhydrostatic compression to
P=17 kbar suppressed the tunneling peak, which was
related to the residual elastic stresses in the sample. This
work presents an INS study of the effect of hydrostaticpressure on the INS spectra of α-MnH0.07 up to P=30
kbar, and ab initio calculations of the potential well forhydrogen in α-Mn and estimation of tunneling splitting [4].

pressure. The first-principles calculations predict a 3D
potential with a double-well shape in the direction ofhydrogen tunneling, and describe the experimental datareasonably well. Both experiment and calculations revealthat an increase of pressure results in an increase of thepotential stiffness and a decrease of the barrier forhydrogen tunneling, and we predict that at P=1 Mbar the
potential can be considered a single-well potential.

Energy (meV)Introduction

2

3

4

5

6

7

8

9

10

Energy transfer (meV)Fig. 1. Calculated 3D-potential at 1 bar (left) and INS
spectra of hydrogen in α-Mn measured at T=1.5 K anddifferent pressures (right).

References[1] V.E. Antonov et al. J. Alloys Compd. 330-332 (2002)
462.
[2] A.I. Kolesnikov et al. Physica B 263-264 (1999) 421.
[3] V.E. Antonov et al. JETP Lett. 76 (2002) 318.
[4] A.I. Kolesnikov et al. Phys. Rev. B 94 (2016) 134301.

Alexander Kolesnikov, Instrument Scientist, Senior R&D Staff, Chemical and Engineering Materials
Division, Oak Ridge National Laboratory, holds a Ph.D. (Physics & Mathematics) form the Institute ofSolid State Physics, Russian Ac. Sci., Chernogolovka, Russia. His employment history includes:
Inst. Solid State Physics Russian Ac. Sci., Chernogolovka, Russia; IFF Forschungcentrum Juelich,
Germany; Salford University, UK; Un. Manchester Inst. Science and Technology, UK; Argonne
National Laboratory, IL, USA; Oak Ridge National Laboratory, TN, USA. He was an Alexander von
Humboldt Research Fellow. His research interests and expertise include: vibrational dynamics &structure of metal hydrides, hydrogen storage materials, carbon nano-materials, water/ice, liquids
and gases under nanoscale confinement, etc. by using neutron scattering technique.

Corresponding author: Alexander Kolesnikov, kolesnikovai@ornl.gov +1-865-576-9145

32

th

11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

LI-N-H MEDIATED NH3 SYNTHESIS AND DECOMPOSITION
JianpingGuo, Peikun Wang,Fei Chang, Wenbo Gao, Guotao Wu, Teng He, Ping Chen*
Dalian Institute of Chemical Physics, Dalian, 116023,China
Abstract:Ammonia is a potential hydrogen carrier. Efficient catalysts that allow ammonia synthesis and decomposition
under mild conditions are highly needed. Our experimental results demonstrate that Li-N-H, an intensively investigatedhydrogen storage material, exhibits unique synergistic effect on 3d transition metalsin catalysing ammonia synthesis anddecomposition which leads to superior activities that are orders of magnitude higher than the neat 3d metal catalysts.

Introduction
With a high hydrogen content (17.6 wt.%), high energy-1density (4 kWh kg ), facile storage and transportation,
NH3 has been regarded as a potential COx-free hydrogen
carrier.[1]The pursuit of low-temperature NH3 synthesis
and decomposition catalysts encouraged tremendous
research efforts over the past few decades. Significant
progresses have been made in the development of Ruand alloy-based catalysts, the size and morphology
controls of catalyst to maximize the number of active
centers, and the employments of alkali or alkaline earth
promoters. The ideal scenario, i.e., a catalyst of highcapability in activating reactants and of relatively weakbonding with intermediates, however, is difficult to beachieved as long as the catalysis is carried out ontransition metal surface.[2]Results
Ammonia decomposition
Our experimental results show that lithium imide (Li 2NH)synergizes with Fe2N leading to high catalytic activities inNH3 decomposition through a two-step reaction pathcomprising of:
I –Li2NH+Fe2N→Li3FeN2+H2
II – Li3FeN2+NH3→Fe2N+Li2NH+N2
By extending the transition metal from Fe to other 3delements, a universal and unexpectedly high catalytic
activity was identified.[32] Specifically, the catalytic
activity of Li2NH-MnN composite is superior to the highly
active Ru/CNT catalyst. [3] Kinetic analyses disclose thatthe H2-release step (I) has a higher barrier than that of

the N2-release (II), in contrast to the occurrence of NH3
decomposition over neat transition metals or their nitrides.

Ammonia Synthesis
In ammonia synthesis LiHserves as the second reactive
centerfavoring NH3 synthesis at relatively low
temperatures. Our experimental results show thattransition metals (TM) serve as the active site for N 2
activation; LiH, on the other hand, is responsible for thehydrogenation. LiH participates in the overall catalysis
and is regenerated via the heterolytic dissociation of H2
on LiNH2. The removal of N from TM by Li refreshes theTM surface allowing more sites for continuous N2
activation; the occurrence of hydrogenation on LiNH x
rather than on TM site further intervenes in the direct
dependence of NH3 formation rate on the properties ofTMs. The unique chemistry among TM, Li, N and H
creates a two-reactive center mediated pathway
favouring NH3 synthesis under mild condition over both
early and late 3d TMs, i.e., detectable NH3 formation
rates can be obtained at 423 K over the Mn-, Fe- and CoLiH composite catalysts, respectively.[4]References[1] F. Schuth, R Palkovits, R.Schlogl, &D. S. Su, EES 5(2012) 6278-6289.
[2] A. Vojvodic et al., Chem. Phys. Lett. 598 (2014) 108112.
[3] J. P. Guo et al.,Angew. Chem. Int. Ed. 54 (2015)
2950-2954.
[4] P. K. Wang et al., Nature Chem. DOI:
10.1038/nchem.2595

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 afaculty member 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, and catalytic ammonia synthesis and decomposition by employing
hydrides or imides as co-catalysts.
Ping Chenpchen@dicp.ac.cn, 86-0411-84379905

33

DEVELOPMENT AND PERSPECTIVES OF METAL HYDRIDES ANDMETAL HYDRIDE BASED SYSTEMS FOR HYDROGEN STORAGE
M. Dornheim, H. Cao, F. Karimi, S. Boerries, N. Bergemann, J. Jepsen, A. Santoru, T. Le,
G. Capurso, G. Gizer, A. Chaudhary, O. Metz, C. Horstmann, J. Bellosta von Colbe, C.
Pistidda, K. Taube, T. Klassen
Hydrogen Technology Center, Helmholtz-Zentrum Geesthacht, Germany
In this presentation recent results concerning the sorption behaviour and cycling properties of selected metal hydrides forhydrogen storage will be presented and their possible usage in hydrogen storage systems discussed.

Introduction
In the context of reducing CO2 emissions and therewith
the usage of fossil fuels, novel energy storage solutions
are urgently required. Recently huge improvements inbattery technologies, i.e. Li-ion batteries, were achieved.
However, so far Li-ion batteries still suffer from rather low
energy densities if compared with conventional fuels.
Depending on the size of the system fuel cell – 700 barhydrogen storage systems very often show higher energy
storage densities. Unfortunately, there are not many
options to further improve the energy density and lower
the costs of such high pressure hydrogen gas cylinders
and high pressure infrastructure. The development of
new light weight hydrides, however, offers the possibility
to develop systems with a) higher energy density and b)
at lower cost.

Results
Sorption properties of selected metal hydrides as well as
different results obtained by in-situ synchrotron XRD,
small angle scattering, DSC, neutron radiography etc.
helping to understand the reaction mechanism or to
optimise the material behaviour for hydrogen storage
applications will be shown.

Discussion
Possible methods to produce the storage material inlarger quantities as well as its potential usage for energy
storage are discussed.

Education:
Dr. rer. nat. (PhD) in experimental Material Physics, Universität Göttingen, Germany, 2002.
Dipl.-Phys. (~Master of Science): diploma thesis in computational solid state physics at
Universität Göttingen, Göttingen, Germany, 1998.
Vordiplom (~bachelor) in Physics: Universität Hamburg, Hamburg, Germany 1994
Employment records:
Scientific and Strategic Deputy of the Director of the Materials Technology division
at HZG since 2014.
M. Dornheim

Lecturer at Helmut-Schmidt University, Hamburg, Germany since 2012
Lecturer at Hamburg University of Technology since 2005.
Head of the Nanotechnology Department, at HZG since 2005.

Corresponding author: Martin Dornheim, martin.dornheim@hzg.de, Tel.+49152872604

34

HYDROGEN STORAGE PROPERTIES OF COMPOSITE MATERIALSBETWEEN BORON- AND TRANSITION METAL-BASED COMPLEX HYDRIDES
Guanqiao LI1, Motoaki MATSUO2, Shigeyuki TAKAGI2, Toyoto SATO2, Shin-ichi ORIMO1,2
1 WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan
2 Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

When the composite materials (1-x)MBH4 + xMg2FeH6 were heated up continuously, MBH4 and Mg2FeH6
dehydrogenated simultaneously in the Mg2FeH6 rich compositions (x ≥ 0.5) despite the huge difference in their
thermodynamic properties. Taking the composite materials between Mg2FeH6 and LiBH4 as model case, we tried toclarify the thermodynamic and kinetics factors of the simultaneous dehydrogenation by pressure-composition-isothermal(PCT) experiments.

Introduction
Boron-based complex hydrides such as LiBH4, haspreferable high gravimetric hydrogen density of 18.3
mass%, while the dehydriding temperature of above
420 ̊C is in disadvantage.[1] By combining with metal
hydrides such as MgH2, LiBH4 was thermodynamicallydestabilized because of the formation of MgB2.[2] Basedon the same theory, composite materials between LiBH4
and transition metal-based complex hydrides such as
Mg2NiH4, Mg2FeH6 have also caught interests.[3,4] The
results of preceding studies suggested that beside theexpected formation of boride, dehydrogenation property
of both the starting complex hydrides were modified andthe mechanism needed to be discussed case by case.
In the preceding study, we have found out that thedehydriding temperatures of MBH4 (M = Li, Na, K)
decreased drastically when the composite materials (1x)MBH4 + xMg2FeH6 (0.17 ≤ x ≤ 0.9) were heated upcontinuously. For example, the dehydriding temperatureof LiBH4 was 350 ̊C when x = 0.5, which was 100 ̊Clower than that of pure LiBH4.[5]Fig.1 Simultaneous dehydrogenation of LiBH4 andMg2FeH6 when x ≥ 0.5.[5]

2006
2013
2016

Beside of the decreased dehydriding temperature, MBH4
and Mg2FeH6 dehydrogenated simultaneously withmediate dehydriding temperature between those of theparent complex hydrides as shown in Fig.1. Also, thetemperature was strongly related to the molar ratio of[BH4]－ and [FeH6]4－ anions.[6]Results and discussion
In order to distinguish the thermodynamic and kinetics
factor of the simultaneous dehydrogenation, we took (1x)LiBH4 + xMg2FeH6 (0.25 ≤ x ≤ 0.75) as model case andthe dehydrogenation property was studied by PCT
experiment. The results suggested that reaction between
Mg2FeH6 and LiBH4 was stoichiometric with a molar ratioof 1:1 in all the compositions, and the equilibriumpressure was much higher than those of thedehydrogenation reactions of the pure parent complex
hydrides. The results were also compared with those ofcomposite materials between MgH2 and LiBH4.

References[1] S. Orimo, Y. Nakamori, J.R. Eliseo, A. Züttel, C.M. Jensen,
Chem. Rev., 107 (2007) 4111.
[2] J.J. Vajo & S.L. Skeith, J. Phys. Chem. B., 109,
(2005) 3719.
[3] P. Javadian, C. Zlotea, C.M. Ghimbeu, M. Latroche &T.R. Jensen, J. Phys. Chem. C., 119, (2015) 5819.
[4] M.R. Ghaani, M. Catti & A. Nale, J. Phys. Chem. C.,
116, (2012) 26694.
[5] G. Li, M. Matsuo, S. Deledda, R. Sato, B.C. Hauback,
S. Orimo, Mater. Trans., 54 (2013) 1532.
[6] A.L. Chaudhary, G. Li, M. Matsuo, S. Orimo, S. Deledda,
M.H. Sørby, B.C. Hauback, C. Pistidda, T. Klassen &M. Dornheim, Appl. Phys. Lett., 107, (2015) 073905.

2015－

Bachelor of science, Peking University, China
Master degree of interdisciplinary studies, Tohoku University, Japan
Philosophy degree, Tohoku University, Japan
Research Fellow of Japan Society for the Promotion of Science (Project: 10604)

Present

WPI-Advanced Institute for Materials Research, Tohoku University

Research on complex hydrides and composite materials in Prof. ORIMO Shin-ichi’s group
Guanqiao LI
Corresponding author: Guanqiao LI, Email: likk@imr.tohoku.ac.jp, Tel.81-22-215-2094

35

MULTI-FUNCTIONAL ENERGY STORAGE MATERIALSTorben R. Jensen
Center for Materials Crystallography, iNANO Interdisciplinary Nanoscience Center and
Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C, Denmark.
Hydrogen is recognized as a potential and extremely interesting energy carrier, which can facilitate efficient utilization of
unevenly distributed renewable energy. Furthermore, hydrogen has an extremely interesting chemistry and form
compounds with most elements in the periodic table and with a variety of different types of bonds. Metal hydrides has
recently become very interesting as new classes of energy materials for batteries and hydrogen storage. Here we reportan overview of our recent results within new hydrogen containing materials: (i) synthesis of novel metal borohydrides andstudies of their properties for hydrogen storage or as ion conductors, (ii) tailoring materials properties by anion
substitution or neutral molecule derivatives, and (iii) in situ powder X-ray diffraction studies. We conclude that thechemistry of hydrides is very divers, towards multi-functional materials.

Introduction
We have plenty of renewable energy available but sun
and wind are unevenly distributed over time andgeographi-cally, therefore energy storage is increasingly
important. Metal hydrides have extremely diverse
chemistry, structure and reactivity and often high energy
density and multi-functionality [1,2].

Results and Discussion
We have recently developed new synthesis strategies
and discovered new classes of important ‘energy
materials’, e.g. >30 novel perovskite-type complex metalborohydride, with interesting photophysical, electronicand hydrogen storage properties [3]. Furthermore, anionmixing provides a link to the known perovskite ABX3
halides [3]. New metal hydrides, which are fast lithium,sodium and magnesium ion-conductors are also
discovered and are now tested in batteries [4,5]. The
more stable closo-boranes are highly interesting as new
solid state ion conductors [6-8]. New synthesis
techniques have recently produced series of ammine
metal borohydrides, M(BH 4)m∙nNH3, M = Mg, Ca, Sr, Mn,
Y, La, Ce, Gd and Dy, >30 new compounds e.g. the firstlong series, Y(BH 4)3∙nNH3, n = 1, 2, 4, 5, 6 and 7 [9-11].
We present new mechanisms for gas release, which
depends on the ammonia release temperature and thestability of the metal borohydride. Interestingly, thehydrogen and ammonia content in the released gas
appear to have little correlation to the strength of the dihydrogen bonds and the NH3/BH4 (n/m) ratio.

The structures of all new compounds are solved frompowder X-ray diffraction, spectroscopy and optimized by
DFT calculations and recently reviewed [12]. We
demonstrate that structural dynamics in the solid state,i.e. entropy effects, are of extreme importance fordetailed material property analysis. We present a ‘paddle
wheel’ mechanism, which may be responsible for fastionic conductivity [13]. We conclude that the chemistry of
hydrides is very divers, towards rational design of multifunctional materials, including new ion-conductors forbatteries, hydrogen storage materials, and possibly
materials with new types of optical properties.
References[1] Ley, et al, Mater. Today 2014, 17(3), 122[2] Jepsen, et al, Mater. Today, 2014, 17(3), 129[3] Schouwink, et al, Nature Comm., 2014, 5, 5706
[4] Ley, et al, Chem. Mater. 2012, 24, 1654[5] Ley, et al, J. Phys. Chem. C 2012, 116, 21267[6] Paskevicius, et al, Nature Comm. 2017[7] Paskevicius, Chem. Mater., 2017[8] Hansen, Coor. Chem. Rev. 2016, 323, 60–70[9] Jepsen, et al, ChemSusChem. 2015, 8, 3472[10] Jepsen, et al, Inorg. Chem. 2015, 54, 7402[11] Jepsen, et al, ChemSusChem. 8, 1452 (2015).
[12] Paskevicius, Jensen et al, Chem. Soc. Rev., 2017
DOI:10.1039/c6cs00705h[13] Skripov, et al., J. Phys. Chem. C 2013, 117, 14965

Torben received a Ph.D. degree in materials chemistry and did postdoctoral research at Risø
National Laboratory and DESY, Hasylab, Hamburg. He was awarded a Steno research stipend(2002) by the Danish research council, a Carlsberg research stipend (2005) form the Carlsberg
Foundation and a doctor of science degree (D.Sc.) from the faculty of science and technology at
Aarhus University. He was awarded the Hydrogen Energy Award in Japan 2016. His researchinterests are focused on synthesis, structural, physical and chemical properties of new inorganic
materials and utilisation of synchrotron X-ray radiation for materials characterization. He has
published >220 research papers and received >5400 citations (H = 42).
Torben R. Jensen, Professor, D.Sc., PhD, trj@chem.au.dk, mobile: +45 2272 1486.

36

TIME-RESOLVED X-RAY ABSORPTIONHYDROGEN STORAGE MATERIALSFINESTRUCTURE

FOR

D. Matsumura
Japan Atomic Energy Agency
Abstract X-ray absorption fine structure (XAFS) which has element selectivity and local structure sensitivity is a unique
technique for the study of functional systems including hydrogen storage materials. We observed time-resolved XAFS
spectra for some hydrogen-related samples in order to understand dynamic structure change under reaction process.

Introduction
We have developed time-resolved X-ray absorption finestructure (XAFS) system in order to reveal the relation of
structure and property during reaction. XAFS technique isan element specific photon-in photon-out probe andsensitive for local structure. These features allow us toobserve only structure change of the target element
under in situ condition.

of peak shift), and water formation reaction on Pt metal
nanoparticles occur at the same time [3].

Experiments
XAFS spectra were taken at BL14B1 and BL28B2 ofSPring-8, Japan. Time-resolved measurement wasachieved by using dispersive optics.

Results and discussion
Pd metal nanoparticles show different hydrogen
adsorption and desorption properties from bulk materials.
The hydrogen absorption and desorption processes wereobserved by time-resolved XAFS at a rate of 200 Hz. It
was succeeded to observe the change of Pd-Pd
interatomic distance with 5 ms exposure time anddetermine the reaction time below 10 ms [1].
Local structure of TiCl3 additive in Mg(BH4)2 was studied
to understand correlation between the structure of theadditive and dehydrogenation property of Mg(BH4)2.
Simultaneous measurement of the dehydrogenation
curve and XAFS spectra revealed that a part of TiCl3
additive is converted to Tix(BH4)y just after ball milling
mixture and then promptly resolved to TiB2 at 100-150 °C
with the first dehydrogenation peak [2].
Hydrogen removal by water formation reaction is one of
the candidates for creating hydrogen safe system. We
observed structure change of Pt metal nanoparticle
catalyst during the reaction with poisoning gas of CO.
Figure 1 shows that the creation of oxidized layer(increase of peak intensity), desorption of CO (decrease

Fig. 1 Temporal variations of XAFS peak shift andintensity for Pt nanoparticles with the change of gas
concentration during flow of H2/O2/CO.

References[1] D. Matsumura, et al., J. Phys. Conf. Ser. 430, 012024(2013). [2] D. Matsumura, et al., Mater. Trans. 52, 635(2011). [3] D. Matsumura, et al., Int. J. Hydrogen Energy,
doi: 10.1016/j.ijhydene.2016.08.189

Short CV
D.Sc., The University of Tokyo, 2004
Researcher, Japan Atomic Energy Agency, 2005Research topics: X-ray absorption fine structure (XAFS), time-resolved measurement, metal
nanoparticle catalyst
D. Matsumura
Corresponding author: Daiju Matsumura, daiju@spring8.or.jp, +81-791-58-0975

37

th

11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa$,$Hawaii$2017$

ADVANCE'IN'THE'FORMATION'AND'REGENERATION'OF'
ALANE'FOR'HYDROGEN'STORAGE''
Ragaiy$Zidan,$Patrick$A.$Ward,$Joseph$A.$Teprovich$Jr.,$Scott$Greenway,$
Scott$McWhorter$
Savannah$River$National$Laboratory$Aiken,$SC$29808$
Aluminum$ hydride$ (Alane$ Q$ AlH3),$ has$ a$ gravimetric$ capacity$ of$ 10$ wt.%$ ,$ volumetric$ capacity$ of$
149$g/L$H2$and$hydrogen$can$be$desorbed$at$reasonable$temperature$of$less$than$150 $C.$These$characteristics$make$alane$a$very$attractive$material$for$hydrogen$storage,$capable$of$fulfilling$the$needs$ of$ many$ energy$ storage$ applications$ spanning$ from$ portable$ power$ to$ transportation$
vehicles.$ However,$ the$ main$ challenge$ for$ implementing$ alane$ as$ a$ hydrogen$ storage$ material$ in$applications$ is$ cost.$ For$ this$ reason$ our$ research$ is$ mainly$ focused$ on$ developing$ lowQcost$
methods$ to$ synthesize$ and$ regenerate$ alane$ from$ aluminum.$ In$ this$ work$ the$ use$ of$electrochemical$method$is$discussed$and$compared$to$other$methods.$Problems,$associated$with$using$ electrochemistry$ in$ making$ alane,$ such$ as$ dendrites$ and$ electrolyte$ conductivity$ are$discussed$ and$ solutions$ are$ presented.$ Crystallization$ methods,$ of$ alane$ from$ different$ adducts,$
are$ explored.$ Oxidation$ and$ surface$ treatment$ of$ alane$ as$ ways$ to$ obtain$ a$ stable$ product$ are$shown.$ Thermogravimetric$ measurements,$ XQray$ diffraction$ and$ scanning$ electron$ microscopy$
data$of$alane$produced$by$various$techniques$are$presented.$

38

th

11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

STUDY OF THE DECOMPOSITION OF A EUTECTIC LITHIUM AND
SODIUM BOROHYDRIDE MIXTURE WITH NANO-SIZED NI
Yinzhe Liu, Daniel Reed, David Book
School of Metallurgy and Materials, University of Birmingham, Birmingham, B15 2TT, UK
This work highlights the improvement of nano-sized Ni on the dehydrogenation of eutectic 0.62LiBH4-0.38NaBH4 mixture
that releases 7.3 wt. % H2 upon heating to 600 °C through a 3-step decomposition, rather than a 2-step decomposition
seen in the Ni-free eutectic mixture. The nano-sized Ni addition: 1) decreases the decomposition temperatures by 20 - 40
°C; 2) changes the decomposition pathways where Ni4B3 is formed through a chemical reaction between LiBH4 andnano-sized Ni in the first step and further reacts with LiH (decomposition product), producing Li1.2Ni2.5B2 and releasing H2when temperature is higher than 560 °C.

Introduction
The utilization of eutectic melting in metal borohydrides is
considered as one of the potential routes for achieving
high-capacity hydrogen storage materials: several
borohydrides that contain alkali metals coupled with otheralkali or alkaline metals have been investigated [1]. Oneof the interesting systems received attention is 0.62LiBH4- 0.38NaBH4 because of its relatively low cost among
known eutectic borohydride systems and relatively hightheoretical H2 capacity by weight (14.5 wt%).
The major dehydrogenation of this mixture starts above
350 °C (in Ar) and releases 7.6 wt.% of H2 upon heating
to 500 °C [2]. This process is partially reversible.
However, the reversible H2 content decreases (from 7.2
nd
wt. %) to 2.1 wt. % at the 2 cycle and further decreasesrd
to 1.6 wt. % at the 3 cycle [2]. Thus, the highdecomposition temperatures and limited reversibility are
the major obstacles for the applications for on-board
vehicles, and therefore needs to be improved.
The addition of nano-sized Ni can reduce thedehydrogenation (peak) temperature of LiBH4 (by 47 °C)
by forming nickel boride (Ni4B3) whilst also improving therehydrogenation content of LiBH4 from 4.3 wt. % (withoutnano-sized Ni) to 10.8 wt. % by amending therehydrogenation reaction pathways [6].
Thus, a 20 wt. % nano-sized Ni (~ 100 nm) was added to
0.62LiBH4 - 0.38NaBH4 eutectic mixture in this work,
aiming to reduce its decomposition temperatures and toachieve a better reversibility.

Methodology

TPD-MS were used to identify the phases and study thedehydrogenation behaviours.

