10th INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory andModelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materials.
The 10th International Symposium “Hydrogen & Energy” serves as an information
platform of the fundamental science and technology and the frontiers of research onhydrogen and energy. The symposium consists of invited keynote lectures reviewing
the key elements of the hydrogen cycle, i.e. the hydrogen production, hydrogen storage
and hydrogen combustion and fuel cells. Furthermore, contributions on the conversionof renewable energy in general and energy carriers beside and beyond hydrogen arevery welcome. The world leading experts present the current research challenges andmost 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 LAFORET hotel &resort Zao in the beautiful small village. Zao is known for “Juhyo (The Snow Monster)”which can be viewed in winter. The snowmobile, wildmonster, takes you to the deep
snow Juhyo area from Sumikawa Snow Park.
The number of participants is limited to 60.

21. – 26. February 2016

LAFORET
HOTELS & RESORTS
2-1, Nanokahara, Togatta-onsen, Zao-cho, Katta-gun
Miyagi 989-0916 JAPAN
Phone: +81-224-35-3111
Fax: +81-224-35-3131
http://www.laforet.co.jp/lfhotels/zao/

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

ACKNOWLEDGEMENTSUPPORTED BY

Tohoku University

International Collaboration Center IMR (ICC-IMR)

Institute for Materials Research(IMR)

Collaborative Research Center on Energy Materials (E-IMR)WPI Advanced Institute for Materials Research (WPI-AIMR)

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016     Modeling  

International Collaboration Center IMR (ICC-IMR),WPI Advanced Institute for Materials Research(WPI-AIMR), Institute for Materials Research(IMR),
Collaborative Research Center on Energy Materials(E-IMR).

SUPPORTED BY
Tohoku University        

SUBJECTS

http://hesymposium.ch/

21.-26. February 2016
Laforet Hotels & Resorts, Zao, JAPAN

10th INT.SYMPOSIUM
HYDROGEN & ENERGYPROGRAM

Etsuo AKIBA, Japan
Katsutoshi AOKI, JapanTom AUTREY, USA
Ping CHEN, China
Young Whan CHO, Korea
Martin DORNHEIM, Germany
Bjorn C. HAUBACK, Norway
Michael HIRSCHER, Germany
Craig M. JENSEN, USA
Torben R. JENSEN, Denmark
Xing Guo LI, China
Craig BUCKLEY, Australia
Tejs VEGGE, Denmark
Min ZHU, China
Andreas ZÜTTEL, Switzerland

INVITED SPEAKERS

Bernard DAM, Netherlands
Shin-ichi ORIMO, JapanJan ROSSMEISEL, Denmark
Min ZHU, China
Andreas ZÜTTEL, Switzerland

STEERING COMMITEE
IMR

Registration and abstract submission:
before 6th November, 2015

Conference fee
General : ¥100,000.
Room Shared Students : ¥70,000
Incl. room (5 nights), proceedings and social
event, breakfast, coffee breaks, lunch, dinner,conference dinner, non alc. bevarages.

REGISTRATION

AirportSENDAI st.

2-1, Nanokahara, Togatta-onsen, Zao-cho,
Katta-gun, Miyagi 989-0916 JAPANhttp://www.laforet.co.jp/lfhotels/zao/

LAFORET Hotels & Resorts

5km

LAFORETLOCATION

10th Int. Symposium "Hydrogen & Energy"
Sendai, JAPAN 2016

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016
Abstracts
SUNDAYafternoon
17:0017:10

opening:ShinichiORIMO

17:1017:50

I1:AndreasZÜTTEL:DOWENEEDHYDROGEN?

㸫㸫

13

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

MONDAYmorning

Chair:EtsuoAKIBA

09:0009:40

I2:MichaelHIRSCHER:HYDROGENADSORPTIONINPOROUSMATERIALS

14

09:4010:20

I3:PingCHEN:AMIDESANDAMMONIAASHYDROGENCARRIERS

15

10:2010:40

CoffeeBreak

10:4011:00

T1:BillDAVID:EXPLORINGTHEENERGYSTORAGEVERSATILITYOFTHELITHIUM
IMIDE/AMIDESYSTEM

16

11:0011:20

T2:MichelLATROCHE:MECHANOCHEMICALSYNTHESISANDCRYSTALLOGRAPHICPROPERTIESOFTHELiMgNHSYSTEMUNDERHYDROGENGAS

17

11:2011:40

T3:MattiaGABOARDI:HYDROGENINNOVELCARBONNANOSTRUCTURES

18

MONDAYafternoon Chair:MichaelHIRSCHER
14:0014:40

I4:BjørnC.HAUBACK:Mg(BH 4)2–STUDIESOFADDITIVESANDISOTOPICEXCHANGE

19

14:4015:00

T4:ChiaraMILANESE:REVERSIBLEHYDROGENSORPTIONFORTHEINFILTRATEDMAGNESIUMBOROHYDRIDE

20

15:0015:20

T5:AnnaLisaCHAUDHARY:SynchrotronTechniquesfortheMg 2FeH6Mg(BH4)2
HydrogenStorageSystem21