Results
No reaction between nano-sized Ni and borohydrides isobserved during ball milling. Dehydrogenation (in flowingAr) starts at ~250 °C with three peaks observed at 468°C, 515 °C and 586 °C (indicating three different
decomposition pathways), where the Ni-free eutectic
mixture dehydrogenation begins at 287 °C with peaks
seen at 488 °C and 540 °C. Therefore, the addition of
nano-sizedNidecreases
thedehydrogenation
temperatures of 0.62LiBH4 - 0.38NaBH4 by 20 - 40 °C.
With the addition of nano-sized Ni, the H2 released ateach step is accompanied by the precipitation of 1) LiH,
Li2B12H12, B and Ni4B3; 2) Na and B; 3) Li1.2Ni2.5B2 andunknown phase(s) (2θ (°) = 12.4, 20.4 and 25.0). A totalof 7.3 wt. % of H2 is released upon heating to 600 °C(corresponding to 63 % of the available H2 in the sample
content), which is slightly lower than 7.8 wt. % (80% of
9.8 wt. % for Ni-free eutectic mixture).
This study suggests the addition of nano-sized Ni
decreases the dehydrogenation temperatures of
0.62LiBH4 - 0.38NaBH4 by changing reaction pathways.

References[1] M. Paskevicius et al. Phys. Chem. Chem. Phys. 15(2013) 19774-19789[2] P. Javadian et al. Int. J. Hydrogen Energy 40 (2015)
149-14924[3] H. Li et al. Mater. Trans. 55 (2014) 1134-1137

The 0.62LiBH4 - 0.38NaBH4 with nano-sized Ni sample
was prepared by ball-milling in Ar. XRD, Raman andYinzhe Liu

Yinzhe Liu was born in China and studied in China, United States of America, Belgium and United
Kingdom. He received his bachelor degree in Material Chemistry from the University of Science andTechnology Beijing (USTB, 2012) and spent one year at the University of California, Riverside(UCR) as a visiting student and completed his bachelor thesis. He finished his master thesis in imec
(Leuven, Belgium) and obtained his master degree in Material Engineering from the KU Leuven(2014). Currently, he is a 3rd year Ph.D. candidate in the field of energy material at the University ofBirmingham as part of the ECOSTORE Marie Curie Initial Training Network.

Corresponding author: Yinzhe Liu, Y.LIU.3@bham.ac.uk, +44 (0) 774 911 3888

39

Halogenated sodium-closo-dodecaboranes as solid-state ion
conductors
Mathias Jørgensen, Bjarne R. S. Hansen, Mark Paskevicius and Torben R. Jensen
Center for Materials Crystallography (CMC) at the Department of Chemistry and the Interdisciplinary
Nanoscience Center (iNANO), Aarhus University, Langelandsgade 140, 8000 Aarhus, Denmark
The halogenated sodium closo-boranes Na2B12Cl12, Na2B12Br12 and Na2B12I12 have been investigated for theirpotential as solid-state ion conductors. Based on synchrotron powder X-ray diffraction data the structures of
the room temperature and high temperature polymorphs of the compounds were determined with spacegroups Pa-3 and Fm-3m, respectively, and increasing unit cell size with anion size. Furthermore,
electrochemical impedance spectroscopy measurements were performed showing remarkable ion
conductivities of up to 0.162 S/cm when heated above the polymorphic transition temperature.
Metal closo-boranes as solid-state electrolytes
Metal closo-boranes [1], as well as halogenatedderivatives, have shown great potential as electrolytes
both in the solid state and in liquids [2-3]. The high solidstate ion conductivity often found in metal closo-boranes
is facilitated by the fast reorientational dynamics of thelarge anion allowing for higher mobility of the cations,thus the ion conductivity increases by orders ofmagnitude upon phase transition into the highly
disordered high temperature phase.
Ion conductivity in Na 2B12X12 (X= Cl, Br, I)
Differential scanning calorimetry was utilized todetermine the transition temperatures between the room
temperature and high temperature polymorph, showing
an increasing transition temperature with anion size andmass ranging from 475 ˚C for Na2B12Cl12 to 570 ˚C for
Na2B12I12. The phase transition was found to bereversible upon cooling with hysteresis of about 50 ˚C.
Different factors apart from anion mass are believed toinfluence the transition temperature such as the nature of
the bonding between the halogens of the closo-borane
cage and the cation. The bonding was evaluated basedon theoretical calculations of the electron distribution of
the anion and indicated a directionality of the
halogen/cation interaction which was more pronounced
the larger the halogen. This directionality could inhibit
anion motion.
Above the transition temperature the compounds
showed remarkable ion conductivities, values of 0.014

and 0.162 S/cm for Na2B12Cl12
respectively, are here reported [4].
Crystal structure

andNa2B12I12,

The structures of Na2B12Cl12, Na2B12Br12 and Na2B12I12
were determined based on powder X-ray diffraction fromboth synchrotron and in house sources. All threecompounds were found to have a cubic room
temperature (α) and a cubic high temperaturepolymorph (β) and to be isostructural with one another.
The room temperature structures were described in thespace group Pa-3, with a = 12.6496(4) Å, a = 13.1412(7)Å and a = 14.0229(5) Å, respectively, showing an
increasing unit cell with increasing anion size, as
expected. Upon heating to the respective transition
temperature a polymorphic transition to the highsymmetry space group Fm-3m occurred owing to thehighly disordered anions and cations.
References[1]

B. R. S. Hansen et al., Metal boranes: Progress andapplications, Coor. Chem. Rev., 323, 60–70 (2016).

[2] T. J. Udovic et al., Sodium superionic conduction in
Na2B12H12., Chem. Comm., 50, 3750-3752 (2014).
[3] A. N. Dey et al., Primary Li / SOCl2 Cells: VII.
Effect of Li2B10Cl10 and Li2B12Cl12 Electrolyte Salts on
the Performance. J. Electrochem. Soc., 126, 1445-1451(1979).
[4] B. R. S. Hansen et al., Halogenated sodium-closododecaboranesassolid-stateion
conductors,
Chem.Mater., submitted (2017)

In 2014 Mathias achieved his bachelor’s degree in Nanoscience from Aarhus
University. The following year was spent in Beijing studying Nanoscience and Technology at University of Chinese Academy of Sciences in collaboration with
the Danish Universities through Sino Danish Center. In October 2015, a year
prior to finishing the Master’s degree, he was offered a Ph.D. in Torben R.
Jensen’s group at Aarhus University.
Corresponding author: Mathias Jørgensen, mathias.j@inano.au.dk, +45 42 68 72 43.

40

ALTERATION IN SODIUM AMIDE DECOMPOSITION BY THE ADDITION OF
METAL HYDRIDES
Ankur Jain1, Sanjay Kumar1, Hiroki Miyaoka1, Takayuki Ichikawa1,2, Yoshitsugu Kojima1
1Institute for Advanced Materials Research, Hiroshima University, Japan

2Graduate School of Integrated Arts and Science, Hiroshima University, Japan

Abstract: The decomposition of NaNH2 has been reported, mainly transforming into NaH, N 2 and H2. Ammonia is also
produced in addition to N2 and H2. To suppress NH3 evolution, NaH has been tested as an additive. It is observed that theentire process follows NH3 mediated reaction, where the generated NH3 from the decomposition of NaNH2 reacted with
NaH to form NaNH2 and H2. This process continues until the consumption of NaH. The investigation was further extended
to the other metal hydrides and it is found that the addition of other metal hydride i.e. LiH, KH, MgH 2, and CaH2 also
effectively suppresses NH3 evolution.

Introduction
Sodium amide decomposition was first reported byTitherley in 1894 as follows [1]:NaNH2 → Na + 0.5 N2 + H2
Later it is found that ammonia is also produced in addition
to N2 and H2. Although the above reactions were proposed
long back but there are no other reports with the solid
experimental evidence on the above system. There arefew scattered reports available in literature on NaNH 2MgH2 [2], NaNH2-CaH2 [3] etc. However, to the best of ourknowledge, no report except our recent article [4], contains
the thermal desorption data of sodium amide
decomposition with proper characterization of resultant
products. As a first attempt we choose NaNH2 – MH (M =Li, Na, K, Mg, Ca) system to be investigated.

Experimental
The NaNH2-MH systems were prepared by milling under
0.1MPa Ar. The samples were characterized using X-ray
diffraction and Fourier Transform Infrared (FTIR)
spectroscopy. The thermal decomposition was observed
using differential scanning calorimetry (DSC) under 0.1
MPa Ar atmosphere. The weight loss and desorbed
gaseous species were tracked using TG – TDMS system.

Results
In case of NaNH2 – NaH system the entire process follow
NH3 mediated reaction, where the generated NH3 from thedecomposition of NaNH2 reacted with NaH to form NaNH2
and H2. This process continues until the consumption of
NaH, thus suppresses NH3 evolution to a great extent. The
NaNH2 – LiH system first transformed to LiNH2 – NaH
system with the traces of Li3Na(NH2)4 through solid cationexchange process at near to ambient temperature. Further
heating to elevated temperature enhanced the NH3formation rate thus suppressed the ion migration process
and pronounced the NH3 mediated process over it.

Figure 1 : TG/MS plot for NaNH2-MH system (M=Li, Na)

Eventually, the addition of other metal hydride i.e. KH,
MgH2, and CaH2 also posses NH3 mediated reaction [5].
The detailed mechanism for all the systems is proposed
herein.

References[1] A.W. Titherley, J. Chem. Soc. Trans., 65 (1894) 504.
[2] D.A. Sheppard, M. Paskevicius, C.E. Buckley, J.
Phys. Chem. C, 115 (2011) 8407.
[3] O. Dolotko, H. Zhang, S. Li, P. Jena, V. Pecharsky, J.
Alloy Compd., 506 (2010) 224.
[4] Ankur Jain, Hiroki Miyaoka, Takayuki Ichikawa, J.
Phys. Chem. C, 2016, doi: 10.1021/acs.jpcc.6b10611[5] Ankur Jain, S. Kumar, H. Miyaoka, T. Zhang, S.
Isobe, T. Ichikawa, Y. Kojima, communicated to J.
Alloy Compd., 2016.

Dr. Ankur Jain is working as Assistant Professor at Institute of Advanced Materials Research,
Hiroshima University, Japan. He obtained his Ph.D. in 2007 from University of Rajasthan-Jaipur, India.
He has been recipient of several prestigious fellowships and awards including ICTP-TRIL, Italy; DST
Young Scientist Award, DST, India; Visiting Scientist Award under Indo-Swiss Joint research
programme; JSPS-PDF, Japan; Young Scientist Award from young division of International
Association of Hydrogen Energy, DST-INSPIRE Award, India. He has published more than 50
research papers in reputed Journals and authored 4 book chapters.
Ankur Jain
Corresponding author: Ankur Jain, ankur@hiroshima-u.ac.jp, +81-82-424-4604

41

11th Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

ROOM TEMPARATURE DEHYDROGENATION OF AMMONIA BORANE
Tessui Nakagawa and Sho Sashida
University of the Ryukyus
We demonstrated the dehydrogenation of ammonia borane (AB) at RT by mixing metal hydride (MH) and ionic liquid(IL). LiH-AB-IL mixture desorbed ~2 eq. H2 for 7 days at RT and ~2.3 eq. H2 at 90 ºC for 1 h. Functional groupdependence of IL clearly appeared and alkaline metal hydrides drastically accelerate. NaH/LiH-AB-BmimCl showed thebest initial kinetics/largest yield (1 eq. H2 for 1 min/~2 eq. H2 for 7 days). MH-AB-IL after dehydrogenation formed MCl,
indicating “ionic liquid amidoborane” could form via the reaction between MAB (from MH-AB) and ILs.

Ammonia borane (AB; NH3BH3) is a promising hydrogenstorage material for hydrogen career because of highcapacity (19.6 wt%) and moderate dehydrogenation
temperature (~100 °C). There are several drawbacks for
AB to be commercial use such as on-board regeneration,
impurity emission, and slow kinetics. In order toovercome the dehydrogenation issues, ionic liquids (IL)and metal amidoborane (MAB; M(NH2BH3)n) have beendeveloped separately but they have not met the DOE
target. Since we have found slow dehydrogenation of ABIL by thermolysis at RT[1], we improved the kinetics ofAB dehydrogenation at RT using MAB-IL and MH-AB-IL(MH = metal hydrides) In this study.

Experimental
Starting materials of ILs were dry (water: <100 ppm)
imidazolium-type salts which are shown in Fig. 1 and MH
were LiH, NaH, KH, MgH2, and CaH2. MAB wassynthesized in our lab. Dehydrogenation of MAB-IL and
MH-AB-IL (AB/LiAB : IL = 7 : 3 molar ratio) at RT and 90ºC were monitored and quantified by Sievert’s method.
Dehydrogenated products were identified by XRD.

R2
R1
N

N

R3 EmimCl : R1 = C H , R2 = H, R3 = CH
2 5
3
BmimCl : R1 = C4H9, R2 = H, R3 = CH3
BmmimCl : R1 = C4H9, R2 = CH3, R3 = CH3

Fig. 1. Imidazolium-type ionic liquids

Results
Thermolysis of LiAB-BmimCl immediately proceeded
when mixing and reached 0.77 eq. H2 (theoretical: 3 eq.
H2) after 7 days (Fig. 2). LiH-AB-BmimCl desorbed 1.93
eq. H2 after 7 days, which are better than that of ABBmimCl (0.01 eq. H2). Although yield of LiAB-BmimCl at

T. Nakagawa

90 ºC for 1 h was the almost the same as neat LiAB (~1eq. H2), LiH-AB-BmimCl desorbed twice amount ofhydrogen (2.25 eq. H2) with two steps. Yield of LiH-ILEmimCl at RT for 7 days was slower than but close to
LiH-AB-BmimCl, while yield of LiH-AB-BmmimCl was lessthan LiH-AB-BmimCl. These results indicate that theacidity of proton in R2 in Fig.1 is important. Initial kinetics(desorption time to 1 eq. H2) of NaH and KH-AB-BmimCl,
which were 1 and 100 min, respectively, were better than
LiH-AB-BmimCl (11 h) but their yields after 7 days (Na:
1.7, K: 1.5 eq. H2) were less than LiH-AB-IL. However,CaH2 and MgH2 did not accelerate dehydrogenation of
AB-IL. LiCl was observed in the XRD profile after
dehydrogenation of LiH-AB-IL, which indicates that anion
exchanging between LiAB and IL could proceed to form
“ionic liquid amidoborane (ILAB)” and then ILAB could
decompose during dehydrogenation.

2.0 Dehydrogenation@RT
Yield（eq. H2）

Introduction

LiH-AB-BmimCl(1.93 eq.H2 AB)

1.5

LiAB-BmimCl(0.77 eq.H2 AB)

1.0

AB-BmimCl(0.01 eq.H2 AB

0.5
0.0

0

1

2

3
4
5
Time （days)

6

7

Fig. 2 Dehydrogenation kinetics of AB, LiAB, and LiH-AB
with BmimCl at RT

References[1] T. Nakagawa, et all, RSC Adv, 4, 21681 (2014).

Tessui Nakagawa is an assistant professor in the Chemistry course, Faculty of Science, Universityof the Ryukyus. Nakagawa received Ph.D from Hiroshima University in 2009 (Prof. Kojima group)and then worked at Hiroshima University (2009), Los Alamos National Laboratory in the U.S. (20092012), and University of Tsukuba (2012). His research topics are (1) hydrogen storage alloys,
materials for ammonia capture, recycle chemistry, and ammonia borane especially metal
amidoboranes, ionic liquids, and regeneration. Web: http://chem.sci.u-ryukyu.ac.jp/?page_id=2791.

Corresponding author: Tessui Nakagawa, tessui@sci.u-ryukyu.ac.jp, +81-92-895-8535

42

SOLVENT-COORDINATED COMPOUNDS FORMED FROM MAGNESIUMHYDROBORATES AND TETRAHYDROFURANMark Bowden, Marina Chong, Phuong Nguyen, Sunil Shrestha, Bojana Ginovska, Iffat
Nayyar, Abhi Karkamkar, Craig Jensen and Tom Autrey
Pacific Northwest National Laboratory, Richland WA 99352 USA
Mg(BH4) 2 has been studied extensively as a potential hydrogen storage material because of its high gravimetric andvolumetric capacities, and because the heat of reaction is favorable for low temperature release and high pressure
rehydrogenation. In practice, however, the release of hydrogen is constrained by slow reaction kinetics and some of the
products are irreversible. We have recently made substantial improvements to both of these drawbacks through theaddition of solvent, in particular THF, to Mg(BH4)2. To understand this behavior, we report here the results of studies tocharacterize the adducts formed between Mg(BH4)2 and THF, as well potential dehydrogenation products. We focus ondiffraction and structural characterization, supported by ab initio calculations.

Introduction
Magnesium borohydride (Mg(BH 4)2) forms a number ofcompounds in which solvent molecules coordinate with
Mg to produce new stoichiometric products. Adducts with
THF, ethers, amines, and glymes have been described in
the literature. We have recently studied thedecomposition of Mg(BH4)2∙xTHF materials and foundthat their dehydrogenation occurs much more readily
than for unsolvated Mg(BH4)2.1 In additions, the products
contain large yields of MgB10H10 compared to MgB12H12.
This is desirable from a standpoint of easier hydrogen
release, but also because MgB10H10, unlike MgB12H12,
can be rehydrogenated back to Mg(BH4)2. The crystal
structure of Mg(BH4)2∙3THF has been described
previously2, but our work shows that a composition
corresponding to Mg(BH4)2∙0.5THF produces the
optimum yield of MgB10H10. In this work, we haveexamined samples of Mg(BH4)2∙xTHF (0 < x < 3) to see if
any intermediate compounds are formed, using x-ray
powder diffraction and vibrational spectroscopy. We alsostudied the structures of two possible dehydrogenatedproducts, Mg(B3H8)2∙xTHF, and MgB12H12∙xTHF, as abasis for relating hydrogenated and dehydrogenatedmaterials containing THF.

Results
X-ray diffraction patterns of the Mg(BH4)2∙xTHF samples
showed at least 2 intermediate phases between x = 0
and x = 3. The compositions which gave the strongest
peaks belonging to new compounds without peaks fromknown compounds were x = 0.5 and x = 2. A structure ofcell for the x = 2 compound has so far proved elusive, but
the former pattern is successfully indexed on a
monoclinic unit cell with a = 13.680 Å, b = 9.667 Å, c =16.383 Å, β = 79.78°. Structure determination of thiscompound is ongoing.

gas phase of -85, -60, and -23 kJmol-1 for the first,
second and third THF molecules respectively. The
differences in these energies suggests that as THF isadded to a Mg(BH4)2 solution, population of the second
Mg-THF site will not take place until nearly all Mg atoms
are coordinated to one THF. The identification ofMg(BH4)2∙0.5THF is not entirely consistent with thisscheme, and therefore may contain a combination of
THF and solvent (diethyl ether) coordination.
THF adducts of Mg(B3H8)2 and MgB12H12 were alsosynthesised as pure compounds and their structures
solved from powder XRD. The former compoundcontains equal quantities of [Mg(THF)6]2+ and[Mg(B3H8)4]2- complex ions in a FCC lattice. Symmetry
considerations impose an unusual “face-on” coordinationfor B3H82- which may be the average structure fromdynamic reorientations. MgB12H12∙3THF has a more
orthodox coordination where each Mg2+ binds to one
B12H122- and three THF molecules.
Acknowledgements We would like to thank the Fuel
Cell Technology Office in the U.S. Dept. of Energy’s
Office of Energy Efficiency and Renewable Energy. Partof this research was carried out at EMSL, at DOE Officeof Science User Facility sponsored by the Office of
Biological and Environmental Research. PacificNorthwest National Laboratory is operated by Battelle for
the U.S. Dept. of Energy.

References[1] Chong, M., Nguyen, P., Shrestha, S. Bowden, M.,
Karkamkar, A., Jensen, C.M. Autrey, T. This
Symposium, 2017[2] Noth, H. Z. Naturforsch. B, 1987, 37, 1499; Visseaux,M., Terrier, M., Mortreux, A., Rousse, P. Eur. J.
Inorg. Chem., 2012, 2867

Sequential coordination of THF to Mg(BH4)2 is supported
by DFT calculations which gave binding enthalpies in theMark Bowden is a researcher in the Environmental Molecular Sciences Laboratory at the PacificNorthwest National Laboratory. His research interests encompass the structure and chemistry ofcompounds with applications in sustainable energy, including materials for hydrogen storage.
Corresponding author: Mark Bowden, mark.bowden@pnnl.gov, +1 (509)371-7816

43

th

11 Int. Symposium Hydrogen & Energy

Waikoloa, Hawaii 2017

BEYOND-IDEAL MODELING OF (DE)HYDROGENATION IN COMPLEXMETAL HYDRIDES
ShinYoung Kang, Keith G. Ray, Patrick T. Shea, Tae Wook Heo, Joel B. Varley, Tadashi
Ogitsu, Stanimir A. Bonev, Brandon C. Wood
Lawrence Livermore National Laboratory, Livermore, California 94550, USA
Unlike simple metal hydrides, complex metal hydrides undergo solid-state phase transformations that result in deviations from
ideal bulk descriptions of isolated materials. Moreover, these factors evolve continuously during the non-equilibrium conditionsof cycling. This lends additional importance to factors associated with structural, dynamical, and chemical inhomogeneity.
Consequently, modeling properties beyond the ideal limit is critical to understand the (de)hydrogenation processes of complex
metal hydrides and ultimately help optimize their performance. This presentation will introduce the modelling efforts of the DOE
Hydrogen Storage Materials — Advanced Research Consortium (HyMARC) to investigate non-ideal behaviors of complex metal
hydrides ranging from anharmonic vibrations; modeling of point defects, interfaces and amorphous phases; and transport andreaction kinetics.

Introduction
Computational investigations have provided key insights into
many challenges associated with (de)hydrogenation of metal
hydrides. For simple hydride systems like Pd/PdHx(0 < x < 1) and Mg/MgH2, both the thermodynamics andkinetics were studied by computing the mixing energies of
two end compounds, energy barriers for H2 adsorption anddesorption, interface energies, and H migration energy inbulk [1-4]. On the other hand, for complex metal hydrides
such as Mg(BH4)2, which are comprised of cations andmolecular anion complexes, conventional computations havegenerally been limited to the ideal bulk thermodynamics andstructure predictions of possible intermediates [5,6].
Moreover, finite-temperature effects have typically been
approximated to the ideal harmonic oscillations extrapolated
from the 0 K limit. However, it is not clear such ideal
modeling is enough to capture the non-ideal behavior ofcomplex metal hydrides arising from anharmonic rotations ofmolecules, lack of crystallinity of phases, role of interfaces
and surfaces, and so forth. Also, direct comparison withexperiments is relatively challenging, which hinders
verification of the models. Therefore, in order to explain thepoor reversibility and slow kinetics observed in experiments
and further design a viable hydrogen storage system, moresophisticated computational approaches are critical.

Modeling efforts in HyMARC beyond-ideal
approaches
Within HyMARC, our theory effort aims to develop a newcomputational set-up focusing on the non-ideal behavior ofcomplex metal hydrides. To better assess the finitetemperature thermodynamics of complex metal hydrides andtheir intermediates, we have used large-scale ab initio
molecular dynamics calculations to include anharmonic
vibration energies that go beyond conventional approaches
only with harmonic oscillations of bonds from 0 K
approximations. Because real hydrogen storage materials
feature complex reactions involving nucleation and growth ofintermediate phases, we have also been evaluating surface
and interface effects that may play a role during(de)hydrogenation. Furthermore, our calculation framework

allows us to explore the structural, energetic, and chemical
properties of complex hydrides and their intermediates
beyond the ideal crystalline bulk approximation, since many
phases are known to be amorphous or non-stoichiometricduring actual reactions. Combining all of these effects, wewill provide examples where the phase equilibria candramatically change with respect to those predicted from
ideal bulk calculations.
Along with thermodynamic impacts, we will discuss how thepresence of surfaces and interfaces can also havesignificant effects on kinetics of, particularly such as, phasenucleation and growth. They can also promote masstransport in otherwise sluggish materials, or alter thechemical evolution of molecular anions.
Finally, we will discuss how our atomistic simulations may becoupled with phase field modeling to compare withexperimental observations for model validation. In this way,
we can predict the phase fraction evolution under(de)hydrogenation conditions as a function of particle size.
Besides multiscale modeling, we will also show how direct
spectroscopic simulations can be used in conjunction withexperimental measurements to refine models and interpretchemical pathways.

References[1] R. Grau-Crespo, K. C. Smith, T. S. Fisher, N. H. de Leeuw,
and U. V. Waghmare, Physical Review B 80, 174117 (2009).
[2] A. J. Du, S. C. Smith, X. D. Yao, and G. Q. Lu, Surface
Science 600, 1854 (2006).
[3] D. Tomanek, Z. Sun, and S. G. Louie, Physical Review B 43,
4699 (1991).
[4] S. Matar, Progress in Solid State Chemistry 38, 1 (2010).
[5] J. Voss, J. Hummelshoj, Z. Lodziana, and T. Vegge, Journalof Physics-Condensed Matter 21, ARTN 012203 (2009).
[6] Y. Zhang, E. Majzoub, V. Ozolins, and C. Wolverton, Journalof Physical Chemistry C 116, 10522 (2012).
This work of was performed under the auspices of the U.S.
Department of Energy by Lawrence Livermore National
Laboratory under Contract DE-AC52-07NA27344.

ShinYoung Kang is a postdoctoral researcher in the Materials Science Division at Lawrence Livermore National
Laboratory. Kang received her B.S. in Materials Science and Engineering in 2007 from Seoul National University,
South Korea and her Ph.D. in Materials Science and Engineering in 2014 from MIT, USA. Her research interests
focus on computational design and understanding fundamentals of new materials for a clean energy future, suchas hydrogen storage materials and batteries.
Corresponding author: ShinYoung Kang, kang10@llnl.gov, +1 (925) 253-5785

44

ENABLING REVERSIBILITY IN COMPLEX METAL HYDRIDESMark D. Allendorf 1,* Vitalie Stavila,1 Brandon Wood,2 Keith Ray,2 Tae-Wook Heo,2 Jonathan R. I.
Lee,2 James L. White,1 Rob Kolasinski,1 Farid El Gabaly,1 Lennie L. Klebanoff,1 Tom Autrey3
1 Sandia National Laboratories, Livermore, CA, 94551, USA
2 Lawrence Livermore National Laboratory, Livermore, CA, 94551, USA
3 Pacific Northwest National Laboratory, Richland, WA 99354, USA
We demonstrate that doping and catalysis coupled with high-pressure hydrogen (350 bar and above) are promisingstrategies to improve the reversibility and cycle life in metal alanates, amides and borohydrides. Thermodynamic
calculations reveal that anharmonic contributions are important in accurately predicting the behaviour of complex metal
hydrides at equilibrium, especially at high temperatures and pressures.

Introduction
Complex metal hydrides (CMH) are attractive hydrogenstorage media due to their high gravimetric and volumetrichydrogen densities and potential reversibility. In the
Hydrogen Materials Advanced Research Consortium(HyMARC), we are evaluating strategies to decrease H2
desorption temperatures and improve reversibility of thesematerials, with the goal to provide enabling proof-ofconcept that will motivate and accelerate materials
discovery. Amorphization and nanostructuring are among
several strategies being considered. Here, we describe
recent results concerning the role of additives targeted atthermodynamic destabilization and high-pressure H2 (350
and 700 bar), a strategy enabled by newly constructedcharging stations.

Computational thermodynamics of Mg-B-H compounds asa function of T and p(H2) is aiding interpretation of theresults. We computed the vibrational density of states byquantum molecular dynamics and determined the quasiand anharmonic contributions. As shown in the figure(right), the vibrational component of the standard enthalpy
within the harmonic approximation (dashed lines) and fully
dynamical enthalpy descriptions (solid lines) differ
significantly, particularly at high temperatures.

Results
Considering first the role of additives, the ability of Ti
species to improve the kinetics of reversibility of alanatesand other CMH is well known. Interestingly, we also findthat Ti affects the plateau pressure in both bulk LiAlH4 and
NaAlH4, indicating that thermodynamics are also affected.
In-situ Al K-edge XAS and AP-XPS studies reveal that TiAl alloying is responsible for the thermodynamic effect.
Similarly, potassium doping of amides (LiNH2/LiH and
LiNH2/MgH 2) both accelerates the reaction rate andslightly increases the plateau pressure. Understanding themechanism of these behaviors is crucial to assessing thegenerality this strategy.
Concerning CMH regeneration at high pressures, we findthat M2B12H12 (M=Li,Na,K) converts to the corresponding
M2(BH4)2 in almost quantitative yield in high-pressure H2
at temperatures above the borohydride melting point [1].
Similarly, H2 pressures ≥350 bar enable hydrogen uptake
by MgB2 to form Mg(BH 4)2 (figure, left) [2].

Mark Allendorf

Conclusions
In conclusion, we demonstrated that doping and highpressure H2 are effective strategies for improving
reversibility in CMH. Computational thermodynamics is avaluable tool for understanding the behavior of thesematerials under high-pressure H2 if anharmonic
contributions to the energetics are included.

References[1] White, J.L. et al. J. Phys. Chem. C., 2016, 120, 2572525731.
[2] Severa G. et al, Chem. Commun, 2010, 46, 421-423.

Dr. Mark D. Allendorf is Director of the Hydrogen Advanced Materials Research Consortium(HyMARC) and a Senior Scientist at Sandia National Laboratories in Livermore, California. He holds
degrees in chemistry from Washington University in St. Louis (A.B.) and Stanford (Ph.D.). His research
focuses on the science and applications of metal-organic frameworks (MOFs), and on solid-statematerials for hydrogen storage. Current interests include effects of nanoconfinement on metal
hydrides and the use of MOFs for chemical sensing, electronic devices, and catalysts for biofuels
production. He is President Emeritus and Fellow of The Electrochemical Society and has received
awards for research, leadership, and teamwork, including a 2014 R&D100 Award.

Corresponding author: Mark Allendorf, Email: mdallen@sandia.gov, Tel. 925.294.2895

45

11th Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

Cyclic hydrogen storage performance of MgH2 with V-based additives*Sanjay Kumar a, b, Ankur Jaina, H Miyokaa, T Ichikawac, Y Kojimaa, G.K Deyb
aInstitute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Hiroshima, 739-8530, Japan
bMaterials Processing and Corrosion Engineering Division, BARC Mumbai-400085, India

cGraduate School of Integrated Arts & Sciences, Hiroshima University, 1-3-1 Kagamiyama, Hiroshima, 739-8530, Japan

Abstract: The kinetics of hydrogenation-dehydrogenation Mg-MgH2 have been studied with respect to vanadium based
additives. The apparent activation energies of all the composite were evaluated and compared. It has been found that V 2O3
additive remarkable reduced the hydrogenation-dehydrogenation temperature. The catalytic mechanism was proposed in
the current study.

Introduction
The Mg-MgH2 system has been considered as a potential
candidate for onboard hydrogen storage application due tohigh hydrogen storage capacity (> 7.3 wt. %). The highhydrogenation-dehydrogenation temperatures (Tdesor >300 oC, Treabs > 350 oC) are the major issues. These issues
could be resolved by a suitable dopant. In the present
study vanadium based compounds have been doped tofine tune the kinetics and cyclic performance of Mg-MgH2
systemenergies of catalyzed MgH2 were substantially reduced ascompared to un-catalyzed MgH2 which were found to be
78 and 143 kJ/mol for hydrogenation-dehydrogenation,
respectively. All the results with suitable mechanism will
be presented in the paper.

Experimental
The samples were prepared by ball milling of MgH2 withand without dopant (10 wt. % V, VCl3, and V2O3 were used
as a dopant) for 20 hours in inert atmosphere. The
hydrogenation-dehydrogenation were conducted in athermogravimetric (TG) – equipped with DTA-MS and
Differential Scanning Calorimetry (DSC).The phase andthe morphological characterizations were done by powder
X-ray Diffraction (XRD) and Scanning Electron
Microscope (SEM) respectively. The chemical state of thecatalyst was determined by X-ray photoelectron
Spectroscopy (XPS). The hydrogenation rates were
measured in a Sievert's apparatus.

Results and Discussion
The catalytic effect of vanadium, VCl3, and V2O3 dopant
have been investigated. A typical hydrogenationdehydrogenation curves are shown in the Fig. 1. Amongothers, V2O3 is the best catalyst. It has decreased thedehydrogenation temperature by more than 150 OC as
compared to un- catalyzed MgH2. Moreover, V2O3
catalyzed Mg (dehydrogenated MgH2) was able tohydrogenate even below room temperature. The apparent
activation energies of hydrogenation-dehydrogenation of
MgH2-10 wt. % V2O3 were calculated and found to be 40
kJ/mol and 98 kJ/mol respectively. The apparent activation

Sanjay Kumar

Acknowledgements
This work has supported by JSPS under JSPS-PDF
program granted to Sanjay Kumar (JSPS ID P15078)

References[1] Andre Zuttel, Materials for hydrogen storage, Materials
Today 2013; 24-33.
[2] Gagik Barkhoradarian, Thomas Klassen, Rudiger
Bormann. Fast hydrogen sorption kinetics ofnanocrystalline Mg using Nb2O5 as Catalyst, Scripta
Mater 2003; 49: 213-217

Dr. Sanjay Kumar obtained his PhD degree in Chemical Sciences from Homi Bhabha National Institute
Mumbai. Currently, Dr. Kumar is a JSPS-PostDoc fellow at Institute for Advanced Materials Research,
Hiroshima University- Japan. His research interests include the development of materials for hydrogenstorage and permeation applications and development of nanomaterials for various energy conversion
applications. He has in his credit more than 100 research papers and articles published in reputed
international/national journals and conference proceedings. He is recipient of several best paper
awards in various conferences and seminar at national & international levels. He has been conferredgroup achievement award by the Department of Atomic Energy, Govt. of India for his contribution to
the development of materials for fusion reactor.

*Corresponding author: Sanjay Kumar, sanjay.barc@gmail.com, Tel. +81 70 23536279

46

th

11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa$,$Hawaii$2017$

SEPARATION*OF*HYDROGEN*ISOTOPES*IN*POROUS*MATERIALS*
Michael$Hirscher1,$Thomas$Heine2,$Hyunchul$Oh3$$
1

Max$Planck$Institute$for$Intelligent$Systems,$Heisenbergstr.$3,$70569$Stuttgart,$Germany$2

WilhelmMOstwaldMInstitute$of$Physical$and$Theoretical$Chemistry,$Leipzig$University,$Linnéstr.$2,$04103$Leipzig,$Germany$

3

Department$ of$ Energy$ Engineering,$ Gyeongnam$ National$ University$ of$ Science$ and$ Technology,$ Jinju,$ Gyeongnam,$
52725,$Republic$of$Korea$
In$microporous$materials$hydrogen$isotopes$can$be$separated$by$either$confinement$in$small$pores$i.e.$“Quantum$Sieving”$
or$ by$ strong$ adsorption$ sites$ i.e.$ “Chemical$ Affinity$ Quantum$ Sieving”.$ MetalMorganic$ frameworks$ (MOFs)$ are$ excellent$candidates$for$studying$these$quantum$effects$due$to$their$wellMdefined$pore$structure$and$the$possibility$to$introduce$strong$
adsorption$ sites$ directly$ into$ the$ framework.$ After$ exposure$ to$ an$ isotope$ mixture,$ the$ separation$ capability$ is$ directly$
measured$by$lowMtemperature$thermal$desorption$spectroscopy.$
The$separation$of$hydrogen$isotopes$has$always$been$a$challenge$for$the$wellMknown$techniques$because$of$their$
identical$ size,$ shape$ and$ thermodynamical$ properties.$
Nowadays$ the$ extraction$ of$ Deuterium$ is$ done$ with$cryogenic$distillation$at$24K,$or$the$GirdlerMsulfide$process,$which$produces$heavy$water$and$further$electrolysis,$leads$
to$ Deuterium.$ Unfortunately$ these$ methods$ have$ low$
separation$ factors$ (1.5$ and$ 2.3,$ respectively)$ and$ high$energy$costs.$Deuterium$is$needed$for$many$applications$in$ industry$ and$ science,$ like$ for$ nuclear$ fusion,$ in$ fission$
reactors$ as$ a$ cold$ source,$ neutron$ scattering$ and$ in$isotopic$tracing.$$
One$ mechanism$ is$ kinetic$ quantum$ sieving$ (KQS),$ a$method$first$proposed$by$Beenakker$et$al.* [1],$who$have$shown$that$D2$has$a$shorter$de$Broglie$wave$length,$and$
thus$a$smaller$effective$radius$than$H2.$In$consequence,$it$
penetrates$ easier$ through$ small$ openings.$ KQS$ shows$higher$ mobility$ of$ heavier$ hydrogen$ isotopologues$ and$hence$ acts$ opposite$ to$ the$ tunnel$ effect,$ where$ the$opposite$ phenomenon$ would$ be$ expected,$ and$ also$ to$classical$diffusion,$where$lightMweight$species$have$higher$
velocities.$ In$ a$ different$ mechanism,$ strongly$ attractive$
interaction$ sites$ of$ MOFs$ preferably$ adsorb$ heavy$hydrogen$ isotopologues$ due$ to$ their$ smaller$ zeroMpoint$energy$ (ZPE)$ and$ resulting$ in$ a$ stronger$ adsorption$enthalpy.$ We$ will$ call$ this$ effect,$ in$ analogy$ to$ KQS,$
chemical$affinity$quantum$sieving$(CAQS)$[2M7].$
MOFs$ are$ excellent$ candidates$ for$ studying$ these$quantum$ effects$ due$ to$ their$ wellMdefined$ pore$ structure$
and$ the$ possibility$ to$ introduce$ strong$ adsorption$ sites$
directly$ into$ the$ framework.$ Doped$ or$ functionalized$

M.$Hirscher$samples$of$the$robust$MFUM4$series$possessing$optimized$
pore$aperture$or$open$metal$sites,$respectively,$have$been$
investigated$for$their$hydrogen$separation$capability.$The$
samples$have$been$exposed$to$an$isotope$mixture$and$the$adsorbed$ quantity$ of$ each$ isotope$ was$ detected$ by$ lowM
temperature$thermal$desorption$spectroscopy$(TDS).$The$
ratio$of$the$desorbed$amount$of$deuterium$and$hydrogen$leads$ directly$ to$ the$ selectivity$ (separation$ factor).$ The$
selectivity$ is$ determined$ as$ a$ function$ of$ exposure$ time$
and$temperature$and$exhibits$the$highest$value$observed$
at$ temperatures$ well$ above$ the$ boiling$ point$ of$ liquid$
nitrogen$ [8].$ The$ results$ will$ be$ discussed$ regarding$possible$technical$applications.$

References*[1]$ J.$Beenakker$et$al.,$Chem.$Phys.$Letters$232,$379$(1995)$[2]$J.$Teufel$et$al.,$Adv.$Mater.$25,$635$(2013)$[3]$H.$Oh$et$al.,$J.$Mater.$Chem.$A,$1,$3244$(2013)$[4]$H.$Oh$et$al.,$Angew.$Chem.$Int.$Ed.,$52,$13219$(2013)$[5]$H.$Oh$et$al.,$ACS$Nano$8,$761$(2014)$[6]$Savchenko$I.$et$al.,$Micro.$Meso.$Mater.$216,$133$(2015)$[7]$H.$Oh$and$M.$Hirscher,$Eur.$J.$Inorg.$Chem.$27,$4278$(2016)$[8]$ I.$Weinrauch$et$al.,$Nature$Communications$in$press$

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.$For$his$achievements$during$his$PhD$studies$in$Stuttgart$he$was$awarded$
the$Otto$Hahn$Medal$of$the$Max$Planck$Society$in$1988.$After$this$he$spent$a$postMdoctoral$fellowship$
at$the$University$of$Pennsylvania,$Philadelphia,$USA.$Since$2013$he$is$Operating$Agent$of$Task$32$“HydrogenMbased$ Energy$ Storage”$ in$ the$ Hydrogen$ Implementation$ Agreement$ of$ the$ IEA.$ He$threceived$ Hydrogen$ &$ Energy$ Award$ 2015$ in$ Switzerland.$ He$ has$ been$ the$ vice$ chair$ of$ the$ 15 $International$Symposium$on$MetalMHydrogen$Systems$MH2016$and$is$one$of$the$vice$chairs$of$the$
GRC$on$HydrogenMMetal$Systems$this$year.$$

Corresponding$author:$Michael$Hirscher,$hirscher@is.mpg.de,$Tel.$+49M711M689M1808$

47

A NEW ROLE FOR SOLVENTS: FROM UNDESIRABLE RESIDUE TO
USEFUL ADDITIVE
Marina Chong, Phuong Nguyen, Sunil Shrestha, Mark Bowden, Abhi Karkamkar, Craig
Jensen and Tom Autrey
Pacific Northwest National Laboratory, Richland WA 99352 USA
In spite of near optimum thermodynamics that should allow for cycling of H2 moderate conditions Mg(BH4)2 is hindered byslow kinetics and high temperature requirements. Studies have typically focused on the pure complex but the presenceof solvent coordinated to Mg(BH4)2 has been found to significantly alter its dehydrogenation pathway and lower thetemperature at which hydrogen release begins. The role of solvents as additives to Mg(BH4)2 was investigated and THF
was found to alter the dehydrogenation path to selectively yield MgB10H10 as determined by NMR. Various analyticaltechniques were utilized to characterize both starting materials and dehydrogenation products to understand how thepresence of THF affects the mechanism of hydrogen cycling.

Introduction
Magnesium borohydride (Mg(BH4)2) has been studied
extensively as a potential hydrogen storage material.
Although calculations suggest optimal thermodynamics
for dehydrogenation under more moderate conditions
than the Group I borohydrides, experiments reveal
temperature requirements >300°C to release asubstantial fraction of its hydrogen content. At a lower
decomposition temperature of 200°C it has been foundthat H2 can be cycled through the intermediate species,
Mg(B3H8)2.1
Upon hydrogenation of independently
synthesized Mg(B 3H8)2yTHF2 (where THF could not be
removed without decomposition of the complex) it wasobserved that conversion to Mg(BH 4)2 occurred much
more readily than in the unsolvated material.
Wesurmised that presence of THF has a role in altering theenergetics of hydrogen cycling.
To test this, Mg(BH4)2yTHF was prepared, as well asother solvates, and dehydrogenated. The materials werecharacterized by a combination of NMR, XRD, IR, and
DSC to elucidate structural differences between
unsolvated and solvated Mg(BH4)2 and to identify the
species formed upon dehydrogenation.

Results
It was found that certain solvates significantly lowered theonset dehydrogenation temperature and the THF solvate,in particular, enabled up to 50% conversion of thestarting material. Of even more interest was the selective
dehydrogenation of Mg(BH 4)2yTHF to MgB10H10 witheither no or minimal formation of MgB 12H12, a species
that acts as a thermodynamic barrier to reversibility.
Cycling through the MgB 10H10 intermediate is appealing
due to its much higher hydrogen weight capacity of 8.5%
compared to the 2.5% wt% H2 released bydehydrogenation to Mg(B3H8)2. In addition, preliminary
results show that MgB10H10 can be rehydrogenated backto Mg(BH4)2.

These results are supported by in situ solid state variable
pressure Magic Angle Spinning NMR, which allows forthe observation of intermediate formation during heating
to 200°C. The presence of MgB 10H10 was confirmed in
the early stages of dehydrogenation by this method. Ex
situ solution state NMR of the revealed up to 60% yield of
MgB10H10 after dehydrogenation at 180°C for 24 hours,
typically along with trace levels of an identified species at-13 ppm, MgB12H12, and Mg(B3H8)2.
IR analysis of the THF solvates indicated a change in thecoordination mode between the Mg cation and thetetrahedral BH4- unit from ionic in the unsolvated complex
to covalent in the presence of THF. DSC scans revealed
endothermic events occurring below 100°C in the THF
solvates corresponding to melting of the materials. It is
likely that the combination of modified structure andphysical properties alters the dehydrogenation route ofMg(BH4)2. High throughput studies comparing thedehydrogenation of Mg(BH 4)2yxTHF (x=0.25-3) under thesame conditions indicated that Mg(BH 4)2y0.5THF may
result in the highest yield of MgB 10H10 with minimal
formation of side products.
Acknowledgements We would like to thank the Fuel
Cell Technology Office in the U.S. Dept. of Energy’s
Office of Energy Efficiency and Renewable Energy.
Pacific Northwest National Laboratory is operated byBattelle for the U.S. Dept. of Energy. We would also liketo acknowledge the invaluable discussions with Tom
Gennett, Gary Edvenson, Mira Dimitrievska, Terry
Udovic, Bojana Ginovska, and Iffat Nayyar.

References[1] Chong, M., Karkamkar, A., Autrey, T., Orimo, S.,
Jalisatgi, S., Jensen, C. M. Chem. Comm., 2011, 47(4), 1330[2] Chong, M., Matsuo, M., Orimo, S., Autrey, T., Jensen,
C. M. Inorg. Chem., 2015, 54 (8), 4120

Marina Chong is a post-doctoral researcher in the Physical and Computational Science Directorate at
the Pacific Northwest National Laboratory. She is currently studying how additives moderate thedehydrogenation of Mg(BH 4)2.
Corresponding author: Marina Chong, marina.chong@pnnl.gov, +1 (509)375-3784

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11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

HYDROGEN STORAGE OPTIONS
A. ZÜTTEL, M. SPODARYK, K. ZHAO, W. LUO, R. MUTSCHLER, H. YANG
Laboratory of Materials for Renewable Energy (LMER / ISIC / SB), École polytechnique fédérale de Lausanne (EPFL)
Valais/Wallis, Energypolis, Sion, Switzerland
Empa Materials Science and Technology, Dübendorf, Switzerland
Currently hydrogen storage for mobile applications and for large quantities is realized either as pressurized hydrogen or
as liquid hydrogen. Physisorbed hydrogen on materials with a large specific surface area, metal hydrides and complex
hydrides are found in demonstration projects. The reduction of CO2 with hydrogen to synthetic hydrocarbons has a great
potential to store large quantities of renewable energy in a easy and safe form.

Storage requirements
Mobile as well as seasonal storage of hydrogen require ahigh gravimetric energy density on one side for autonomy
and on the other side for economic reasons. Mobile
applications need approx. 10 kWh/100 km per passenger(divided by the efficiency) and seasonal storage requires
approx. 5000 kWh per capita. Hydrogen storage in
MOF's reaches >9 mass% of hydrogen at around 100 K[1] and functionalization of MOF's may lead to evenhigherphysisorption
capacities.
Some
organic
compounds e.g. perhydro-N- ethylcarbazole (H12-NEC)[2] exhibit 6 mass% of hydrogen as a liquid at room
temperature. Hydrogen absorption takes place at 150°C
and 50 bar on Ru/Al2O3 catalyst (ΔHr = -50 kJ/mol) anddesorption at 260°C and 3 bar.

Complex hydrides
The alanates and boohydrides available are stablecompounds and do not spontaneously release hydrogenat ambient conditions. According to the stability model [3]borohydrides with a cation electronegativity of En > 1.4
develop a hydrogen pressure >1bar at room temperature.
It is of fundamental importance for the application, wether
this pressure is an equilibrium pressure or the hydrides
are spontaneously decomposing, i.e. if the hydride
formation and desorption reaction pathways are thesame. Some transition metal complex borohydrides are
liquid at room temperature, e.g. Ti(BH4)3, and can bestabilized by infiltration in nanostructures [3].

Synthetic Hydrocarbons
The reaction of hydrogen with carbon dioxide leads to
products and allow to store hydrogen in large quantities.

AndreasZÜTTELIn water CO2 dissolves and forms carbonic acid (H2CO3).
The reduction of H2CO3 leads to formic acid (HCOOH),
this reaction exhibits a hydrogen storage capacity of 4.5
mass%. Further, reduction of CO2 on the cathode of anelectrochemical cell produces ethene and ethane andprobably higher CH compounds. The gas phasereduction of CO2 on a heterogeneous catalyst with thereversed water gas shift reaction leads to CO and with
the Sabatier reaction to CH4. Furthermore, methanol is apossible product of the CO2 reduction with hydrogen.
The pure hydrogen cycle is realized by purely technicalmeans, production and use of hydrogen are establishedtechnologies. The main challenge is the dense, safe andeconomic storage of hydrogen. On the other side thechallenges for the realization of the hydrocarbon cycle isthe extraction of the CO2 from the atmosphere and thecontrol of the CO2 reduction reaction to a specificproduct, while the storage of hydrocarbons is based on awell established technology and economy. Hydrocarbons
exhibit a energy storage density of >10 kWh/kg and
3>10000 KWh/m .

References[1] Michael Hirscher, “Hydrogen-based Energy Storage”,
talk at WHEC2016, Zaragoza, Spain, 15th June, 2016[2] W. Peters, Eypasch,T. Frank, J. Schwerdtfeger, C.
Körner, A. Bösmanna and P. Wasserscheid, Energy &Environmental
Science(2015),
DOI:
10.1039/c4ee03461a[3] Callini, E., Atakli, Z.Ö.K. et al. Appl. Phys. A (2016)
122: 353. doi:10.1007/s00339-016-9881-5

Short CV: 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 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 the sciencefaculty UniFR. President of the Swiss Hydrogen Association „HYDROPOLE“. 2006 Head of thesection “Hydrogen & Energy” at EMPA and 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, 2014 Full Professor for Physical Chemsitry, Institut des Sciences etIngénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland

Corresponding author: Andreas ZÜTTEL, email: andreas.zuettel@epfl.ch, M: +41 79 484 2553, T: +41 21 695 8304
(Secretary), URL: http://lmer.epfl.ch

49

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11 $Int.$Symposium$Hydrogen$&$Energy$

Waikoloa$,$Hawaii$2017$

CO2$adsorption$reaction$on$Ni$and$Cu$powder$surface$
Kun$Zhao,$Andreas$Züttel$
Laboratory$of$Materials$for$Renewable$Energy$(LMER)$
Institute$of$Chemical$Sciences$and$Engineering$(ISIC)$
Ecole$Polytechnique$Fédérale$de$Lausanne$(EPFL)$Valais,$1951$Sion,$Switzerland$
Abstract:$ CO2$ reduction$ processes$ initiate$ from$ CO2$ chemisorption$ and$ activation,$ preparing$ for$ the$ following$hydrogenation,$ CWO$ bond$ cleavage,$ CWH$ and$ CWC$ bonds$ formation.$ The$ different$ adsorption$ structures$ could$ not$ only$
lead$ to$ different$ reaction$ intermediates,$ but$ also$ the$ controversial$ electronWtransfer$ mechanisms.$ Thus,$ it$ is$ primarily$
important$ to$ figure$ out$ the$ exact$ adsorption$ structures$ together$ with$ the$ intermediates$ in$ order$ to$ understand$ the$ CO2$
reduction$mechanisms.$CO2$adsorption$reactions$on$Ni$and$Cu$powders$were$monitored$in$Diffuse$Reflectance$Infrared$
Fourier$ Transform$ Spectroscopy$ (DRIFTS).$ The$ resulting$ spectra$ pointed$ out$ that$ CO2$ converted$ to$ carbonates,$
bicarbonates,$and$formates$while$chemically$adsorbed$on$the$powder$surfaces.$

Experiments$and$results$
CO2$ adsorption$ reaction$ on$ Ni$ and$ Cu$ powder$ surfaces$
has$ been$ investigated$ in$ DRIFTS.$ The$ measurements$
were$ taken$ at$ CO2$ pressure$ of$ 1$ or$ 200$ mbar$ with$ the$W6background$pressure$of$10 $mbar.$
W1

Peaks$ appear$ between$ 850$ –$ 1800$ cm $ carry$ the$ CWO$
bond$ information$ of$ monodentate,$ bidentate,$ and$ bridge$
2WW
W 1,$ 2$structure$ of$ CO3 ,$ HCO3 ,$ and$ HCO2 .
The$ manifest$
W1
peaks$ at$ 1060,$ 1383,$ and$ 1600$ cm $ are$ ascribed$ to$
2W!" , !$,% ,$and$!$,&% $of$monodentate$of$CO3 .$When$heating$oW1
up$to$100$ C,$the$peak$intensities$at$1060$and$1383$cm $disappeared$ gradually.$ Whereas,$ peaks$ at$ 900$ –$ 1050,$
W1
1100$–$1300,$and$1400$–$1800$cm $ranges$arose$up$with$the$ increasing$ of$ the$ temperature.$ The$ strong$ peak$ at$
W1
2W
1005$ and$ 1166$ cm $ belong$ to$ the$ bidentate$ of$ CO3 .$W1
2W
Peaks$ at$ 1262$ and$ 1731$ cm $ are$ from$ bridge$ CO3 .$Others$left$refer$to$bicarbonate$and$formate$(Fig.$1$(a)).$While$increasing$the$pressure$of$CO2$to$200$mbar$(Fig.$1$(b)),$ the$ monodentate$ carbonate$ becomes$ more$ stable$
and$ the$ most$ obvious$ species$ other$ than$ bidentate$carbonate$at$1$mbar.$Besides,$the$stretching$of$CWH$bond$
W1
of$ formate$ at$ 2800$ –$ 3000$ cm $ protrudes$ apparently$(inserted$in$Fig.$1$(b)).$Comparing$to$Cu$powder$surface,$monodentate$ carbonate$ is$ also$ the$ major$ species$ while$other$chemisorption$products$are$weak$(Fig.$1$(c)).$These$
imply$that$Ni$powder$is$more$reactive$than$Cu$powder$for$
CO2$activation.$$References$[1]$Taifan,$W.$Surf.&Sci.&Rep.$2016,$71,$595.
[2]$Seiferth,$O.$et&al.$Surf.&Sci.$1999,$421,$176.$

Fig.$1.$CO2$chemisorption$on$(a)$Ni$at$pressure$of$1$mbar,$(b)$Ni$
powder$at$pressure$of$200$mbar,$and$(c)$Cu$powers$at$pressure$of$ 200$ mbar$ in$ DRIFTS.$ CWH$ and$ OWH$ stretching$ bonds$ are$inserted$on$the$top$of$each$graph.$

Kun$Zhao.$2012$B.S.$in$Applied$Chemistry,$and$B.S.$in$Physics$in$Central$China$Normal$University,$
Wuhan,$China.$2015$M.S.$in$Physical$Chemistry$in$Central$China$Normal$University,$Wuhan,$China.$
Since$ February$ 2016$ PhD$ candidate$ in$ the$ group$ of$ Prof.$ Andreas$ Züttel,$ LMER,$ ISIC,$ SB,$ EPFL$
Valais/Wallis$in$Sion,$investigating$CO2$reduction$mechanisms$through$spectroscopic$methods.$
Email:$kun.zhao@epfl.ch$50

NEUTRON SCATTERING STUDIES OF HYDROGENOUS MATERIALS FOR
NEXT-GENERATION ENERGY STORAGE
Mirjana Dimitrievska,1,2, Wan Si Tang,1,3, Hui Wu,1 Wei Zhou,1 and Terrence J. Udovic1
1NIST Center for Neutron Research, National Institute of Standards andTechnology, Gaithersburg, MD 20899-6102,

United States
2National Renewable Energy Laboratory (NREL), Golden, CO 80401, United States
3Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742-2115, United States

This work will focus on the recent neutron scattering results from the NIST Center for Neutron Research involving a varietyof energy-related materials, ranging from borohydride-based and silanide-based hydrogen-storage materials to novel Li
and Na closo-polyborate superionic-conducting solid electrolytes. The relationship among the structural and dynamical
properties obtained from different neutron scattering techniques and the thermodynamic and conductivity properties ofthese various hydrogenous materials will be discussed.

Hydrogen and hydrogenous materials are considered among
the most promising choices for providing clean energy fortransport and other applications across the world, as well as
for future electrochemical energy storage. Understanding thefundamental properties of these materials and theirfunctionality at the atomic and molecular level is crucial toaddressing their role in the global challenge confronting
renewable energy technologies.
Hydrogen has the largest incoherent scattering interaction
with neutrons of all the elements in the periodic table and asizable coherent scattering interaction, making neutron
scattering techniques such as neutron powder diffraction(NPD), neutron vibrational spectroscopy (NVS), andquasielastic neutron scattering (QENS) invaluable forelucidating the structural and dynamical natures of thesematerials over a broad space and time domain. For example,
the combination of NPD and NVS coupled with density
functional theory (DFT) computations can be highly effective
for determining the detailed structures and vibrational
properties of hydrogenous energy-related materials.
Additionally, neutron-scattering fixed window scans (FWS)
and QENS can be used to track the mobilities andfundamental dynamical natures of the hydrogen within thesematerials over a broad temperature range.
In that regard, the main focus of this work will be on the recent
neutron scattering results from the NIST Center for Neutron
Research involving a variety of energy-related materials.
Fundamental information regarding the structural andvibrational properties of different Mg(BH 4)2 polymorphs fromboth theoretical and experimental points of view will bepresented, as well as how the measured NVS spectra of theMirjana
Dimitrievska

different Mg(BH4)2 phases can be used as references to help
identify the presence of a particular polymorph in materials of
unknown structure.1
Furthermore, structures and alkali-metal-dependent anion
reorientational dynamics of silanide-based hydrogen-storage
materials (MSiH3, M = K, Rb, Cs) will be described andanalyzed.2 Insights of rotational dynamics in these systems,
including the reorientational mobility of the anions and theirjump frequencies, should lead to better understanding of thehydrogen absorption/desorption process in these materials.
Finally, the dynamical properties of the novel Li and Na closopolyborate
superionic-conducting
solidelectrolytes
investigated by QENS will be presented. 3,4 These results
show the relative importance of anion charge and cation
concentration on anion reorientational mobilities andultimately on the ionic conductivity.

References[1] M. Dimitrievska, J. L. White, et. al., Phys. Chem. Chem.
Phys., 2016, 18, 25546–25552.
[2] W. S. Tang, M. Dimitrievska, et.al., J. Phys. Chem. C,
2016, 120, 21218–21227.
[3] W. S. Tang, K. Yoshida, et. al., ACS Energy Lett., 2016,
1, 659–664.
[4] A. V. Soloninin, M. Dimitrievska, et. al., “Comparison ofAnion Reorientational Dynamics in MCB9H10 andM2B10H10 (M= Li, Na) via Nuclear Magnetic Resonanceand Quasielastic Neutron Scattering Studies”,J. Phys.
Chem. C, submitted.

Mirjana Dimitrievska is a Post-Doctoral Fellow at NREL and the NIST Center for Neutron Research. She
obtained her PhD in Physics at the University of Barcelona while she had been working as a Marie Curie
Fellow at the Catalonia Institute for Energy Research in Barcelona and Helmholtz-Zentrum in Berlin. Her
previous experience is in structural, vibrational and defect characterization of materials for solar cellapplication, using Raman, photoluminescence and diffraction techniques, as well as theoretical simulations
and modeling. Currently, her research is focused on understanding the physics and chemistry underpinninghydrogen interactions in hydrogen storage-related materials, using various neutron scattering techniques.
She is an author of more than 40 scientific peer-reviewed publications and more than 15 oral presentations
at conferences.

Corresponding author: Mirjana Dimitrievska, Mirjana.Dimitrievska@nrel.gov, Tel: +1 301 250 3351

51

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11 $Int.$Symposium$Hydrogen$&$Energy$$

Waikoloa$,$Hawaii$2017$$

ADSORPTION* BEHAVIOR* OF* BORON* DOPED* GRAPHENE* OXIDE* FOR*AMMONIA*Heena$Yanga,$Andreas$Züttela,$Whajung$Kimb$a$$LMER,$ISIC,$SB,$École$polytechnique$fédérale$de$Lausanne$(EPFL)$Valais/Wallis,$Energypolis,$Rue$de$l’Industrie$17,$
CP$440,$CHY1951$Sion,$Switzerland$b$Department$of$Materials$Chemistry$and$Engineering,$College$of$Engineering,$Konkuk$University,$$1YHwa$Yang$Dong,$
Kwang$Jin$Gu,$Seoul,$S.$Korea$
Abstract:$ various$ ratios$ of$ Boron$ doped$ graphene$ oxide$ (BYGO)$ have$ been$ shown$ as$ highly$ effective$ adsorbent$ for$ammonia$due$to$a$high$density$of$strong$Lewis$acid$sites$arising$from$boron.$GO$is$doped$by$different$amount$of$Boron$based$on$xBYGO$(x$=$1.0,$3.0,$and$5.0).$BYGO$is$successfully$synthesized$and$confirmed$by$XRD,$FTYIR,$and$XPS.$The$
adsorption$ characteristics$ of$ BYGO$ are$ investigated$ by$ Temperature$ programmed$ desorption$ (TPD)$ and$ adsorption$
isotherm.$The$adsorption$isotherm$is$observed$to$increase$with$the$amount$of$B$up$to$3$times$of$GO$such$12.03,$and$16.30$
Y1
Y1$
mol$kg ,$beyond$which$it$is$rather$decreased$to$15.58$mol$kg due$to$reduce$of$Lewis$acid$sites$by$BYO$bonds.$B$doped$
into$GO$significantly$enhances$the$adsorption$capacity$of$ammonia.$$

Introduction*

Results*and*discussion*

Hydrogen$production$and$storage$is$a$very$important$clean$energy$ source.$ Among$ several$ hydrogen$ sources,$
ammonia$has$recently$received$attention$as$nonYfossil$fuel$energy$ source.$ However,$ ammonia,$ as$ a$ one$ of$ air$pollutant,$ is$ widely$ produced$ chemical.$ Various$
researches$ have$ been$ studied$ for$ handling$ ammonia.$
Among$ the$ researches$ carbonaceous$ materials$ such$ as$
activated$carbons$are$known$as$a$multiYpurpose$adsorbent$material$due$to$its$high$surface$area$[1].$There$are$many$studies$modifying$surface$of$carbon$to$increase$adsorption$
force$with$ammonia,$such$as$oxidation$for$formation$of$acid$groups$ [2],$ impregnation$ with$ inorganic$ compounds$ like$metal$ oxide$ [3],$ acids$ and$ bases$ [4].$ On$ the$ other$ hand$different$mechanism$for$adsorption$of$ammonia$has$been$
investigated$ which$ is$ using$ Lewis$ and$ Brønsted$ basic$characters$ [5].$ Ammonia$ can$ strong$ interact$ with$ Lewis$
and$ Brønsted$ site$ due$ to$ the$ structure$ of$ ammonia$ has$lone$pair$of$electrons$on$the$nitrogen$[6].$Graphene$oxide$has$ functional$ groups$ such$ as$ epoxy,$ hydroxyl,$ and$carbonyl/carboxyl$ groups.$ The$ ammonia$ is$ possible$ to$react$with$carboxylic$acids$as$either$Brønsted$and$Lewis$
acid$ site$ [7].$ In$ this$ study,$ graphene$ oxide(GO)$ was$investigated$ as$ an$ adsorbent$ of$ ammonia$ to$ increase$adsorption$ force$ using$ functional$ groups$ in$ GO.$ Further,$
GO$was$doped$with$different$ratio$of$boron$to$add$Lewis$
acid$for$ammonia$adsorption.$The$adsorption$behavior$of$
GO,$and$various$B$doped$GO$was$reported$with$different$
concentration$of$ammonia.$$

The$ various$ BYGO$ were$ then$ synthesized$ through$pyrolysis$and$confirmed$by$XRD.$The$FTYIR$analysis$was$
conducted$ to$ confirm$ the$ functional$ groups$ of$ the$ BYGO.$
The$XPS$analysis$is$conducted$and$the$relative$intensities$
of$BYC$are$2.8%$for$1.0BYGO,$6.4%$for$3.0BYGO,$and$6.7%$
for$5.0BYGO,$respectively.$It$indicates$that$B$is$not$doped$
up$to$3$times$of$GO.$The$TPD$analysis$shows$strong$peak$oat$150$ C$and$the$ammonia$adsorption$of$BYGO$at$a$low$
temperature$is$made$mainly$from$GO$due$to$a$weak$bond$
between$ functional$ group$ of$ GO$ and$ ammonia.$ The$
adsorption$ between$ B$ and$ ammonia$ which$ is$ strong$binding$and$maintained$up$to$a$high$temperature$can$be$available$from$electron$deficient$boron.$Through$the$TPD$
results,$ the$ B$ which$ is$ bonded$ to$ carbon$ primarily$
adsorbed$ammonia$by$strong$bond,$and$then$the$adsorbed$
ammonia$are$increased$by$physical$adsorption.$$
The$ isotherm$ results$ and$ the$ adsorption$ capacity$ is$ in$order$to$1.0BYGr$<$5.0BYGr$<$3.0BYGr:$12.03$mol/kg,$16.30$
mol/kg,$and$15.58$mol/kg,$respectively.$$

References*[1]$ Activated$ carbon$ surfaces$ in$ environmental$
remediation.$Elsevier,$UK,$2006.$[2]$Interf.$Sci.$291$(2005)$597Y599.$[3]$Carbon$45$(2007)$568Y578.$[4]$J.$Colloid.$Interf.$Sci.$212$(1999)$186Y189.$[5]$ Principles$ of$ Chemistryp$ The$ Molecular$ Science,$
Cengage$Learning,$Boston,$2009.$[6]$Thermochim$Acta$312$(1998)$27Y32.$[7]$Chem.$Soc.$Rev.$38$(2009)$1477Y1504.$$*

Born$in$1986$in$Seoul,$Republic$of$Korea,$Heena$Yang$graduated$with$a$Ph.D.$degree$in$Materials$
Chemistry$ and$ Engineering$ from$ Konkuk$ university$ in$ 2016.$ During$ this$ time,$ she$ worked$ as$ an$undergraduate$research$assistant$in$the$field$of$nanostructured$materials$and$proton$exchange$fuel$cells$at$Konkuk$university.$Her$current$research$is$focused$on$complex$hydride$for$hydrogen$storage$
at$Ecole$Polytechnique$Fédérale$de$Lausanne$(EPFL),$Switzerland$

Heena$Yang$
Corresponding$author:$Heena$Yang,$email:$Heena.yang@epfl.ch,$Tel:$+41$21$69$58214.$
$

$$

$

52

USING NEUTRONS TO PROBE HYDROGEN STORAGE IN METALORGANIC FRAMEWORKS
Jacob Tarvera, Craig Brownb, Tom Gennettaa) National Renewable Energy Laboratory, Golden, CO 80401, United Statesb) National Institute of Standards and Technology Center for Neutron Research, Gaithersburg, MD 20899, United States
Neutron scattering techniques provide unique opportunities to study hydrogen storage in a variety of media. Here we
report recent neutron measurements on hydrogen adsorption in a number of metal organic frameworks. Neutron powder
diffraction is shown to precisely identify preferred sequences of hydrogen binding locations as well as quantitatively
reveal mass uptake, while inelastic neutron scattering spectra reveal complementary information on the dynamics ofadsorbed hydrogen.

Introduction

Results

Metal-organic frameworks (MOFs) are a class of
crystalline materials comprising metal ions linked byorganic ligands to form robust structures. They havedemonstrated promising hydrogen storage ability due totheir high porosity, large internal surface area, and thepotential for coordinatively-unsaturated metal centers[1,2]. Interactions with hydrogen are strongly dependent
on the specific chemistry of the particular MOF. Neutron
scattering offers a powerful suite of characterization
techniques uniquely suited to understanding the influenceof pore chemistry on hydrogen stored in these materials.
Here, we report the use of neutron powder diffraction(NPD) employing 2H to precisely determine hydrogenbinding locations and inelastic neutron scattering (INS)employing 1H to probe the dynamics of adsorbedhydrogen within a variety of MOFs.

Comparison of NPD patterns obtained on Co2(m-dobdc)
before and after equilibration with increasingly highpressures of D 2 will be described. Precise fractional
coordinates of binding sites and site occupancies are
obtained through Rietveld refinement. The calculated
equivalent uptake of H2 demonstrates strong agreementwith adsorption isotherms determined via volumetricmethods. INS measurements of Mn2(dsbdc) show
negligible changes in hydrogen dynamics as dosing
increases from 0 to 2.0 H2 per metal site. At higher
dosages the emergence of weakly-bound H2 is observed,
providing strong support for the first report of adsorptionof two gas molecules at a single metal site [3].

Experimental
Neutron scattering measurements were obtained on
activated samples of Co2(m-dobdc) (m-dobdc4-=4,6dioxido-1,3-benzene dicarboxylate) and Mn2(dsbdc) (2,5disulfido-1,4-benzedicarboxylate). NPD and INS data
were collected on the high-resolution powder
diffractometer, BT1, and the Filter Analyzer Neutron
Spectrometer, BT4, respectively, at the National Instituteof Standard and Technology's Center for Neutron
Research. The samples were sealed in cans equippedwith valves for gas loading prior to loading on closedcycle refrigerators. NPD measurements on Co2(m-dobdc)
were obtained at 198 K at D2 pressures ranging from 0 to
79 bar. Mn2(dsbdc) samples were quantitatively dosedwith 0.2-2.3 equivalents of H2 per metal site andmeasured at 7 K using INS.

Acknowledgment
This research is supported by the U. S. Department ofEnergy, Office of Energy Efficiency and Renewable
Energy, Fuel Cell Technologies Office, under Contract
no. DE-AC36-08GO28308.

References[1] N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J.
Kim, M. O'Keefe, and O. M. Yaghi, Science,
300(5622), 1127-1129, 2003.
[2] M. Dincă, A. Dailly, Y. Liu, C. M. Brown, D. A.
Neumann, and J. R. Long, Journal of the American
Chemical Society, 128(51), 16876-16883, 2006.
[3] T. Runčevski, M. T. Kapelewski, R. M. TorresGavosto, J. D. Tarver, C. M. Brown, and J. R. Long,
Chemical Communications, 52(53), 8251-8254, 2016.

Jacob Tarver is a staff scientist in the Hydrogen and Fuel Cell Research group at the National
Renewable Energy Laboratory on detail at the National Instrument of Standards and Technology’s
Center for Neutron Research. He has a Ph.D. in Chemical Engineering from Princeton University in2012. Dr. Tarver’s current research interests focus on using neutron scattering techniques to better
understand structure-property relationships of hydrogen storage in sorbent media.

Jacob Tarver
Corresponding author: Jacob Tarver, Jacob.Tarver@nrel.gov, (301) 975-6840.

53

11th Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

CRYSTAL SHAPE CONTROLLED H2 STORAGE RATE IN NANOPOROUS
CARBON COMPOSITE WITH ULTRA-FINE PT NANOPARTICLE
Tsan-Yao Chena*, Cheng-Si Tsaob, Alice Huca Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan; b Institute of

Nuclear Energy Research, Atomic Energy Council, Executive Yuan, Taoyuan City 32546, Taiwan; c Department of
mechanical and biomedical engineering, City University of Hong Kong
This study demonstrates that the hydrogen storage rate (HSR) of nanoporous carbon supported platinum nanocatalysts(NC) is determined by their heterojunction and geometric configurations. Among the steps in hydrogen storage,
decomposition of H2 molecule into 2H atoms on Pt NC surface is the deciding factor in HSR that is controlled by the
thickness of Pt NC. For the best condition, HSR of Pt NC in 1 ~ 2 atomic layers thick (4.7 μg/g min) is 2.6 times faster thanthat (1.3 μg/g min) of Pt NC with higher than 3 atomic layers thick.

Introduction
Hydrogen is one of the most effective energy forms interms of power density and conversion efficiency forkeeping human civilization sustainable. However, incurrent development of technologies, the capacity ofhydrogen storage is often too low to be used as a dailyenergy supply, except for carbon supported Pt
nanocatalyst (NC). This material has been classified as apotential means to the on-board H2 storage material
according to the Department of Energy (DOE), U.S.A.
Although many studies have been devoted to spillover
mechanism, difficulty to reproduce earlier results indicatesthat gaps between experiment and fundamental theory inheterogeneous catalysis still exist1.

Results
In this study, X-ray diffraction (XRD) and theoreticalgeometry calculation are employed to reveal the bulk
structure parameters, oxidation ratios, as well as η inrelation to the shape of Pt NC. To investigate the impactsof crystal shape on HSR of Pt NC, density functional theory(DFT) calculation on proper atomic models is performed
which showing relocation of Pt atoms to carbon sitesaround metal clusters (Scheme 1). Our finding shows thatthe rate of H2 decomposition is controlled by the crystal
thickness of carbon supported Pt NC. For the best
condition, HSR of Pt NC in 1 ~ 2 atomic layers thick (4.7μg/g min) is 2.6 times faster than that (1.3 μg/g min) of Pt
NC with higher than 3 atomic layers thick.

Scheme 1 Relocation of Pt atom in different cluster shapesby reacting with H2 molecules.

Acknowledgements
T.-Y. Chen acknowledges the funding support from the
National Tsing Hua University, Taiwan (N103K30211 and103N1200K3), joint project of AOI-NTHU collaboration
105F8019K3, and the Ministry of Science and Technology,
Taiwan (MOST 103-2112-M-007-022-MY3 and MOST
105-3113-E-006-019-CC2).

References[1] Wang, L. & Yang, R. T. Hydrogen Storage on
Carbon-Based Adsorbents and Storage at Ambient
Temperature by Hydrogen Spillover. Catalysis
Review 52, 411-461,
doi:http://dx.doi.org/10.1080/01614940.2010.520265(2010).

Tsan-Yao Chen received the Young Faculty Research Award at National Tsing Hua University,
Taiwan in the third year of his Faculty track. He is currently an assistant professor in Engineering and
System Science from NTHU Taiwan. Professor Chen is working on the project of in-situ X-ray
characterizations on atomic relocation of nanocrystallite in homo-/heterogeneous nucleation andcrystal growth processes. His research interests include nanocrystal design and development forheterogeneous catalysis in energy conversion, storage, and environmental pollutant degradations.
Tsan-Yao Chen
Corresponding author: Tsan-Yao Chen, chencaeser@gmail.com, Tel. +886-3-5715131 ext.34271

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11 $Int.$Symposium$Hydrogen$&$Energy$$

Waikoloa$,$Hawaii$2017$$

HYDROGEN)ADSORPTION,)DISSOCIATION)AND)SPILLOVER)ON)METAL)
CLUSTERS)SUPPORTED)ON)TIO2)AND)CARBON7BASED)SURFACES)
Hsin@Yi$Tiffany$Chen$
Department$of$Engineering$System$and$Science,$National$Tsing$Hua$University,$HsinChu,$Taiwan$
Abstract$This$work$is$to$study$the$mechanism$of$hydrogen$spillover$promoted$by$metal$particles$on$oxide$surfaces$or/and$graphene$at$the$atomistic$level.$By$using$Density$Functional$Theory$calculations$with$Hubbard$corrections$(DFT+U),$we$have$ analyzed$ the$ adsorption,$ dissociation$ and$ spillover$ of$ molecular$ hydrogen$ on$ TiO2$ surfaces$ in$ the$ presence$ of$ a$
supported$Ru10$nanocluster.$The$role$of$the$supported$metal$particle$is$essential$as$it$favours$the$spontaneous$dissociation$
of$H2,$a$process$that$does$not$occur$on$the$bare$oxide$surface.$At$low$hydrogen$coverage,$the$H$atoms$prefer$to$stay$on$
the$ Ru10$ particle,$ charge$ accumulates$ on$ the$ metal$ cluster,$ and$ reduction$ of$ the$ oxide$ does$ not$ take$ place.$ On$ an$hydroxylated$surface,$the$presence$of$a$Ru$nanoparticle$is$expected$to$promote$the$reverse$effect,$i.e.$hydrogen$reverse$
spillover$from$the$oxide$to$the$supported$metal.$It$is$only$at$high$hydrogen$coverage,$leading$to$the$adsorption$of$several$
H2$molecules$on$the$metal$cluster,$that$it$becomes$thermodynamically$favourable$to$have$a$hydrogen$transfer$from$the$metal$to$the$O$sites$of$the$oxide$surface.$The$migration$of$an$H$atom$from$the$Ru$cluster$to$the$a@TiO2$(101)$surface$is$
accompanied$by$an$electron$transfer$to$the$empty$states$of$the$support$with$reduction$of$the$oxide$surface$$the$formation$
3+
1$
of$Ti $center$is$therefore$observed. The$study$of$H$spillover$mechanism$of$Pt$clusters$on$graphene$surface$is$still$ongoing$$

Hydrogen)spillover)
The$classical$hydrogen$spillover$process$is$composed$of$(1)$dissociative$chemisorption$of$H2$on$the$metal$particleX$(2)$migration$of$H$atom$from$the$metal$to$the$supportX$(3)$diffusion$of$H$atoms$on$the$substrate$surface.$The$spillover$behavior$ will$ be$ influenced$ by$ the$ metal@support$interactions.$Hydrogen$spillover$has$been$proposed$to$be$
a$ possible$ mechanism$ to$ reach$ high@density$ hydrogen$storage$in$light$weight$material$like$graphene$at$RT.$$$

Methodology)Density$ functional$ theory$ calculations are$ applied$ to$investigate$ the$ thermodynamic$ and$ kinetic$ properties$ of$hydrogen$ interacting$ with$ metal/TiO2/graphene$ surfaces.$
This$ study$ will$ involve$ the$ analysis$ of$ geometric$ and$energetic$ properties$ and$ Bader$ charge.$ Nudge$ Elastic$
Band$method$is$employed$to$locate$transition$states.$

Results)and)Discussion)
We$ have$ considered$ the$ energetic$ of$ adsorption,$
dissociation,$diffusion$and$spillover$of$hydrogen$on$models$of$ Ru$ nanoparticles$ supported$ on$ titania$ surfaces.$ The$
metal$ nanoparticle$ plays$ a$ significant$ role$ to$ split$ H2$
spontaneously.$When$the$metal$particle$is$saturated$with$
H$atoms,$the$H$will$migrate$from$the$metal$to$the$support$
surface.$The$next$stage$of$this$study$is$to$understand$if$the$same$ hydrogen$ spillover$ mechanism$ will$ be$ found$ in$
metal/graphene$system?$$

References)[1]$ H.@Y.$T.$ChenX$S.$TosoniX$G.$Pacchioni,$Hydrogen$adsorption,$dissociation,$and$spillover$on$Ru10$
clusters$supported$on$anatase$TiO2$and$tetragonal$
ZrO2$(101)$surfaces,$ACS$Catalysis$2015,$5,$5486@
5495.$

Acknowledgement)
Thanks$the$joint$project$of$AOI@NTHU$collaboration$
105F8019K3$for$financial$support.$$
Hsin@Yi$Tiffany$Chen$received$her$BEng$(Honors)$in$Resource$Engineering$from$National$Cheng$Kung$
University$and$$MSc$$in$Materials$Science$and$Engineering$from$National$Taiwan$University$in$Taiwan,$
before$obtaining$her$PhD$in$Chemistry$from$University$College$London$in$the$UK$in$2012$under$the$supervision$of$Prof.$C.$Richard$A.$Catlow$FRS.$She$had$worked$with$Prof.$Gianfranco$Pacchioni$as$a$
Postdoctoral$ Associate$ Researcher$ in$ Materials$ Science$ at$ University$ of$ Milano@Bicocca$ in$ Italy$ till$
2016.$She$is$currently$an$assistant$professor$in$Engineering$System$and$Science$at$National$Tsing$
Hua$University$in$Taiwan.$Her$research$interests$include$quantum$mechanical$simulations$applied$on$)
homo@$ and$ hetero@geneous$ catalysis,$ oxides$ surfaces,$ interfaces,$ 2D$ materials$ (thin$ films),$ metal$
Hsin@Yi$ Tiffany$ clusters,$carbon$based$materials$by$analyzing$their$electronic$structures,$acid$and$basic$properties,$Chen$simulated$STM$images,$transition$states$and$reaction$mechanisms.$
Corresponding$$$author:$Hsin@Yi$Tiffany$Chen,$hsinyi.chen@mx.nthu.edu.tw,$+886(0)3@5715131@34248$

$$

$

55

A MULTI-LABORATORY COMPARISON STUDY OF VOLUMETRICCAPACITY MEASUREMENTS ON HYDROGEN-SORPTION MATERIALS
K.E. Hurst, T. Gennett, and P.A. Parilla
National Renewable Energy Laboratory
Hydrogen storage sorbent materials have shown continuous improvement in the past decade and many DOE targets
have been met in isolation, however, further advancements in materials development are needed to meet all of theperformance targets simultaneously. This is especially true for achieving storage at higher volumetric densities andrecent emphasis has been placed on increasing this density and accurately determining the volumetric capacity ofcandidate materials. This talk will summarize the recent findings from a comparison of hydrogen capacity measurements
on identical materials among different laboratories to assess the reproducibility of such measurements.

Introduction
Accurate measurements and precise metrics are
essential for determining the true potential of newmaterials for vehicular hydrogen storage applications.
Previously, a round-robin report by Zlotea et.al, 1 haddiscovered large discrepancies among the different
participating laboratories for hydrogen gravimetriccapacity measurements on a standard sorbent material.
This study brought attention to the challenges ofhydrogen adsorption measurements and provided
recommendations, and possible sources of errors. In alater study, we demonstrated an improved reproducibility
amongst a smaller number of laboratories for the excess
gravimetric capacity of standard sorption samples. 2
These studies both emphasized hydrogen gravimetric
excess capacity of standard sorbent samples.
With the recent advances in developing prototype
systems, it has become clear that volumetric hydrogencapacities are especially important for materials
comparison. We have proposed several figures of meritthat are recommended to be used for describing sorption
capacities of materials.3 By using well-defined definitions
and methodologies for figure of merit calculations, ameaningful comparison for the capacities of standard
samples can be made.

Summary
In the present work, the hydrogen storage capacities of
two different sorbent samples are compared in order tocharacterize the measurement reproducibility amongst
the participating laboratories. These participating labs
include national laboratories, industry and academia.

Each laboratory was asked to measure and calculate
gravimetric excess, excess volumetric and total
capacities at ambient and liquid nitrogen temperatures.
The samples were sent to the laboratories with detailed
instructions for degas procedures and calculation
methodologies. We will present how common errors canoccur in calculating capacities and the level of uncertainty
associated with random error. The importance of
accurate skeletal density and packing density will be
discussed.
Common analysis protocols and figure of merits forreporting data allows the materials to be compared on an
equal basis, and provides insight into the uncertainty ofmeasurements amongst the hydrogen storage researchcommunity.
We are grateful for the participation of the collaborating
laboratories for providing data for this study. We
acknowledge research support from the U.S. Departmentof Energy, Office of Energy Efficiency and Renewable
Energy, Fuel Cell Technologies Office, under Contract
No. DE-AC36-08-GO28308.

References[1] C. Zlotea, P. Moretto, and T. Steriotis, International
Journal of Hydrogen Energy 34, 3044 (2009).
[2] K.E. Hurst, P.A. Parilla, K.J. O’Neill, and T. Gennett.
App. Phys. A 2016, 122, 42.
[3] P. Parilla, K. Gross, K. Hurst, T. Gennett, Applied
Physics A. 2016, 122, 201.

Katherine Hurst is a senior scientist in the Chemical and Nanoscience Center at the National Renewable
Energy Laboratory. Her work focuses on understanding gas-solid interactions.
This includes
characterization of gas adsorption properties and chemical vapor deposition including atomic layer
deposition synthesis of new materials for applications in energy storage and catalysis.
Corresponding author: Katherine Hurst; Katherine.hurst@nrel.gov, 303-384-7673

56

Advanced Hydride Research for
All-Solid-State Energy Storage Devices
Hiroyuki OGUCHI1, Koji YOSHIDA2, Toyoto SATO2, Shigeyuki TAKAGI2, Shin-ichi ORIMO1,2
1 WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
2 Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Complex hydrides exhibit various energy-related functions as shown below; such as high-density hydrogen storage andmicrowave absorption for future fuel cell technologies [1], as well as fast-ionic conduction for energy devices [2-5]. In thepresentation, recent studies on lithium/sodium superionic conduction and development of all-solid-state lithium-ion battery
devices (both the high-energy-density and high-thermal-durability types) using complex hydrides are to be explained [6].

Positive ElectrodeC

Complex
HydrideC

Negative Electrode[1] S. Orimo, C.M. Jensen, A. Züttel et al., Chem. Rev.
107, 4111 (2007). (HCP, Times Cited: >1000)[4] T.J. Udovic, S. Orimo et al., Chem. Comm. 50, 3750
(2014); Adv. Mater. 26, 7622 (2014).

[2] M. Matsuo and S. Orimo, Adv. Energy Mater. (Review
Article) 1, 161 (2011).

[5] W.S. Tang, T.J. Udovic, S. Orimo et al., Energy
Environ. Sci. 8, 3637 (2015).

[3] A. Unemoto et al., Adv. Functional Mater. (Feature
Article) 103, 133903 (2014).

[6] R. Mohtadi and S. Orimo, Nature Reviews Materials, inpress.

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 (19952002), and a guest researcher of Max-Planck Institute for Metal Research awarded by Alexandervon Humboldt Fellowship and MEXT Fellowship (1998-1999); and is a professor of WPI-AIMR / IMR,
and the Head of Integrated Materials Research Center for a Low-Carbon Society, Tohoku University.
His research interests are fundamentals and energy-related applications of hydrides. He wasawarded “The Prize for Science and Technology (Research Category), The Commendation for
Science and Technology 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.

57

Pressure-induced phase transitions in LiBH4 and synergistic effect ofLi–Ti and K–Ti co-doping on NaAlH4: first-principles study
Xin Ju*，Shina Li, Suye Yu
Department of Physics, University of Science and Technology Beijing, Beijing, China, 100083, P. R. China
Abstract
Using pseudopotential density functional theoretical (DFT) methods, we have studied the effects of high pressure on
the phase transitions and hydrogen evolution of LiBH4. The high pressure reduces the volume requirement of hydrogenstorage. We also studied dimetal doping on the hydrogen evolution of NaAlH4. The synergistic effect of Li–Ti and K–Ti
dopants on the energy, structure and electronic properties of NaAlH4 has been investigated using DFT and ab initio
molecular dynamics (AIMD). That a Li2Ti dopant, with lighter weight than K2Ti, can be applied as a favorable catalyst for
NaAlH4 has been given for the first time.

Introduction
As a member of complex light metal hydrides, lithium
borohydride (LiBH4) has been given widespreadattention. Using pseudopotential density functional
theoretical (DFT) methods, we systematically study thephase stability, elastic properties, structural properties
and high-pressure behaviors of LiBH4 [1, 2]. Comparedwith single-doped NaAlH4, multi-doped NaAlH4 exhibits
more significant effect on the kinetic and thermodynamic
properties of NaAlH4. K, Ti and F exhibit strong
synergistic effect on the dehydrogenation of NaAlH4
experimentally [3]. However, the destabilizing mechanism
remains ambiguous. Here we reported the mechanism of
Li-Ti and K-Ti synergistic effect on NaAlH4 [4].

DFT calculations
Our calculations were performed within the firstprinciples density functional theory (DFT) as implemented
in the Vienna ab-initio simulation package (VASP). We
performed AIMD simulations using the constant particle
number, volume and temperature (NVT) ensemble at thetemperature of 300 K in the cases of co-doped system.

Results and Discussion
The calculated Pnma structure is more stable than theother proposed structures at 0 K and 0 GPa. With thepressure extracted directly, Fig.1 presents that the Pnma
to Pnma* and the Pnma* to P-421c structural phasetransitions occur at 2.0 and 11.6 GPa respectively. For
Li–Ti and K–Ti co-doping on NaAlH4, pair distributionfunctional analyses show that Li2Ti and K2Ti favor not
only the release of H2 but also the reductions in thebarrier energies of (AlH4) units.

Fig. 1 Calculated structural parameters of the Pnma
structure versus pressure are shown in (a). Pressure
evolutions of volumes of the Pnma, Pnma*, and P-421c
structural LiBH4 at 0 K are shown in (b). The twotransition pressures are specified by vertical dot lines.

References[1] S.N. Li, et al. Computational Materials Science, 81:
378-385 (2014)[2] S.N. Li, et al. Int. J. Hydrogen Energy, 39: 9330-9338(2014)[3] Y. F. Liu, et al. Chem. Commun, 47: 1740–1742(2011)[4] S.Y. Yu, et al. RSC Advances, 6: 89895-89900 (2016)

Prof. Xin Ju was born in Shaanxi province of China in 1962. Graduated from Applied Physics Dept.
at National University of Defense Technology in 1982. 1993 PhD of Nuclear Physics and Detecting
Technique from University of Science and Technology of China. 2001 become Professor in
University of Science and Technology of China. He mainly engaged in energy physics and materials,
including nuclear, optical and hydrogen-storage materials.

Xin Ju*Corresponding author: Xin Ju, jux@ustb.edu.cn, +86 10 62333921.

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11 Int. Symposium Hydrogen & Energy

Waikoloa , Hawaii 2017

POROUS NICKEL- AND COBALT-BASED OXIDES NANORODSCATALYTIC EFFECTS ON IMPROVING LiBH4 DEHYDROGENATIONPROPERTIES
Lei Zang, Yijing Wang*, Qiuyu Zhang, Lifang Jiao and Huatang Yuan
College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin
300071, China*
Abstract: Lithium borohydride (LiBH4) with a theoretical hydrogen storage capacity of 18.5 wt% has attracted intenseinterest as a high-density hydrogen storage material. However, high dehydrogenation temperatures and limited
reversibility restrict its practical applications. The porous nickel- and cobalt-based oxides nanorods (NiCo2O4, Co3O4 andNiO) were controlled synthesized by hydrothermal method and mixed with LiBH 4 by ball milling. The metal oxides
nanorods exhibit the enhanced catalytic effects on the dehydrogenation properties of LiBH 4. When the mass ratio of
LiBH4 and oxides is 1:1, the NiCo2O4 nanorods display the best catalytic performance owing to the synergistic effect ofnickel and cobalt elements. The initial hydrogen desorption temperature of LiBH 4-NiCo2O4 decreases to 80 °C, which islowered 220 °C than that of pure LiBH4. And 14.6 wt% H2 is released at 500 °C for LiBH4-NiCo2O4 composite, incomparison with only 7.8 wt% H2 for pure LiBH4. Simultaneously, the composites also exhibit superior hydrogen
desorption kinetics, with 10.8 wt% H2 liberated from LiBH4 at 350 °C within 1 h.

Introdution
Lithium borohydride (LiBH4) with a high theoretical-3hydrogen storage capacity (18.5 wt%, 121 kg m ), hasbeen widely accepted as a leading candidate for onboard
applications. However, the practical applications are
restricted due to its harsh thermodynamics, kinetics andreversibility. Numerous studies have proven that catalyst
doping is one of the most effective ways to improve thethermodynamic and kinetic properties of LiBH4. In recent
years, transition metal oxides have been proved to beeffective catalysts for various applications such as
electronic devices, catalysis and sensing. In this work,
porous nickel- and cobalt-based oxides nanorods(NiCo2O4, Co3O4 and NiO) were synthesized byhydrothermal method. These nanorods were introduced
into LiBH4 with different mass ratio (2:1, 1:1, 1:2) by ball
milling.

Results and conclusion
Experimental results show that the dehydrogenation
properties of LiBH4 are significantly improved after dopingwith the metal oxides nanorods. When the mass ratio of
LiBH4 and oxides is 1:1, the NiCo2O4 nanorods display
the optimal catalytic performance owing to the synergistic
effect of nickel and cobalt elements. The initial hydrogen
desorption temperature of LiBH4-NiCo2O4 decreases to

80 °C, which is lowered 220 °C than that of pure LiBH4.
There are four distinct dehydrogenation peaks at 106.1°C,
197.8 °C, 212.4 °C and 331.5 °C, respectively. And the
LiBH4-NiCo2O4 composites release total 14.6 wt% H2 at
500 °C, in comparison with only 7.8 wt% H2 for pure
LiBH4. Simultaneously, the LiBH4-NiCo2O4 composites
also exhibit superior hydrogen desorption kinetics, with
10.8 wt% H2 liberated from LiBH4 at 350 °C within 1 h.
Subsequently, corresponding catalytic mechanisms ofthe nickel-and cobalt-based oxides have been also
discussed.

Acknowledgment
We are grateful to the NSFC (51471089, 51501072,
51571124), MOE (IRT13R30), 111 Project (B12015) for
financial support of this work.

References[1] Züttel, A. Wenger, P. Rentsch, S. Sudan, P. Mauron,Ph. Emmenegger, Ch. Journal of Power Sources, 2003,
118: 1-7.
[2] Schlapbach L, Züttel A. Hydrogen-storage materials
for mobile applications. Nature 2001, 414: 353-358.
[3] Zhang, Y. Liu, Y. F. Zhang, X. Li, Y. Gao, M. X. Pan,
H. G. Dalton Trans., 2015, 44:14514-14522.

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 focus on：Synthesis and Characteristics of Hydrogen Storage
Materials and High-performance Electrode Materials.

Yijing Wang
Corresponding author: Name: Yijing Wang, E-mail: wangyj@nankai.edu.cn, Tel.: +86-22-23503639.

59

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11 $Int.$Symposium$Hydrogen$&$Energy$$$

Waikoloa$Village,$Hawaii,$USA$2017$!
!
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.!!

$

60

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11 $Int.$Symposium$Hydrogen$&$Energy$$$

Waikoloa$Village,$Hawaii,$USA$2017$

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! and!
Mathematics!at!the!Swiss!Federal!Institute!of!Technology!(ETH)!
in! Zürich! and! finished! with! a! DiplomaZthesis! on:!
"Magnetostriction! of! typeZII! superconductors".! From! 1969! –!
1973!he!was!PhD!student!in!the!Low!Temperature!Physics!Group!
of! Prof.dr! J.L.! Olsen! at! the! ETH.! PhDZthesis! on:! "Oscillatory!
Magnetostriction! and! the! stress! dependence! of! the! Fermi!
Surface!of!Al,!In,!Zn!and!Mg".!From!1974!–!1976!he!was!Research!
Associate!at!the!McLennan!Physical!Laboratory!of!the!University!
of!Toronto,!Canada!where!he!worked!on!the!electronic!structure!
! of! spinZdensityZwave! systems! and! quantum! oscillations.In! 1976!
he!was!visiting!scientist!at!the!ETH,!Zürich!and!from!1976!–!1980!
senior! lecturer! at! the! Vrije! Universiteit! in! Amsterdam.! Since!
1980! he! is! Full! Professor! in! charge! of! the! Department! of!
Condensed!Matter!Physics.!

!

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

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2008!
!

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.!From!
1988!till!2001,!Louis!Schlapbach!was!Full!Professor!for!Physics!at!
the!University!of!Fribourg.!As!such!he!built!up!a!research!team!of!
20Z25! people! working! on! the! topic! „New! Materials! and! their!
Surfaces“! resulting! in! about! 40! PhD,! 200! scientific! papers! and!
! some! patents.! A! strong! collaboration! with! industry! was!
Prof.!Dr.!Louis!Schlapbach! established.!In!spring!2001,!he!has!been!appointed!CEO!of!Empa,!
the! materials! science! and! technology! institution! of! the! ETH!
domain!with!750!coworkers!in!Dübendorf,!St.!Gallen!and!Thun.!

!

Louis!Schlapbach!started!his!scientific!work!in!1970,!38!years!ago,!with!the!investigation!of!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!and!Waldirich!on!a!paper!about!the!
hydrides! of! LaZNi! compounds.! LaNi5! was! subsequently! investigated! in! view! of! the! structure,!
surface!segregations,!hydrogen!occupation!of!interstitial!sites!and!as!electrode!material.LaNi5!
is!still!the!base!material!for!most!of!the!electrochemical!applications!of!metal!hydrides!today.!
The!work!on!LaNi5!was!complemented!by!the!research!on!FeTi.!Louis!Schlapbach!realized!the!
importance!of!the!surface!composition!for!the!hydrogen!sorption!process!and!he!was!able!to!
describe! the! role! of! the! surfaceZactive! species.! Furthermore,! he! investigated! the! changes! of!
the! surface! composition! of! LaNi5! and! FeTi! in! oxidizing! atmospheres! and! he! found! the!
formation! of! metallic! clusters! as! superparamagnetic! particles! acting! as! the! active! sites! in!
hydrogen! dissociation! and! recombination.! The! investigation! of! the! surface! of! metal! hydrides!
was! further! intensified! by! means! of! XZray! 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! the! elements! in! a! surface!
profile.!He!also!succeeded!to!analyze!the!electronic!structure!of!raere!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! of!
Technology,! Cleveland! in! 1965! and! his! Ph.D.! from! the! Western!
Reserve! University,! Cleveland! in! 1971.! He! worked! from! 1962Z
1969! as! a! research! metallurgist! in! the! NASA! Lewis! Research!
Center,! Cleveland,! Ohio.! From! 1971Z1983! he! was! Section!
Manager!of!Energy!Systems!at!Inco!Research!and!Development!
Center,!Suffern,!NY.!From!1983Z1991!he!was!Vice!President!and!
Director! of! Technology! at! Ergenics,! Inc.,! Ringwood,! NJ.! From!
1992Z1993!Gary!Sandrock!was!visiting!professor!at!the!Kogakuin!
University,! Hachioji,! Tokyo,! Japan! where! he! developed! a! new!
chemical! surface! treatment! and! investigated! the! activation!
characteristics!of!chemical!treated!AB5!alloys.!Gary!then!became!
the! president! of! SunaTech,! Inc.,! Ringwood,! NJ,! where! he!
developed! reversible! hydrogen! storage! systems.! At! the! same!
time! Gary! Operating! Agent,! International! Energy! Agency!
Hydrogen! Implementing! agreement! Tasks! 12! &! 17! (Hydrogen!
Storage! Materials)! and! worked! as! a! consultant! for! the! US! DOE!
via!Sandia!National!Laboratories,!Livermore,!CA.!!

!

In!1995!Gary!Sandrock!started!to!creat!and!mainten!Hydride!Databases!of!IEA(HIA)/DOE/SNL!
(http://hydpark.ca.sandia.gov)! and! he! is! author! of! several! book! chapters! and! review! papers!
e.g.!“A!panoramic!overview!of!hydrogen!storage!alloys!from!a!gas!reaction!point!of!view”.!His!
recent! research! concentrates! on! the! catalysis! of! the! hydrogen! desorption! from! alanates! and!
most! recently! Gary! investigated! the! hydrogen! 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!hydrogenZfueled!vehicles”!where!he!
shows! the! possible! ways! to! change! the! activation! barrier! for! the! hydrogen! desorption! in! a!
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!was!
affiliated!with!Nordita,!(Nordic!Institute!for!Theoretical!Physics)!
in! Copenhagen! before! he! became! a! member! of! the! scientific!
staff! of! Haldor! Topsøe! A/S,! Lyngby! in! 1981.! He! continued! the!
investigation! of! gas! molecules! at! the! surface! of! metals! and!
developed! a! picture! of! adsorption! and! desorption! of! hydrogen!
emerging! from! selfZconsistent! model! calculations.! In! 1992! he!
was! appointed! as! a! professor! of! theoretical! physics! in! the!
department! of! physics! at! the! Technical! University! of! Denmark,!
Lyngby! and! became! the! director! of! the! Center! for! AtomicZscale!
Materials! Physics! (CAMP),! Department! of! Physics,! Technical!
University!of!Denmark,!Lyngby.!!
!

!

Recent!research!of!the!group!of!Jens!Norskov!covers!several!of!the!most!relevant!topics:!1)!The!
development! of! theoretical! methods! e.g.! “Scaling! Properties! of! Adsorption! Energies! for!
HydrogenZContaining!Molecules!on!TransitionZMetal!Surfaces”;!2)!Theoretical!surface!science!
e.g.! “Role! of! strain! and! ligand! effects! in! the! modification! of! the! electronic! and! chemical!
properties! of! bimetallic! surfaces”;! 3)! Nanostructures! and! materials! properties! e.g.! AtomicZ
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! the! Dept.! of! Applied! Physics! at! Stanford! University,! U.S.A.!
From! 1982! to! 1988! he! was! Assistant! Professor!
(Hochschulassistent)! at! the! University! Göttingen! where! 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! from! 1996! to! 2009! he! was! director! of! the!
Prof.!Dr.!Rüdiger!Bormann!Institute! for! Materials! Research,! GKSS! Research! Centre,!
Geesthacht!and!since!2009!he!is!!Professor!of!Applied!Materials!
Physics! and! President! of! the! 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!and!kinetics!of!the!
amorphous!phase!formation!by!mechanical!alloying.!This!was!the!basis!for!the!investigation!of!
Mg! and! MgZNi! 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! of! hydrogen! 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!for!hydrogen!storage.!Therefore,!we!aword!Prof.!Rüdiger!Bormann!with!the!
Science!of!Hydrogen!&!Energy!prize!2010.!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2010!
!

!

Ivor!Rex!Harris!was!born!August!31,!1939!in!United!Kingdom.!In!
1960! he! rewceived! his! B.Sc.! in! Physical! Metallurgy! from! the!
University! of! Birmingham),! 1964! his! Ph.D! and! became! a! ICI!
Research!Fellow.!From!1966!he!was!lecturer!in!the!Department!
of! Physical! Metallurgy! and1988he! became! a! full! Professor! of!
Materials! 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! of!
Metallurgy!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!longZstanding!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!to!the!manufacture!of!NdFeB!magnets.!
The!HD!process!resulted!in!up!to!a!25%!saving!in!production!cost!and!is!now!used!worldZwide!
in! the! fabrication! of! NdFeB! sintered! magnets.! These! materials! are! playing! a! vital! role! in! the!
production! of! energy! efficient! electric! drives,! actuators! and! generators.! The! latest!
development!within!the!group!is!the!use!of!the!HD!process!in!the!recycling!of!2/17!and!NdFeB!
magnets.! His! research! also! made! a! very! significant! contribution! to! the! development! and!
understanding! of! the! Hydrogenation,! Disproportionation,! Desorption! and! Recombination!
(HDDR)! process! which! enabled! coercive! powder! and! hence! bonded! magnets! to! be! formed!
from!bulk!NdFeB!alloys.!He!has!published!over!500!scientific!papers!and!edited!and!coZedited!a!
number!of!books.!During!these!years!he!has!successfully!supervised!around!120!postgraduate!
students,! many! of! whom! are! still! working! in! applied! materials! science! and! occupy! senior!
positions!in!industry,!government!and!academia!throughout!the!world.!Since!stepping!down!as!
group! leader! and! head! of! school! he! has! focused! his! activities! on! the! application! of! NdFeB!
magnets!and!hydrogen!storage!materials!to!practical!demonstrators!such!as!the!Ross!Barlow!
hybrid!canal!boat.!This!zeroZ!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!of!climate!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!
1966Z1971! and! received! the! diploma! for! the! work!
“Electrochemical! studies! of! oxygen! solid! solutions! in! high!
melting!
metals”!
at!
the!
MaxZPlanckZInstitut!
für!
Metallforschung/University! of! Stuttgart.! He! received! his! Ph.D.!
for!the!thesis!entitled!“ThermoZ!and!electrotransport!of!oxygen!
and! nitrogen! in! Va! metals! “! from! the! University! of! Stuttgart,!
MaxZPlanckZInstitut! für! Metallforschung! in! 1973.! In! 1988! he!
received! the! Habilitation! “Measurements! and! modelling! of!
! hydrogen! solubility! and! diffusivity! in! disordered! metal! lattices“!
Prof.!Dr.!Rainer!Kirchheim! from! the! University! of! Stuttgart,! Faculty! of! Chemistry!
Metallurgy.!!
Since!1993!he!is!Full!Professor!(Gustav!Tamman!Chair)!University!
of! Göttingen! Göttingen! Germany! and! Director! GeorgZAugustZ
Universitaet! Goettingen,! Institut! für! Materialphysik! Göttingen!
Germany!.!
!
Prof.! Rainer! Kirchheim! has! investigated! 30! years! ago! oxygen! in! metals,! especially! diffusion,!
thermoZtransport! and! thermoZpower! of! oxygen! in! transition! metals! and! alloys.! In! 1980! he!
started!to!study!diffusion!of!hydrogen!in!dillute!alloys!of!copper!and!niobium!in!palladium.!He!
developed! an! electrochemical! method! for! the! measurement! of! the! hydrogen! diffusion! in!
palladium! and! palladium! alloys! and! performed! fundamental! studies! on! the! diffusion!
mechanism! of! interstitial! species.! The! interaction! of! hydrogen! with! dislocations! in! palladium!
and! the! interpretation! with! a! model! based! on! the! FermiZDirac! 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!in!metals!as!
well!as!the!hydrogen!interaction!with!dislocations,!grain!bounderies!and!interfaces!we!award!
Prof.!Rainer!Kirchheim!with!the!Science!of!Hydrogen!&!Energy!prize!2010.!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2011!
!

!
Prof.!Dr.!Koji!Hashimoto!

!

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!
degree! in! sciences! from! the! Tohoku! University! and! in! the! same!
year! he! became! 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!
Chemistry!of!the!National!Research!Council!in!Canada.!!
From! 1987! to! 1999! he! was! a! Professor! ! in! the! Institute! for!
Materials! Research! (IMR)! of! the! Tohoku! University! and! from!
1999! to! 2006! he! was! Professor! at! the! Tohoku! Institute! of!
Technology.!

!

Prof.!emeritus!Koji!Hashimoto!has!published!over!520!papers!in!scientific!journals!in!addition!
to!review!articles!and!book!chapters.!He!has!worked!on!corrosionZresistant!alloys,!electrolysis,!
especially! he! pioneered! the! electrolysis! of! seawater.! He! tailored! the! catalysts! 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!of!carbon!dioxide!with!hydrogen,!carbon!
dioxide! recovery! at! an! energy! consuming! district,! and! transportation! of! carbon! dioxide.! The!
plant! uses! tailored! key! materials! with! high! performance! and! durability,! that! is,! cathodes! for!
hydrogen!production,!anodes!for!only!oxygen!evolution!without!chlorine!evolution!in!seawater!
electrolysis,! and! catalysts! for! rapid! and! selective! production! of! methane! by! the! reaction! of!
carbon!dioxide!with!hydrogen.!The!performance!of!the!plant!has!substantiated!that!global!CO2!
recycling!can!supply!abundant!energy!generated!from!solar!energy!on!deserts!in!the!form!of!
methane!and!can!really!prevent!global!warming!induced!by!carbon!dioxide!emissions.!In!2003,!
he!has!built!a!pilot!plant!of!global!CO2!recycling!at!Tohoku!Institute!of!Technology!which!is!the!
minimum!unit!of!industrial!scale!for!seawater!electrolysis!and!carbon!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.! Member! of! 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! of! Japan,! 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! and! technology,! 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!hydrogen!and!
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!
!

!
Prof.!
Dr.!
MOGENSON!

Mogens!Mogenson!is!research!professor!in!the!fuel!cells!and!solid!
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! of! Metallurgy,! DTU.! After! a!
postdoctoral!period!at!the!Department!of!Chemistry!A,!DTU,!and!a!
short! period! in! the! battery! 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!
practical! electrochemical! 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!
Mogens! 16!patents/patent!applications.!

!

Prof.! Mogens! Mogensen! from! the! Risø! National! Laboratory! for! sustainable! Energy! made! an!
enormous! 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! and!
especially! 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! the!
development!of!new!materials!for!better!performance!and!competitive!prices.!In!the!field!of!
advanced! materials! he! was! very! active! and! successful! in! the! development! of! catalytic! metal!
oxides!with!fluorite!and!perovskite!related!structures.!These!compounds!are!extremely!flexible!
with! respect! to! substitution! of! host! cations! and! nonZstoichiometry.! 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! agingZ! 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! is!
interesting! as! the! produced! syngas! (H2! +! CO)! can! react! to! form! methane,! which! is! a! more!
suitable!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! of!
electrolysers!and!fuel!cells!with!the!Science!of!Hydrogen!&!Energy!prize!2012.!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2013!
!

!
Mr.!Katsuhiko!HIROSE!

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.!

!

Katsuhiko! HIROSE! has! a! very! important! role! in! the! development! of! hydrogen! for! mobility! by!
building! the! bridge! between! industry! (Toyota)! and! academia! as! well! as! the! bridge! between!
Asia!and!Europe.!!
!
He! initiate! the! hydrogen's! economical! value! assessments.! Hydrogen! fuel! is! valuable! for! the!
economy! as! well! as! for! the! environment.! The! valueZchain! analysis! of! Fuel! Cell! vehicles! and!
Hydrogen!Energy!analysis!identifies!the!big!economical!value!of!the!use!of!hydrogen!as!a!fuel.!
This!analysis!has!reZignited!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!powerZtrains!for!Europe:!a!
factZbased!analysis,!which!stimulated!the!hydrogen!activities!world!wide!again.!
The! large! number! of! keyZnote! speeches! in! both! engineering! conference! and! academic!
conference! stand! for! his! continuous! efforts! as! an! interpreter! between! the! industries! and!
academic!scientists.!!
He!is!responsable!for!the!world!leading!research!in!hydrogen!storage!by!means!of!hybrid!tank!
systems,!i.e.!the!combination!of!pressurized!hydrogen!gas!and!metal!hydrides,!which!leads!to!a!
hydrogen! storage! with! greater! gravimetric! and! volumetric! hydrogen! density! as! compared! to!
the!individual!system.!Furthermore,!he!also!developed!a!CryoZadsortion!tank!system.!
!
We!award!Mr.!Katsuhiko!HIROSE!for!his!outstanding!work!on!the!implementation!of!hydrogen!
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!
!
!

!
Prof.!Dr.!Hans!GEERLINGS!

Hans!Geerlings!studied!experimental!physics!in!Amsterdam,!
where! he! received! his! PhD! degree! in! 1987.! In! that! year! he!
moved!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!as!a!part!time!professor!at!the!Delft!University!of!
Technology.!His!current!research!interests!are!in!the!area!of!
‘Solar!Fuel!synthesis’!and!‘Mineralization!of!CO2’.!
!

!

!

Hans!Geerlings!has!worked!on!complex!hydrides,!i.e.!alanates,!especially!on!the!synthesis!and!
the! characterization! of! MgAlH4! and! CaAlH4,! before! he! focused! on! the! CO2! capture! and!
mineralization.! Recently,! he! published! a! paper! in! Environmental! Science! entitled! “Efficient!
Production! of! Solar! Fuel! Using! Existing! Large! Scale! Production! Technologies”! in! which! the!
efficient!production!of!solar!fuels!today!using!existing!technologies!is!described.!The!feasibility!
of!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!alternative!
technologies! 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! and!
storage!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.!Qidong!WANG!

!

Qidong! WANG! is! a! professor! of! Department! of! Materials!
Science!and!Engineering,!Zhejiang!University.!He!was!born!in!
1921,! and! obtained! his! BSc! degree! in! 1943! from! Zhejiang!
University! of! China,! MSc! degree! in! 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! on! hydrogen! storage! materials! and!
their! actual! applications.! Besides! the! researching! tasks! and!
teaching,! he! has! also! done! many! administrative! and! social!
services.!

!
Prof.! Qidong! WANG! from! the! Department! of! Materials! Science! and! Engineering! of! Zhejiang!
University!was!involved!in!the!fields!of!mechanical!engineering,!metallurgical!engineering!and!
functional! 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! and!
applications! 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! metalZhydride!
systems.!His!research!interests!also!focus!on!the!purification!and!transportation!of!hydrogen!
as!well!as!NiZMH!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! lanthanumZrich!
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! to! prepare! mischmetal! cathode! materials! for! hydrogen! storage! batteries,!
which!hereafter!were!widely!accepted!by!peers.!He!has!contributed!with!his!coworkers!more!
than!500!scientific!papers!and!reports!and!he!has!18!patents!and!more!than!20!awards!on!his!
contributions! in! scientific! researches,! teaching! and! social! contributions.! So! far,! his! scientific!
papers! have! been! cited! more! than! 5000! times! and! his! HZindex! 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! and!
their!applications!with!the!Science!of!Hydrogen!&!Energy!prize!2014.!

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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!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!

!

!

Andreas!Züttel!has!worked!on!metal!hydride!electrodes!and!developed!new!overstoichiometric!
AB2! LavesZphase! alloys! wher! the! B! atoms! partially! occupy! AZsites.! He! developed! a!
mathematical! 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!means!of!electrochemical!sorption!measurements!and!described!the!relationship!between!
the!hydrogen!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!
research!on!!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!
the! hydrogen! 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!
close!the!materials!cycle!for!hydrocarbons!as!energy!carriers.!
!
We! award! Prof.! Andreas! Züttel! for! his! outstanding! work! in! the! science! on! the! interaction! of!
hydrogen!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!2015!
!
!

!
Prof.!Dr.!Bernard!DAM!

!

After!the!Thorbecke!Scholengemeenschap!Arnhem!Gymnasium!Beta!
(1969! –! 1975)! Bernard! Dam! studied! chemistry! at! the! Radboud!
Universiteit! Nijmegen! (1975! –! 1982)! where! he! graduated! (cum!
laude)! in! EPRZspectroscopy! and! solid! state! chemistry,! with! a! minor!
in!philosophy!of!science.!His!PhD!in!physical!chemistry!he!received!
from! the! Radboud! Universiteit! Nijmegen! (1982! –! 1986)! for! the!
thesis:! "Growth! and! morphology! of! classical! and! superspace!
crystals".!He!joined!Philips!Research!Laboratories!(NatLab)!where!he!
worked! on! the! growth! and! properties! of! metallic,! superconducting!
and!complex!oxide!thin!films!by!various!vapor!deposition!techniques!
(Sputter! Deposition,! Pulsed! Laser! Deposition! and! Molecular! Beam!
epitaxy)! from! April! 1986! –! May! 1992.! He! became! Associate!
Professor!at!the!vrije!universiteit!amsterdam,!with!the!main!areas!of!
research:! HTcZsuperconductivity,! switchable! mirrors,! hydrogen!
storage,! hydrogen! sensing.! He! is! coZfounder! of! the! Bachelor!
program!'Science,!Business!and!Innovation'!researcher!(May!1992!–!
January! 2009).! Since! January! 2009! he! is! full! professor! in! chemistry!
at! Delft! University! of! Technology,! Department! of! Chemical!
Engineering,! Head! of! the! section! 'Materials! for! Energy! Conversion!
and! Storage',! Scientific! director! Sustainable! Energy! TechnologiesZ
3TU,!Chair!of!the!exam!committee!of!the!applied!science!faculty!

!

Bernard!Dam's!goal!is!to!develop!new!materials!for!sustainable!energy!applications.!He!want's!
to! contribute! to! scientific! breakthroughs! and! see! his! research! transformed! into! commercial!
products.! His! field! is! functional! thin! film! materials! science:! find! relations! between! growth,!
(defect)! structure! and! physical! properties! in! relation! to! their! application.! At! present! he! aims!
for! applications! based! on! metal! hydrides,! such! as! hydrogen! sensors,! hydrogen! storage,!
hydrogen!membranes!and!chemochromic!windows.!In!addition,!he!investigate!the!mechanism!
of! photoZelectrochemical! water! splitting.! The! direct! conversion! of! sunlight! into! fuel! has! the!
advantage!that,!as!compared!to!electricity,!such!fuels!can!be!more!easily!stored.!!
!
We!award!Prof.!Bernard!Dam!for!his!outstanding!work!in!the!science!of!hydrogen!in!thin!films!
witch! lead! to! the! "hydrogenography"! as! a! new! experimental! method! for! the! investigation! of!
the!hydrogen!diffusion!in!solids!as!well!as!the!screening!of!hydries!and!the!development!of!a!
new!type!of!hydrogen!detector!with!the!Science!of!Hydrogen!&!Energy!prize!2015.!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2015!
!
!

!
Prof.!Dr.!Shin]Ichi!ORIMO!

1993Z1995! JSPS! (Japanese! Society! for! the! Promotion! of!
Sciences)!Research!Fellow.!1995!Ph.!D.,!Fac.!Integrated!Arts!
and! Sci.,! Hiroshima! University,! 1995! Z! 2002! Research!
Associate,! Hiroshima! University.! 1998! Z! 1999! Guest!
Researcher,! MaxZPlanck! Institute! for! Metal! Research,! as!
Alexander!von!Humboldt!Foundation!and!Japanese!Ministry!
of!Education!Fellows.!2002!Associate!Professor,!Institute!for!
Materials! Research! (IMR),! Tohoku! University.! 2009!
Professor,! Institute! for! Materials! Research! (IMR),! Head! of!
Hydrogen!Functional!Materials!Division,!Tohoku!University!
!

!

!

ShinZIchi! Orimo's! early! work! was! on! composite! hydrides! based! on! Mg! where! he! synthesised!
new! materials! by! mechanical! alloying! and! characterized! their! hydrogen! sorption! properties.!
His!fundamental!achievements!on!Mg!based!composits!and!nanomaterials!e.g.!grain!boundary!
diffusion,!amorphisation!and!kinetics!of!the!hydrogen!sorption!process!is!of!great!importants!
for!Mg!based!hydrogen!storage!materials.!From!the!year!2000!on!he!investigated!the!hydrigen!
interaction! with! nanostructured! graphite! and! crabon! materials! and! combined! carbon! with!
metal!nanoparticles.!In!2003!the!paper!entitled!"Material!properties!of!MBH4!(M!=!Li,!Na,!and!
K)"! which! presented! the! beginning! of! the! worldwide! intense! research! on! complex!
borohydrides.! Many! essential! contributions! for! the! understanding! of! the! structure,! the!
reaction!mechanism!and!the!hydrogen!sorption!kinetics!came!from!Orimo's!group.!Especially!
to! mention! the! relationship! of! the! hydrogen! desorption! temperature! and! the! cation!
electronegativity.! Very! early! Orimo's! group! also! worked! on! the! combination! of! complex!
hydrides!and!amides.!Recently,!the!high!temperature!phase!of!LiBH4!was!stabilized!by!a!partial!
substitution! of! the! [BH4]Z! with! the! iodinZions! leading! to! a! very! high! ionic! conductivity! at!
ambient!temperature.!!
!
We! award! Prof.! ShinZIchi! Orimo! for! his! outstanding! work! in! the! science! of! hydrides,! the!
discovery! of! new! hydride! systems! and! tunable! properties! of! hydrides! with! the! Science! of!
Hydrogen!&!Energy!prize!2015.!

!
!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2015!
!
!

!
Dr.Michael!HIRSCHER!

Michael!Hirscher!is!group!leader!“Hydrogen!storage”!at!the!
Max! Planck! Institute! for! Intelligent! Systems,! Stuttgart,!
Germany.! He! studied! physics! at! University! of! Stuttgart,!
Germany! and! Oregon! State! University,! Corvallis,! USA.! For!
his! achievements! during! his! PhD! he! was! awarded! the! Otto!
Hahn! Medal! of! the! Max! Planck! Society! in! 1988.! Prior! to!
taking! his! position! in! Stuttgart,! he! spent! a! postZdoctoral!
fellowship! at! the! University! of! Pennsylvania,! Philadelphia,!
USA.! Recently,! he! edited! the! “Handbook! of! Hydrogen!
Storage”! and! is! operating! agent! of! IEAZHIA! Task! 32!
“HydrogenZbased! energy! storage”! since! 2013.! His! current!
research! interests! focus! on! nanoporous! and! nanoscale!
materials!for!gas!storage!and!separation.!
!

!

!

Michael! Hirscher! investigated! the! hydrogen! adsorption! in! carbon! nanostructures! from! the!
beginning!of!there!discovery!and!especially!after!the!publication!of!Michael!Heben!(Heben,!M.!
J.;! Dillon,! A.! C.,! “RoomZtemperature! hydrogen! storage! in! nanotubes”! Science! 2000,! 287,!
(5453),! 593Z593.)! which! turned! out! to! be! a! missinterpretation! of! the! measurements.! M.!
Hirscher! carefully! investigated! the! surface! site! occupation! of! the! carbon! nanostructures! and!
the! interaction! energy.! His! present! studies! focus! on! novel! nanoporous! framework! materials,!
e.g.,! metalZorganic! frameworks! (MOFs),! with! high! specific! surface! area! and! microporosity,!
which!can!be!applied!for!cryoZadsorption!tanks.!
Furthermore,! these! crystalline,! nanoporous! framework! materials! are! investigated! for! their!
ability! to! separate! isotopes! of! light! gases,! e.g.,! hydrogenZdeuterium! mix tures,! by! quantum!
sieving.!
!
We! award! Dr.! Michael! Hirscher! for! his! outstanding! work! in! the! science! of! the! interaction! of!
hydrogen! with! porous! nanostructures,! the! investigation! and! description! of! the! quantity! of!
hydrogen!as!well!as!the!adsorption!energy!of!the!VanZderZWaals!interaction!of!hydrogen!with!
various!nanoporous!materials!with!the!Science!of!Hydrogen!&!Energy!prize!2015.!

!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2015!
!
!

!
Prof.!Dr.!Bjørn!HAUBACK!

!

Head! of! Physics! Department,! Institute! for! Energy!
Technology! (IFE),! 2011Z! Scientific! responsible! Energy!
Storage,! IFE,! 2009ZPrincipal! Scientist! New! Materials,! IFE,!
2007ZAdjunct!Professor!of!Physics,!University!of!Oslo!(UiO),!
2000ZDeputy! Head! of! Physics! Department,! IFE,! 2001Z
2011Principal! Research! Scientist,! Physics! Department,! IFE,!
1993Z2007.! Postdoctoral! Associate,! NTH,! 1988Z1991;! IFE,!
1991Z1993.Fellow,! NTH! and! Research! Council! of! Norway!
(RCN),! 1983Z1988.! Dr.! ing.! (PhD)! Norwegian! Institute! of!
Technology! (NTH),! Trondheim,! Norway! 1988.! Siv.! ing.!
(Master!degree)!NTH,!Trondheim,!Norway!1981.!

!

!

Bjørn! Hauback! has! made! enormous! contributions! to! the! structure! determination! of!
intermetallic! hydrides! and! complex! hydrides,! i.e.! deuterides.! Furthermore,! he! is! an! expert! in!
the!charge!and!magnetic!ordering!of!intercalated!compounds!as!well!as!oxydes.!Hs!group!was!
the!first!determining!the!structure!of!the!LiAlD4!and!NaAlD4!in!the!years!2002!and!2003!and!he!
investigated!the!hydrogen!desorption!reaction!of!alanates!and!borohydrides!in!great!detail!by!
synchrotron!and!neutron!diffraction.!!
Bjørn! Hauback! was! Operating! Agent! for! IEA! Hydrogen! Implementation! Agreement! Task! 22! Z!
"Fundamental!and!Applied!Hydrogen!Storage!Materials!Development"!from!2006.!Within!this!
task! an! enormous! progress! on! the! investigation! and! understanding! of! complex! hydrides! was!
achieved.!
!
We! award! Prof.! Bjørn! Hauback! for! his! outstanding! work! in! the! structur! determination! of!
hydrides!and!the!host!materials!as!well!as!the!complicated!structures!of!substituted!complex!
hydrides!and!composite!hydrides!with!the!Science!of!Hydrogen!&!Energy!prize!2015.!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2016!
!
!

Dr! Young! Whan! Cho! has! been! working! on! hydrogen! storage!
materials! since! 2002! and! is! the! author! of! more! than! 160!
scientific! publications! and! 20! patents.! Following! a! PhD! in!
Materials! Science! and! Metallurgy! at! Cambridge! University! in!
1990,!he!took!up!a!position!as!senior!researcher!with!the!Korea!
Institute!of!Science!and!Technology!where!he!is!now!a!principal!
researcher.! Dr! Cho! is! also! chair! professor! of! Nanomaterials!
Science!and!Engineering!of!University!of!Science!and!Technology.!
Since! 2007,! he! has! been! one! of! the! expert! members! of! IEAZHIA!
Task!22!and!32!and!member!of!ISO!TC197/WG25!for!the!revision!
!
of!ISO!16111.!Materials!design!and!production!of!new!composite!
!
Dr.!Young!Whan!CHO! materials! for! solid! electrolytes! and! active! anode! of! lithium! ion!
rechargeable!batteries!is!one!of!the!recent!research!topics!of!his!
group!in!KIST.!!
!

!

Young! Whan! CHO! 's! early! work! was! on! the! reactive! hydride! composites! based! on! both!
theoretical! and! experimental! works! where! he! applied! computational! thermodynamics! and!
mechanochemical! processing! techniques.! His! achievement! on! reactive! hydride! composites!
including!basic!mechanism!of!thermodynamic!destabilization,!mechanism!of!sorption!reaction!
kinetics!enhancement!through!microstructure!control,!understanding!the!role!of!the!catalytic!
additives,!is!of!great!importance!for!many!high!capacity!reactive!hydride!composite!systems.!
From!the!year!2006,!he!also!investigated!the!basic!sorption!properties!of!calcium!borohydride!
and! its! composites! with! other! metal! hydrides! and! borohydrides,! notably! Ca(BH4)2ZLiBH4!
system.! Many! contributions! for! the! understanding! of! the! crystal! structure! of! newly! found!
intermediates! and! mixedZionic! borohydrides! through! first! principle! calculations! came! from!
Cho’s!group.!His!group!has!been!working!on!the!nanoZconfinement!and!interface!effect!on!the!
desorption! kinetics! of! thermodynamically! stable! hydrides! since! 2011.! Their! work! on! this!
research!topic!has!recently!been!explored!into!another!area!where!Cho’s!group!is!now!trying!
to! design! and! synthesize! novel! interface! controlled! superionic! conductors! with! various!
complex!hydrides!for!electrochemical!energy!storage!applications.!!
We!award!Prof.!Young!Whan!CHO!for!his!outstanding!work!in!the!science!of!metal!hydrides,!
the! discovery! of! new! reactive! hydride! composite! systems! and! method! to! change! the! basic!
properties!of!complex!hydrides!with!the!Science!of!Hydrogen!&!Energy!prize!2016.!!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2016!
!
!

Dr.!Craig!Jensen!is!a!full!professor!of!Chemistry!at!the!University!of!
Hawaii! and! the! founder/president! of! Hawaii! Hydrogen! Carriers,!
LLC.! He! obtained! his! PhD! at! the! University! of! California! at! Los!
Angeles! in! 1984.! Following! a! postdoctoral! appointment! at! the!
University!of!California!at!San!Diego,!he!joined!the!faculty!at!UH!in!
1986.!Prof.!Jensen!has!directed!U.S.!Department!of!Energy!funded!
research! efforts! for! the! development! of! hydrogen! storage!
materials! since! 1988.! In! recognition! of! his! efforts,! he! was! named!
the! US! DOE! Hydrogen! program’s! “1999! Research! Success! Story”!
and!awarded!the!US!DOE!EERE!“R&D”!award!in!2004.!To!date,!he!
!
has! authored! or! coZauthored! 141! peerZreviewed! publications,! 9!
!
Prof.!Dr.!Craig!JENSEN!!! U.S.! patents,! and! one! book.! Additionally,! Prof.! Jensen! has!
presented! over! 160! invited! seminars! at! universities,! government!
labs,!private!companies,!and!conferences!in!24!different!countries.!!
Since!1997,!he!has!been!a!member!of!the!International!Energy!Association’s!hydrogen!storage!
expert’s! groups.! During! the! period! 1999Z2003,! he! was! commissioned! as! the! only! foreign!
“committeeman”! on! the! WEZNET! project,! a! working! group! of! top! Japanese! experts! charged!
with!the!development!of!advanced!hydrogen!storage!materials.!He!was!a!coZchairman!of!the!
2006! International! Symposium! on! MetalZHydrogen! Systems! and! the! 2007! HydrogenZMetal!
Systems!Gordon!Research!Conference.!In!2003,!Dr.!Jensen!founded!Hawaii!Hydrogen!Carriers,!
LLC!and!has!since!served!as!the!company!president.!!

!

Prof.!Jensen's!early!research!activities!focused!on!the!synthesis!and!characterization!of!novel!
organoZtransition! metal! complexes! and! their! utilization! as! homogeneous! catalysts.! These!
efforts!lead!to!the!development!of!the!first!“pincer”!complex!catalyzed!systems!for!the!highly!
efficient,!dehydrogenation!of!hydrogen!saturated!organic!and!main!group!compounds.!In!the!
late! 1990’s,! he! began! his! studies! of! the! reversible! dehydrogenation! of! complex! hydrides.! His!
efforts!in!this!area!were!initially!focused!on!the!obtaining!a!fundamental!understanding!of!the!
profound! enhancement! of! the! kinetics! of! the! reversible! dehydrogenation! sodium! aluminum!
hydrides! that! is! achieved! upon! mechanically! milling! the!hydride! with! titanium! halides.! These!
efforts! led! to! collaborations! that! resulted! in! the! development! of! novel! processes! for! the!
reversible! dehydrogenation! of! lithium! aluminum! hydride! (with! Prof.! Sean! McGrady)! and! the!
first!structural!characterizations!of!gamma!and!beta!alane!(with!Prof.!Bjorn!Hauback).!He!next!
extended!his!studies!of!complex!hydrides!to!boronZbased!materials.!In!2008,!he,!together!with!
Professors! Hans! Hagemann! and! Bjorn! Hauback,! reported! the! first! structural! elucidation! of! a!
mixed!metal!borohydride!complex.!This!was!followed!by!the!first!demonstration!(collaboration!
with! Ewa! Ronnebro)! of! the! reversible! hydrogenation! of! magnesium! boride! to! magnesium!
borohydride!in!2010.!Their!cycling!of!11.2!wt%!hydrogen!through!the!reversible!hydrogenation!
of! MgB2! to! Mg(BH4)2! stands! as! the! highest! hydrogen! storage! capacity! that! has! been!
experimentally! demonstrated! for! any! material! that! can! be! directly! hydrogenated.! However,!
cycling! of! Mg(BH4)2! to! MgB2! requires! extreme! reaction! conditions.! A! recent! collaboration!

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with! Dr.! Tom! Autrey! and! Prof.! ShinZichi! Orimo! has! shown! that! under! moderate! conditions,!
mixtures! of! magnesium! boranes! and! metal! hydrides! undergo! reversible! hydrogenation! to!
metal!borohydrides!and!cycle!up!to!4.5!wt!%!hydrogen.!Dr.!Jensen!has!also!ventured!beyond!
his!university!based,!fundamental!studies!of!hydrides!to!the!design!of!systems!for!the!practical!
utilization! of! metal! hydrides.! Since! 2006,! his! company,! Hawaii! Hydrogen! Carriers,! LLC! has!
focused!on!the!design,!fabrication,!and!integration!of!advanced,!metal!hydride!based!hydrogen!
storage!systems!for!utilization!in!light!duty!vehicles.!In!2011,!HHC!successfully!deployed!a!fuel!
cell!powered!light!cart!featuring!a!solidZstate!metal!hydride!hydrogen!storage!system!for!the!
US! Air! Force! that! still! remains! in! operation.! Most! recently,! as! part! of! a! US! DOE! sponsored!
project,!HHC!designed!and!fabricated!a!low!cost,!high!performance!version!of!their!hydrogen!
storage!system!for!forklift!applications.!!
!!
We!award!Prof.!Young!Whan!CHO!for!his!outstanding!work!in!the!science!of!metal!hydrides,!
the! discovery! of! new! reactive! hydride! composite! systems! and! method! to! change! the! basic!
properties!of!complex!hydrides!with!the!Science!of!Hydrogen!&!Energy!prize!2016.!!

!
!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2016!
!
!

!

Prof.!Dr.!Torben!R.!
JENSEN!!!

!

Torben! received! his! PhD! degree! (1999)! in! materials! chemistry! at!
University! of! Southern! Denmark,! Odense,! and! did! postdoctoral!
research!at!Risø!National!Laboratory!and!DESY,!Hasylab,!Hamburg.!
He!became!an!Assistant!Professor!(2000)!and!a!Research!Associate!
Professor! (2002)! at! the! Interdisciplinary! Nanoscience! Center!
(iNANO)!and!Department!of!Chemistry,!Aarhus!University.!He!was!
awarded! a! 6WHQR+ research! stipend! (2002)! by! the! Danish!
Research!Council,!a!&DUOVEHUJ+research!stipend!(2005)!from!the!
Carlsberg! Foundation! and! a! Doctor! of! Science! degree! (D.Sc.! in!
2014)! from! the! Faculty! of! Science! and! Technology! at! Aarhus!
University.! His! research! interests! are! focused! on! synthesis,!
structural,! physical! and! chemical! properties! of! new! inorganic!
materials! and! utilisation! of! synchrotron! XZray! radiation! for!
materials! characterization.! He! has! published! more! than! 200!
research!papers.!!!

!

Torben! R.! JENSEN! initiated! his! research! career! within! inorganic! materials! science,! and! then!
moved!to!biophysics!and!back!to!materials!science.!In!the!past!decade,!Torben’s!research!focus!
has! been! on! synthesis! and! characterisation! of! new! ‘energy! materials’! for! hydrogen! storage,!
batteries! and! now! also! conversion! of! carbon! dioxide! to! useful! fuels.! Development! of! new!
synthesis!methods!has!been!the!focus!during!all!the!years!along!with!utilisation!of!intense!XZ
ray!beams!generated!by!synchrotrons!for!advanced!materials!characterisation.!Jensen!and!his!
group!have!developed!knowhow,!new!sample!environments!and!gasZcontrol!for!inZsitu!powder!
diffraction! investigations! of! solidZgas! reactions.! This! is! now! implemented! at! several!
synchrotron!facilities!and!has!led!to!a!variety!of!collaborations!worldZwide.!A!multitude!of!new!
advanced! synthesis! techniques! have! also! been! developed,! e.g.! new! approaches! for!
mechanochemistry,! in! particular! investigation! of! the! reaction! mechanisms.! SolventZbased!
methods!have!been!used!for!preparation!of!new!precursors!and!several!synthesis!techniques!
have!been!combined!to!develop!novel!materials.!!
The! first! nanoZporous! metal! hydrides,! t! M(BH4)2,! M! =! Mg! or! Mn,! with! a! 3D! network! of!
interpenetrated! ~9! Å! channels,! which! reversibly! adsorb! smaller! molecules! like! of! H2,! N2,! or!
CO2!were!prepared!by!solventZbased!methods!by!Jensen!and!his!group.!A!wide!range!of!other!
metal! borohydrides! were! also! synthesised! and! investigated! and! anion! substitution! in! metal!
borohydrides! was! discovered! at! Aarhus! University! and! first! presented! in! 2006.! Another! new!
compound,!LiCe(BH4)3Cl,!with!a!unique!structure!is!the!first!member!of!a!new!class!of!fast!ion!
conductors.! New! combined! synthesis! protocols! provide! extensive! series! of! high! hydrogen!
density! compounds,! such! as! Y(BH4)3! QNH3,! Q+ =! 1,! 2,! 4Z7,! of! general! interest,! also! within!
coordination! chemistry.! Detailed! structural! investigations! of! metal! borohydrides! and! their!
ammonia!and!anionZsubstituted!derivatives!reveal!that!dynamic!(entropy)!effects!may!lead!to!
either!a!contraction!or!an!expansion!of!the!solid!state.!Jensen!also!proposed!that!dynamic!or!
entropy!effects!are!responsible!for!fast!cationic!conductivity!and!ion!substitution!in!the!solid!

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state.!Reactive!hydride!composites!have!also!been!investigated!along!with!nanoconfinement.!
New! methods! to! infiltrate! several! hydrides! in! nanoporous! scaffolds,! which! may! also! be!
functionalised!by!catalytic!nanoparticles!are!developed.!!
The! research! has! developed! fundamental! scientific! insights! into! material! structureZproperty!
relationships!towards!rational!design!of!novel,!useful,!and!functional!‘energy!materials’.!During!
the! past! few! years! the! Jensen! research! group! has! been! among! the! most! productive! for!
synthesis! of! new! materials.! The! group! has! published! 130! peerZreviewed! publications! since!
2010!in!a!strong!international!research!network!with!>20!research!groups.!!
We! award! Prof.! Torben! R.! JENSEN! for! his! outstanding! work! in! the! science! of! hydrides,! the!
discovery! of! multitudes! of! new! compounds! and! studies! of! structureZproperty! relationships!
with!the!Science!of!Hydrogen!&!Energy!prize!2016.!!
!

!

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SCIENCE!OF!HYDROGEN!&!ENERGY!AWARD!2016!
!
!

!

Dr.!Min!Zhu!is!a!professor!in!South!China!University!of!Technology.!
His! main! research! interest! lies! in! the! field! of! advanced! energy!
storage!materials,!including!hydrogen!storage!materials,!electrode!
materials!for!NiZMH!and!lithium!ion!batteries.!!
!!

!

Prof.!Dr.!Min!ZHU!
!

Min! ZHU’s! work! is! mainly! focused! on! the! syntheses,! characterization! and! properties! of!
hydrogen! storage! materials! and! anode! materials! of! lithium! ion! battery.! His! fundamental!
researches!help!to!understand!the!hydriding/dehydriding!reaction!mechanisms!related!to!the!
multiZphase! structure,! nanostructure! and! multiZvalence! catalysts! in! different! MgZbased!
nanocomposite! systems.! He! has! developed! some! novel! synthesis! processes! to! obtain! MgZ
based! nanocomposite! with! nanocatalysts! inZsitu! formed! and! enhanced! greatly! the!
hydriding/dehydriding!kinetics!of!Mg!based!materials.!Recently,!Zhu’s!group!realized!reversible!
hydrogenation! reactions! with! greatly! reduced! enthalpy,! i.e.,! thermodynamic! tuning,! by!
forming! MgZbased! solid! solution! in! MgZIn,! MgZInZNi,! MgZInZY! systems.! All! these! are! his!
important! contributions! in! MgZ! based! materials! for! reversible! hydrogen! storage.! Meanwhile,!
Zhu’s! group! found! the! excellent! hydrolysis! performance! of! nanocomposites! in! MgZTMZRE!
systems,!which!explores!great!potential!for!controllable!hydrogen!generation.!He!also!made!a!
unique! contribution! in! developing! a! dielectric! barrier! discharge! plasma! assisted! milling!
technique!which!has!promoted!greatly!the!efficiency!of!mechanical!alloying!and!induced!extra!
activation!for!solid!reaction!in!milling!process.!This!method!has!great!advantage!in!preparing!
hydrogen! storage! and! lithium! storage! nanomaterials! with! multiZphase! and! multiZscale!
structure,! and! the! obtained! Mg,! SnZC,! SiZC! base! materials! composites! have! shown! excellent!
kinetic!and!cycling!performance.!!
We! award! Prof.! Min! ZHU! for! his! outstanding! works! in! the! science! of! MgZbased! hydrogen!
storage! alloys! as! well! as! his! effort! in! developing! materials! synthesis! methods! for! hydrogen!
storage!and!lithium!ion!battery!with!the!Science!of!Hydrogen!&!Energy!Prize!2016.!!
!

!
!

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BEST!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! her!
bachelor! degree! from! Universidad!
Autonoma! del! Estado! de! Mexico! and!
her! master! degree! (cum! laude)! from!
Universidad! Iberoamericana! in! Mexico!
City.! Currently! Alondra! Torres! is!
appointed! as! a! Ph.D.! student! at! Delft!
University! of! Technology! in! the!
Netherlands.!During!her!studies!Alondra!
Torres! has! been! involved! in! several!
projects! including;! heavy! metals!
removal!from!waste!water!with!organic!
material!and!the!formation!of!polymeric!
membranes! with! supercritical! CO2! for!
gas! separation.! Her! current! Ph.D.!
project! involves! the! study! of! the!
potential! of! clathrate! hydrates! for!
hydrogen!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! three!
main! 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!
an! effective! storage! medium,! the! application! of! H2,! for! instance! in! the! automotive! sector,! is!
currently! limited.! Clathrate! hydrates,! have! been! regarded! as! a! favorable! alternative! for! H2!
storage.! Their! profitability,! safety,! fast! and! high! reversibility! and! efficient! production! make!
them!more!suitable!for!this!application!than!other!H2!storage!materials.!

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BEST!POSTER!AWARD!2012!
!
!

Mr.!Andreas!BLIERSBACH!!
!
“How! to! Watch! Hydrogen! Diffuse! in! any!
Absorbing!Material”!
!
Department! of! Physics! and! Astronomy,!
Materials! Physics! Division,! Uppsala!
University,!Sweden.!
!
Born! 1986! in! Cologne,! Germany.! 2011!
Diploma! in! physics! at! the! Rheinische!
FriedrichZWilhelms!
University!
Bonn,!
Germany.! 2008! –! 2009! studies! and!
research,! as! exchange! student,! at! Uppsala!
University,! Sweden.! 2010! –! 2011! research!
on! hydrogen! diffusion! in! nano! sized!
materials! by! direct! imaging! at! Uppsala!
University,! Sweden.! Since! December! 2011!
PhD! student! at! EMPA,! Dübendorf,!
Switzerland! and! involved! in! smart! carbon!
based!hydrogen!storage!materials.!
!

!
!
“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!nanoZsized!materials!motivate!fascinating!applications!and!scientific!
questions.! Even! though! diffusion! is! one! of! the! most! studied! phenomena! the! complex!
combination! of! quantum! effects! and! dynamic! interplay! with! the! displacement! of! host! atoms!
[1,4]!is!still!only!partially!understood.!We!present!a!method!to!quantify!chemical!diffusion!of!
hydrogen!in!nanoZsized!materials.!The!changes!in!the!absorptance!of!a!vanadium!single!crystal!
thinZfilm,!induced!by!hydrogen,!are!observed!visually!and!in!realZtime!as!a!function!of!position.!
Concentration!profiles!and!their!evolution!in!time,!during!chemical!diffusion,!can!be!measured!
down!to!a!hydrogen!content!corresponding!to!just!a!few!effective!monolayers,!randomly!

distributed!within!VHx.!

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BEST!POSTER!AWARD!2013!
!
!

!

Mr.!Moreno!DE!RESPINIS!
!
“Optimization! of! Anneal! Procedure! in! Metal! Oxides:! Case!
Study! of! Nanostructured! Tungsten! Processed! via! LowZEnergy!
HeliumZIons”!
!
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! photoZ
oxidation!by!visibleZlight!driven!Co3O4!catalyst.!He!is!currently!
a!Ph.D.!student!at!Delft!University!of!Technology!where!he!is!
researching!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!their!
morphology,! crystal! phase! and! stoichiometry.! We! present! a! novel! physical! processing! route!
that! uses! highZflux! of! lowZenergy! heliumZ! ion! to! generate! porous! structures! on! tungsten!
targets.!Optimal!anneal!condition!to!form!WO3!photoanode!is!determined!via!inZsitu!XRD.!SEM!
images! show! mesoporous! crystalline! structure,! and! feature! sizes! depend! on! substrate!
temperature!and!can!be!tuned!between!30!nm!and!1!μm.!Our!research!shows!that!a!twoZstep!
anneal!procedure!is!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! thermal! oxidative! 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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BEST!POSTER!AWARD!2014!
!
!

Mr.!Yixiao!FU!!
!
"Study! on! the! hydrogen! exchange!
behavior! in! the! metal! hydrideZLiBH4!
composite"!
!
School! of! Materials! Science! and!
Engineering,! South! China! University!
of! Technology,! Key! Laboratory! of!
Advanced! Energy! Storage! Materials!
of!Guangdong!Province,!P.!R.!China!
!
Born! 1990! in! Jiangxi,! China.! 2011!
Bachelor! in! Metallic! Materials!
Science! and! Engineering! in!
Department! of! Materials,! South!
China! University! of! Technology!
(SCUT),! Guangzhou,! China.! He! is!
currently! a! M.S! candidate! at! SCUT.!
Focused! on! LiBH4ZMgH2! system! and!
Magnesium!coreZshell!structure.!
!

!
"Study!on!the!hydrogen!exchange!behavior!in!the!metal!hydride]LiBH4!composite"!
HydrogenZexchange! effect! discovered! in! hydride! composite! gives! an! angle! to! study! the! nonZ
reaction! interaction! between! components! and! to! study! detailed! desorption! mechanism.!
Although! obvious! phenomena! had! been! observed! to! prove! the! existence! of! this! effect,! the!
detail!mechanism!has!not!been!proposed.!Our!research!presents!a!desorption!model!relating!
to!H!exchange!and!proves!that!interface!between!two!hydrides!and!mobile!H!atoms!from!both!
hydrides! are! crucial! for! the! exchange! to! happen.! Desorption! gas! specie! in! LiBH4ZVD2! system!
drastically! changed! after! melting! of! LiBH4! and! only! then! showed! obvious! HZD! exchange!
phenomena,! in! LiBH4ZMgD2! system! inhibition! of! desorption! of! MgD2! by! 4MPa! H2! nearly!
annihilate!BZD!signal!in!FTIR!indicating!nearly!no!D!atoms!was!found!in!LiBH4.!
!

!

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BEST!POSTER!AWARD!2015!
!
!

!

Dr.!Shunsuke!KATO!!
!
"In! Situ! X]Ray! Photo]electron!
Spectroscopy! Studies! on!
Hydrogen!
Storage!
and!
Catalysis"!
!
2005! Master! of! Engineering!
from! Tokai! University,! Japan.!
2007! PhD! student! at! the!
Laboratory! for! Hydrogen! &!
Energy,! Empa,! Swiss! Federal!
Laboratories! for! Materials!
Science! and! Technology,! and!
at! the! Department! of! Physics,!
the! University! of! Fribourg,!
Switzerland.!2012!Dr.!rer.!nat.!
from! the! University! of!
Fribourg.! The! thesis:! Surface!
properties! of! hydrides! and!
reactions.! 2012! Postdoc! at!
Laboratory! of! RadioZ! and!
Environmental!Chemistry,!Paul!
Scherrer!
Institute,!
Switzerland.!
Since!
2014!
Postdoc! at! Empa,! Swiss!
Federal! Laboratories! for!
Materials!
Science!
and!
Technology.!!
!

!
"In!Situ!X]Ray!Photo]electron!Spectroscopy!Studies!on!Hydrogen!Storage!and!Catalysis"!
The!aim!is!to!develop!XZray!photoelectron!spectroscopy!for!in!situ!investigations!relevant!to!a!
wide! range! of! research! fields! such! as! heterogeneous! catalysis! and! energy! storage.! Near!
ambient! pressure! XZray! photoelectron! spectroscopy! has! become! an! emerging! tool! for!
determining! electronic! structure! and! depth! resolved! chemical! composition! for! interfacial!
reactions.!!
!

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BEST!H2FC!POSTER!AWARD!2015!
!
!

!

Mr.!Nikolai!BILISKOV!
!
"Synthesis! and! Characterisation! of! New!
Aminoboranes"!
!
Laboratory! of! Solid! State! and! Complex!
Compounds! Chemistry,! Ruđer! Bošković!
Institute,! Bijenička! c.! 54,! HRZ10000!
Zagreb,!Croatia!
!
Born! September! 17,! 1974! in! Pula,!
Croatia.1999!Masters!degree!of!inorganic!
chemistry! at! Faculty! of! Sciences,!
University! of! Zagreb;! thesis! at! Faculty! of!
Science! in! Zagreb.2009! PhD! degree! in!
physical! chemistry! at! Ruđer! Bošković!
Institute,!Zagreb!thesis!"”2012!Research!
associate!at!the!Laboratory!of!Solid!State!
and! Complex! Compounds! Chemistry,!
Division! of! Materials! Chemistry,! Ruđer!
Bošković! Institute,! Zagreb2014! Visiting!
scientist! at! EMPA,! Dept.! Hydrogen! and!
Energy,!Dübendorf,!Switzerland!!
!

!
"Synthesis!and!Characterisation!of!New!Aminoboranes"!
A! series! of! singleZ! and! bimetallic! amidoboranes! and! their! complexes! with! ammonia! borane!
were! prepared! by! ball! milling! from! ammonia! borane! and! corresponding! metal! hydrides.!
Products! are! characterised! by! means! of! IR! spectroscopy! and! powder! XRD.! Dehydrogenation!
was! followed! by! DSC! and! variable! temperature! Raman! spectroscopy.! All! of! the! prepared!
systems!dehydrogenate!at!considerably!lower!temperature!with!respect!to!ammonia!borane.!

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BEST!POSTER!AWARD!2016!
!

Ms.!Efi!HADJIXENOPHONTOS!!
!
"Hydrogen!sorption!Kinetics!in!Magnesium!
and!Titanium!Hydride!Thin!Films"!
!

Institute! of! Material! Physics,! University! of!
Stuttgart,!Heisenbergstrasse!3,!70569!Stuttgart,!
Germany!!
!
I! grew! up! in! Cyprus! and! after! high! school,! I!
moved!to!France!to!start!my!studies!in!physical!
chemistry! in! Montpellier.! After! French,! I! added!
English! to! my! science! skills! through! MESC,! an!
international! master's! offering! a! unique!
experience! to! explore! electrochemistry! and!
materials†! science,! while! working! at! various!
European!universities.!During!my!master's!I!was!
elected! class! president! for! my! teamwork! skills!
†and! ability! to! manage! and! coordinate! the!
multiZlingual/multiZcultural!group.!My!academic!
work! stood! out! enough! that! a! position! for! my!
master's! thesis! project! was! created! for! me! in!
Montreal,!Canada,!working!on!modified!carbons!
! and!ionic!liquids!for!electrochemical!capacitors.!!

After!my!thesis,!I!collaborated!with!CIRIMAT!in!Toulouse,!France,!giving!me!the!opportunity!to!
spend!10!additional!months!doing!research!on!nanocarbon!materials!and!ionic!liquids!for!solid!
state! electrochemical! capacitors.! Today,! I! am! combining! my! degrees,! lab! experience,! and!
languages!with!the!ECOSTORE!Marie!Curie!Initial!Training!Network,!as!I!work!towards!a!PhD!in!
Stuttgart,!Germany.!!

!
"Hydrogen!sorption!Kinetics!in!Magnesium!!and!Titanium!Hydride!Thin!Films."!
Magnesium!hydride!(MgH2)!has!been!extensively!studied!over!the!last!decades!because!of!its!
great!potential!for!hydrogen!storage.!Recent!studies!have!focused!on!improving!this!property!
by! mechanoZchemical! treatment,! addition! of! transition! metals! (TM)! and! reduction! of! the!
crystallite! size.! However,! hydrogen! diffusion! remains! a! challenging! fundamental! problem.! In!
this!work,!we!compared!the!HZsorption!behaviour!at!low!temperatures!for!MgH2!and!titanium!
hydride!(TiH2),!and!study!the!influence!of!TM!additives.!Pd!and!Ti!were!exploited!to!improve!
both! dissociation! of! H2! molecules! and! diffusion! of! H! atoms! in! the! material.! Thin! films! were!
deposited! in! order! to! quantitatively! determine! diffusion! coefficients! and! measure! kinetic!
barriers!at!the!interfaces.!A!focus!here!is!the!comparison!of!these!properties!between!TiH2!and!
!
MgH2.!!
$

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BEST!POSTER!AWARD!2016!
!

Ms.!Guanqiao!LI!
!
"Dehydriding! Properties! of! LiBH4!
Combined!with!Mg2FeH6"!
!"!
!

!

Institute! for! Materials! Research,!
Tohoku!University,!Sendai!980Z8577,!
Japan!
WPIZAdvanced!Institute!for!Materials!
Research,! Tohoku! University,! Sendai!
980Z8577,!Japan!
!
2006,! bachelor! of! science,! Peking!
University.!
2011Z2013,! master! course! in! the!
Graduate! School! of! Environmental!
Studies,!Tohoku!University.!
2013!until!now,!Ph.!D!student!in!the!
Graduate! School! of! Environmental!
Studies,!Tohoku!University.!Research!
on! complex! hydrides! for! hydrogen!
storage! materials! in! Prof.! ShinZichi!!
Orimo's!group.!!

!
"Synthesis!and!Characterisation!of!New!Aminoboranes"!
By! mechanically! milling! with! Mg2FeH6,! the! dehydriding! temperature! of! LiBH4! has! decreased!
drastically.! Also,! in! the! Thermogravimetry! analysis! —! Mass! spectroscopy! (TGZMS)!
measurements,! a! unique! oneZevent! dehydrogenation! proces! of! LiBH4! and! Mg2FeH6! has! been!
realized.! This! event! has! been! conﬁrmed! to! be! simultaneous! dehydrogenation! by! using!
Mg2FeD6! instead! of! Mg2FeH6! to! combine! with! LiBH4! by! which! the! hydrogen! related! species!
released!from!the!two!components!could!be!distinguished.!Also,!HZD!exchange!between!LiBH4!
and!Mg2FeDs!occurred!during!the!mechanically!milling!and!heating!process!has!been!found!by!
this!method.!The!HZD!exchange!indicates!active!interaction!between!LiBH4!and!Mg2FeD6!that!is!
crucial!to!the!dehydrogenation!property!of!the!composites.!

!

!

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!

!
!
!

!
!
!
!
!
!
!
!
!
!
!
!
!

!

PARTICIPANTS!
!

!

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Name!

Address!

email!

Mark!ALLENDORF!

Sandia!National!Laboratories!
7011!East!Avenue!
94551!Livermore!
United!States!

mdallen@sandia.gov!

Tom!AUTREY!

Pacific!Northwest!National!Laboratory!
POB!999!MS#K2Z57!
99352!Richland!
United!States!

tom.autrey@pnnl.gov!

Mark!BOWDEN!

Pacific!Northwest!National!Laboratory!
PO!Box!999!
Richland,!WA!99352!
United!States!

mark.bowden@pnnl.gov!

Robert!C.!BOWMAN!

Oak!Ridge!National!Laboratory!
117!Miami!Ave.!
Franklin!OH!45005!
United!States!

rcbjr1967@gmail.com!

Craig!BUCKLEY!

Curtin!University!
Faculty!of!Science!and!Engineering,!GPO!Box!U!1987!
6845!Perth!
Australia!

c.buckley@curtin.edu.au!

Dhanesh!CHANDRA!

University!of!Nevada,!Reno!
3025!Blackthorn!Drive,!1664!N.!Virginia!St.!MS!388!
89523!Reno!/!Nevada!
United!States!

dchandra@unr.edu!

Ping!CHEN!

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

pchen@dicp.ac.cn!

TsanZYao!CHEN!

National!Tsing!Hua!University!
No.!101,!Sec.!2,!KaungZFu!Rd.!
30013!Hsinchu!
Taiwan,!China!

chencaeser@gmail.com!

HsinZYi!CHEN!

!
101,!Section!2,!KuangZFu!Road!
30013!Hsinchu!
Taiwan,!China!

hsinyi.chen@mx.nthu.edu.tw!

$

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Young!Whan!CHO!

Principal!Research!Scientist!
5,!HwarangZro!14Zgil,!SeongbukZgu!
Seoul!02792,!Korea!

oze@kist.re.kr!

Marina!CHONG!

Pacific!Northwest!National!Laboratory!
POB!999!MS#K2Z57!
99352!Richland!
United!States!

marina.chong@pnnl.gov!

Bill!DAVID!

University!of!Oxford!
Inorganic!Chemistry!Laboratory,!South!Parks!Road!
Oxford!OX11!OQX!
United!Kingdom!

bill.david@chem.ox.ac.uk!

Mirjana!
DIMITRIEVSKA!

NREL/NIST!
15013!Denver!W!Pkwy!
Golden!CO!80401!
United!States!

mirjana.dimitrievska@nist.gov!

Martin!DORNHEIM!

HelmholtzZZentrum!Geesthacht!
MaxZPlanck!Strasse!1!
21502!Geesthacht!
Germany!

martin.dornheim@hzg.de!

Michael!FELDERHOFF!

MaxZPlanckZInstitut!für!Kohlenforschung!
KaiserZWilhelmZPlatz!1!
45470!Mülheim!
Germany!

!felderhoff@mpiZ
muelheim.mpg.de!

Mattia!GABOARDI!

STFC!
Rutherford!Appleton!Laboratory.!Harwell!Campus.!R3,!
ISIS!Facility!
OX110QX!/!Chilton,!Didcot!
United!Kingdom!

mattia.gaboardi@stfc.ac.uk!

Noris!GALLANDAT!

EPFL!Valais!/!Wallis!
!
Rue!de!l'Industrie!17,!CP!440!
1950!Sion!
Switzerland!

noris.gallandat@epfl.ch!

Tom!GENNETT!

NREL!
15313!Denver!West!Parkway!
80401!Denver!
United!States!

thomas.gennett@nrel.gov!

Jessica!HAMAD!

Hawaii!
P.O.!Box!702!
96783/Pepeekeo!
United!States!

!
jessica.hamad@cengage.com!

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Bjorn!C.!HAUBACK!

Institute!for!Energy!Technology!(IFE)!
P.O.!Box!40!
NOZ2027!Kjeller!
Norway!

bjorn.hauback@ife.no!

Michael!HIRSCHER!

Max!Planck!Institute!for!Intelligent!Systems!
Heisenbergstr.!3!
70569!Stuttgart!
Germany!

!hirscher@is.mpg.de!

Terry!HUMPHRIES!

WA!
Department!of!Physics!and!Astronomy!
6845!Perth!
Australia!

terry.humphries@curtin.edu.
au!

Katherine!HURST!

NREL!
15013!Denver!West!Parkway!
Golden,!CO!80401!
United!States!

katherine.hurst@nrel.gov!

Ankur!JAIN!

Hiroshima!University!
Institute!for!Advanced!Materials!Research,!Hiroshima!
Univeristy,!1Z3Z1!Kagamiyama!
739Z8530!Hiroshima!
Japan!

ankur@hiroshimaZu.ac.jp!

Craig!JENSEN!

University!of!Hawaii!
Department!of!Chemistry!
Honolulu,!HI!96822!
United!States!

jensen@hawaii.edu!

Torben!R!JENSEN!

iNANO,!Aarhus!University!
Langelandsgade!140!
DKZ8000!Aarhus!
Denmark!

trj@chem.au.dk!

Mathias!JØRGENSEN!

!
Silkeborgvej!154,!kl!
8000!Aarhus!
Denmark!

mathias.j@inano.au.dk!

Xin!JU!

Department!of!Physics,!University!of!Science!and!
Technology!Beijing!
No.!30!Xueyuan!Road,!Haidian!District,!Beijing!China!
100083!Beijing!
China!

jux@ustb.edu.cn!

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ShinYoung!KANG!

Lawrence!Livermore!National!Laboratory!
7000!East!Avenue,!bldg!319!rm!290!
94550!Livermore!
United!States!

kang10@llnl.gov!

Alexander!
KOLESNIKOV!

Oak!Ridge!National!Laboratory!
PO!Box!2008,!MS.!6473!
37831Z6473!/!Oak!Ridge!
United!States!

kolesnikovai@ornl.gov!

Sanjay!KUMAR!

Institute!for!Advanced!Materials!Research,!Hiroshima!
University!
1Z3Z1!Kagamiyama,!!
HigashiZHiroshima!739Z8530!
Japan!

sanjay.barc@gmail.com!

Guanqiaog!LI!

WPIZAdvanced!Institute!for!Materials!Research,!
Tohoku!University!
Katahira!2Z1Z1,!Aoba!ku!
9808577!Sendai!
Japan!

likk@imr.tohoku.ac.jp!

HaiZWen!LI!

Kyushu!University!
744!Motooka!NishiZku!
Fukuoka!819Z0395!
Japan!

!li.haiwen.305@m.kyushuZ
u.ac.jp!

Yinzhe!LIU!

University!of!Birmingham!
University!of!Birmingham!
Birmingham!
United!Kingdom!

y.liu.3@bham.ac.uk!

Daiju!MATSUMURA!

Japan!Atomic!Energy!Agency!
1Z1Z1!Koto,!Sayo!
Hyogo,!679Z5148!
Japan!

daiju@spring8.or.jp!

Motoaki!MATSUO!

Kwansei!Gakuin!University!
2Z1!Gakuen,!Sanda,!
Hyogo!669Z1337!
Japan!

matsuo35@kwansei.ac.jp!

Florian!MERTENS!

Technische!Universität!Bergakademie!Freiberg!
Leipziger!Str.!29!
DZ09599!Freiberg!
Germany!

florian.mertens@chemie.tuZ
freiberg.de!

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Tessui!NAKAGAWA!

University!of!the!Ryukyus!
1!Senbaru,!Nishihara!
903Z0213!Okinawa!
Japan!

tessui@sci.uZryukyu.ac.jp!

Bryson!NAKAMOTO!

University!of!Hawaii!at!Manoa!
2545!McCarthy!Mall,!department!of!Chemistry!
Honolulu,!HI!96822!
United!States!

bryson20@hawaii.edu!

Yumiko!NAKAMURA!

National!Institute!of!Advanced!Industrial!Science!and!
Technology!(AIST)!
AIST!CentralZ5,!1Z1Z1!Higashi!
305Z8565!Tsukuba!
Japan!

yumiko.nakamura@aist.go.jp!

Phuong!NGUYEN!

University!of!Hawaii!at!Manoa!
2545!McCarthy!Mall,!department!of!Chemistry!
Honolulu,!HI!96822!
United!States!

!nguyenph@hawaii.edu!

ShinZichi!ORIMO!

Tohoku!University!
Katahira!2Z1Z1,!Aoba!Ku!
9808577!/!Sendai!City!
Japan!

orimo@imr.tohoku.ac.jp!

Katie!RANDOLPH!

US!Department!of!Energy!
1000!Independence!Avenue!SW!
Washington!DC!20585!
United!States!

katie.randolph@ee.doe.gov!

Hope!SARTAIN!

University!of!Hawaii!at!Manoa!
2545!McCarthy!Mall,!department!of!Chemistry!
Honolulu,!HI!96822!
United!States!

sartainh@hawaii.edu!

Godwin!SEVERA!

University!of!Hawaii!
1680!East!West!Road,!POST!109!
Honolulu,!HI!96822!
United!States!

severa@hawaii.edu!

Sunil!SHRESTHA!

University!of!Hawaii!
31!Coelho!Way!
Honolulu,!HI!96822!
United!States!

sshres@gmail.com!

$

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Samson!SOUZA!

University!of!Hawaii!at!Manoa!
2545!McCarthy!Mall,!department!of!Chemistry!
96822!Honolulu!
United!States!

!sasouza@hawaii.edu!

Mariana!SPODARYK!

EPFL!Valais!/!Wallis!
Rue!de!l'industrie!17!
1950!Sion!
Switzerland!

mariana.spodaryk@epfl.ch!

Vitalie!STAVILA!

Sandia!National!Laboratories!
7011!East!Avenue!
Livermore,!CA!94550!
United!States!

vnstavi@sandia.gov!

Jacob!TARVER!

National!Renewable!Energy!Laboratory!
15013!Denver!W!Pkwy!
Golden,!CO!80401!
United!States!

jacob.tarver@nrel.gov!

Joseph!TEPROVICH!

Savannah!River!National!Laboratory!
301!Gateway!Dr.!
Aiken,!SC!29803!
United!States!

joseph.teprovich@alum.lehigh.edu!

Matthew!THORNTON!

NREL!
15013!Denver!West!PArkway!
80410/Golden!
United!States!

matthew.thornton@nrel.gov!

Constance!VISSER!
WITMAN!

EPFL!Valais/Wallis!
Chemin!des!pâquerettes,!37!
1950!Sion!
Switzerland!

constance.visserwitman@epf
l.ch!

Yijing!WANG!

Nankai!University!
94Weijin!Road!
300071!Tianjin!
China!

wangyj@nankai.edu.cn!

Jim!WEBB!

Griffith!University!
170!Kessels!Rd!
Nathan!QLD!4111!
Australia!

!j.webb@griffith.edu.au!

Heena!YANG!

EPFL!Valais!/!Wallis!
Rue!de!l'industrie!17!
1950!Sion!
Switzerland!

gmlsk29@konkuk.ac.kr!

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Kun!ZHAO!

EPFL!Valais/Wallis!
Rue!de!l'industrie!17!
1950!Sion!
Switzerland!

kun.zhao@epfl.ch!

Ragaiy!ZIDAN!

Savannah!River!National!Laboratory!
Savannah!River!National!Laboratory,!Building!999Z2W!
Aiken!SC!29803!
United!States!

ragaiy.Zidan@srnl.doe.gov!

Andreas!ZÜTTEL!

EPFL!Valais/Wallis!
Rue!de!l'industrie!17!
1950!Sion!
Switzerland!

andreas.zuettel@epfl.ch!

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Information!

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Map!of!Hawaii!

Map!of!South!Kohala!region!
!
!
!

$

Waikoloa$Village,$Hawaii,$USA$2017$

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EMERGENCY!TELEPHONE!NUMBERS!
!
!
!

!

!

!

country!code!
for!The!USA!
+1...!

POLICE!
!
!
!
!
!
FIRE!FIGHTERS!

911!

Craig!Jensen!
Organizer!!

1]808]956]2759!
jensen@hawaii.edu!

Hilton!Waikoloa!Village:!
!69]425!Waikoloa!Beach!Drive,!
Waikoloa,!Hawaii,!96738,!USA!
!
URL:!
! http://www.hiltonwaikoloavillag
e.com/!

1]808]886]1234!

!

!

!

!

!

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CLIMATE!
!
Average!climate!information!in!Hawaii!in!Feb!
!

!
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!
!

!

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SOCIAL!EVENTS!
!
Hilo!:!
!
Hilo!is!the!beating!heart!of!Hawai‘i!Island.!
Hidden!beneath!its!daily!drizzle!lies!deep!
soil!and!soul,!from!which!sprouts!a!
genuine!community!and!aloha!spirit.!!
!

!

!

Liliuokalani!Park!:!!
!
Scenic!Japanese!gardens!overlooking!the!
bay.!Named!for!Hawaii's!last!queen!(r!
1891–93),!the!30Zacre!county!park!
features!soaring!trees,!sprawling!lawns!
! and!quaint!footbridges!over!shallow!
ponds.!
!
!

!
!

!

!

!

Rainbow!falls!:!
!
'instant!gratification'!cascade.!Depending!
on!rainfall,!the!lovely!80ft!waterfall!can!be!
a!torrent!or!a!trickle.!You'll!see!rainbows!if!
the!sun!and!mist!cooperate.!Waianuenue!
('rainbow!seen!in!water')!is!the!Hawaiian!
name!for!these!falls.!
!
Volcanoes!national!park!:!
!
Hawaiʻi!Volcanoes!National!Park!is!a!
microZcontinent!of!thriving!rainforests,!
volcanoZinduced!deserts,!highZmountain!
meadows,!coastal!plains!and!plenty!of!
geological!marvels!in!between.!
!

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HISTORY!OF!HAWAII!
!
Little! is! known! about! Hawaii’s! first! settlers,! who! arrived! around! AD! 500.! Tahitians!
arrived!around!AD!1000!and!for!the!next!200!years!navigated!thousands!of!miles!back!
and!forth!across!the!ocean!in!doubleZhulled!canoes.!Ruled!by!chiefs,!ancient!Hawaiian!
society!was!actually!matriarchal,!and!its!religion!followed!strict!laws!known!as!kapu.!!
By! accident,! famed! British! explorer! Captain! James! Cook! ‘discovered’! the! islands! in!
1778.! The! first! white! Westerner! to! arrive,! Cook! was! mistaken! for! the! god! Lono! and!
treated!like!a!deity.!He!stayed!several!weeks!and!then!resumed!his!journey.!When!he!
returned! to! Hawaii! a! year! later,! his! lessZthanZgodlike! behavior! led! to! fighting! and! he!
was!killed.!!
Beginning! in! the! 1790s,! King! Kamehameha,! chief! of! the! Big! Island,! conquered! and!
united! all! the! Hawaiian! islands.! He! is! credited! with! bringing! peace! and! stability! to! a!
society!that!was!often!in!flux!due!to!wars!and!the!power!struggles!of!the!ruling!class.!
However,! after! his! death! in! 1819! his! son! inherited! the! throne! and,! in! a! stunning!
repudiation!of!their!religion,!deliberately!violated!the!kapu+and!destroyed!the!temples.!!
As!fate!would!have!it,!Christian!missionaries!arrived!not!long!after,!and!in!the!midst!of!
Hawaii’s! social! and! spiritual! chaos! they! found! it! relatively! easy! to! ‘save! souls.’! New!
England!whalers!also!arrived,!seeking!different!quarry,!and!by!the!1840s!Lahaina!and!
Honolulu!were!the!busiest!whaling!towns!in!the!Pacific.!Meanwhile,!foreigners!made!a!
grab!for!Hawaii’s!fertile!land,!turning!vast!tracts!into!sugarcane!plantations.!As!there!
weren’t!enough!Hawaiians!to!work!the!fields,!immigrants!were!brought!in!from!China,!
Japan,!Portugal!and!the!Philippines,!giving!rise!to!Hawaii’s!multiethnic!culture!but!also!
displacing!Native!Hawaiians,!most!of!whom!became!landless.!
In!1893!a!group!of!American!businessmen!overthrew!the!Hawaiian!monarchy.!The!US!
government! was! initially! reluctant! to! support! the! coup,! but! it! soon! rationalized! its!
colonialism! by! citing! the! islands’! strategic! importance! and! annexed! Hawaii! in! 1898.!
Hawaii!played!an!infamous!role!in!US!history!when!a!surprise!attack!on!Pearl!Harbor!
vaulted!America!into!WWII.!Hawaii!became!the!50th!US!state!in!1959.!
In!February!2009,!Hawaii!Senator!Daniel!Akaka!reintroduced!into!the!US!Congress!the!
Native! Hawaiian! Government! Reorganization! Act! –! aka! the! Akaka! Bill.! This! seeks! to!
establish! the! legal! framework! through! which! a! Native! Hawaiian! government! can! be!
formed! and! thereby! gain! federal! recognition! of! Native! Hawaiians! as! the! indigenous!
people!of!Hawaii.!This!would,!in!essence,!finally!put!them!on!the!same!legal!footing!as!
the!over!500!federallyZrecognized!Native!American!tribes.!
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Waikoloa$Village,$Hawaii,$USA$2017$Federal! recognition! of! Native! Hawaiians! is! widely! supported! in! Hawaii! (including! by!
Governor!Lingle),!but!there!is!lots!of!controversy!and!disagreement!over!what!shape!
‘Hawaiian! sovereignty’! should! ultimately! take.! As! a! result,! the! bill’s! sponsors!
emphasize! what! the! legislation! does! not! do:! it! doesn’t! establish! a! government! (it!
provides! the! means! for! doing! so);! it! doesn’t! settle! any! reparation! claims;! it! doesn’t!
take!private!land!or!create!a!‘reservation’;!it!doesn’t!authorize!gambling;!and!it!doesn’t!
allow! Hawaii! to! secede! from! the! US.! Establishing! a! Native! Hawaiian! government,! as!
Senator!Akaka!has!said,!‘is!important!for!all!people!of!Hawaii,!so!we!can!finally!resolve!
the!longstanding!issues!relating!from!the!overthrow!of!the!Kingdom!of!Hawaii.’!!
Another! key! issue! facing! locals! and! politicians! alike! is! that! of! Hawaii's! fragile! island!
ecology.!Like!a!canary!in!a!coal!mine,!Hawaii!is!sounding!a!warning!about!the!need!to!
adopt! a! selfZsustaining! island! mentality.! For! half! a! millennium! Hawaii! existed! in!
complete! isolation! and! its! people! flourished;! today! the! state! imports! over! 85%! of! its!
food!and!fuel,!and!residents!like!to!ask,!'Could!we!survive!if!the!boats!stop!coming?'!
The!answer,!right!now,!is!'no'.!But!Hawaii!sees!what!it!must!do!to!change,!and!there!
has!been!no!greater!validation!of!its!perspective!than!the!2008!election!of!HawaiiZborn!
Barack!Obama!as!the!44th!US!president.!
As! First! Lady! Michelle! Obama! has! said,! 'You! can’t! really! understand! Barack! until! you!
understand! Hawaii.'! For! Hawaii! residents,! a! lot! of! what! that! means! is! understanding!
the! dynamics! of! a! multicultural! household! and! a! multiracial! heritage.! A! large! part! of!
the! reason! Hawaii! was! the! last! state! to! join! the! Union! in! 1959! was! because! of! US!
political! reluctance! to! embrace! its! ethnically! mixed! population.! Now,! 50! years! later,!
President!Obama’s!calls!for!consensusZbuilding!and!respect!for!diversity,!his!emphasis!
on!renewable!energy,!his!hopes!to!build!a!balanced!economy!that!sustains!all!peoples!
and! environments! –! these! national! aspirations! also! exemplify,! and! may! in! part! arise!
from!his!upbringing!in,!Hawaii.!
Even! before! Obama's! election,! however,! the! state! had! begun! developing! a!
comprehensive! sustainability! plan! –! called! Hawaiʻi! 2050! –! that,! when! passed,! will! be!
used! to! help! guide! the! legislature! in! its! decision! making.! As! much! as! its! specific!
proposals,!the!novel,!statewide!effort!to!define!sustainability!–!agreeing!to!a!vision!of!
Hawaii’s! ideal! self! and! then! establishing! concrete! ways! of! measuring! it! –! is! helping!
instill!that!ethic!in!every!community.!
In! 2008! Governor! Lingle! signed! the! Hawaiʻi! Clean! Energy! Initiative! (HCEI),! which! sets!
the!goal!of!having!a!70%!clean!energy!economy!by!2030.!Hawaii!is!the!USA’s!most!oilZ
dependent!state!(spending!$7!billion!annually!on!foreign!oil),!and!it!has!the!high!utility!
bills!to!prove!it.!With!HCEI,!it’s!now!pursuing!every!renewable!and!clean!energy!option!
available! –! wind! farms! on! Maui,! geothermal! and! biomass! on! the! Big! Island,! electric!

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cars!on!Oʻahu,!in!addition!to!remaking!its!electricity!grid.!If!it!succeeds,!Hawaii!would!
become!the!first!economy!based!primarily!on!clean!energy.!
While!locals!freely!acknowledge!all!the!challenges!facing!their!state,!they!are!also!quick!
to! add! that! they! wouldn’t! live! anywhere! else.! Hawaii! may! be! endangered,! but! it!
possesses! a! beauty! and! spirit! that! can! be! found! nowhere! else.! Plus,! if! Hawaii! can!
achieve!a!sustainable!balance,!it!may!do!more!than!save!itself.!It!may!become!a!model!
for!the!nation.!
!
Read!more:!http://www.lonelyplanet.com/usa/hawaii/history#ixzz4YgTCbw4s!
!
Ref.:!http://www.lonelyplanet.com/usa/hawaii/history!!
!

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Hawaii’s!main!island!
!
!

!

!

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NOTES!

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