15:2016:00

CoffeeBreak

16:0016:20

T6:StefanoDELEDDA:QUATERNARYMGBASEDTRANSITIONMETALCOMPLEXHYDRIDESPRODUCEDBYREACTIVEMILLING

22

16:2016:40

T7:HaiWenLI:SOLVENTFREESYNTHESESOFMETALDODECABORATESFOR
ENERGYAPPLICATIONS

23

16:4017:00

T8:LiuzhangOUYANG:HYDROLOSISOFMgH2BASEDHYDRIDES

24

MONDAYevening

POSTERChair:AnnaLisaCHAUDHARY

20:00䇲P1:EfiHADJIXENOPHONTOS:HYDROGENSORPTIONKINETICSINMAGNESIUM
ANDTITANIUMHYDRIDETHINFILMS
P2:HaoZHONG:ENERGYEFFICIENCYOFMgH 2BASEHYDRIDEANDNaBH4HYDROLYSISCYCLE
P3:JianwenLIU:PREPARATIONANDHYDROGENSTORAGEPROPERTIESOF
Mg/TM OX  (TM =Ti,Nb)THINFILMSBYMAGNETRONSPUTTERING䇲21:30

25
26
27

P4:KlausTAUBE:BOR4STORE–BORONBASEDMETALHYDRIDEsFORHYDROGEN
SUPPLYOFSOFC

28

P5:HiroyukiSAITOH:SYNTHESESOFNOVELHYDRIDESUNDERHIGHPRESSURE

29

P6:ToyotoSATO:CRYSTALSTRUCTUREINDICATOR:THEIONICFILLINGFRACTIONOFHYDRIDESWITHARBITRARYARRANGEDIONICCOMPONENTS

30

P7:JunxianZHANG:STRUCTUREANDHYDROGENSORPTIONPROPERTIESOF(A ,Mg)2Ni7(A =La,Sm,GdORY)COMPOUNDS

31

P8:HanWANG:TheimprovedHydrogenStoragePerformancesoftheMulti
ComponentComposite:2Mg(NH2)2–3LiH–LiBH432

P9:KatherinHURST:HYDROGENSORPTIONCAPACITYPROTOCOLSANDRECENT
MATERIALSSYNTHESISEFFORTS

33

P10:ToshiyaOTOMO:STRUCTURALANALYSISDURINGTHEDISPROPORTIONATIONPROCESSOFNaAlH4BYELEMENTSELECTIVEMETHODS

34

P11:PhilippeMAURON:HYDROGENDESORPTIONOFC 60H33/LiDINVESTIGATEDBY
MASSSPECTROMETRY

35

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

TUESDAYmorning

Chair:BjornC.HAUBACK

09:0009:40

I5:XhingguoLI:SYNTHESISANDPROPERTIESOFNANOSTRUCTUREDMATERIALSFORHYDROGENSTORAGEANDLITHIUMBATTERYBYHOTANDCOLDPLASMAS

36

09:4010:20

I6:TejsVEGGE:COMPUTATIONALDESIGNOFMATERIALSFORELECTROCHEMCIAL
ENERGYCONVERSIONANDSTORAGE

37

10:2010:40

CoffeeBreak

10:4011:00

T9:MarkD.ALLENDORF:HYMARC:ACONSORTIUMFORADVANCINGSOLIDSTATEHYDROGENSTORAGEMATERIALS

38

11:0011:20

T10:JeanClaudeCRIVELLO:GROUNDSTATEMAPSOFBINARYMETALHYDROGENSYSTEMS

39

11:2011:40

T11:MarcelloBARICCO:ASSESSMENTOFPHASEDIAGRAMSINCOMPLEXHYDRIDES

40

TUESDAYafternoon Chair:XingguoLI
14:0014:40

I7:CraigBUCKLEY:MetalHydridesforConcentratedSolarThermalEnergyStorage41

14:4015:00

T12:SatyaShekharBHOGILLA:EXPERIMENTALSTUDYONTOTALIZEDHYDROGEN
ENERGYUTILIZATIONSYSTEMUSINGPVPOWERDATA

42

15:0015:20

T13:AsunciónFERNÁNDEZ:PtCucatalyticcoatingsforhydrogencombustion:nanostructureanddealloyingeffects

43

15:2016:00
16:0016:20

CoffeeBreakT14:ShunsukeKATO:CO2ReductionviaaMetalHydrideCatalyst

44

16:2016:40

T15:TengHE:CovalentTriazineFrameworkSupportedPalladiumNanoparticles
forCatalyticHydrogenationof Heterocycles

45

16:4017:00

T16:RyotaKONDO:INITIALACTIVATIONMECHANISMSOFPALLADIUMADDEDTi
ALLOYUSINGCROSSCOUPLINGREACTION

46

TUESDAYevening

POSTERChair:ShunsukeKATO

20:00䇲P12:AnnaWOLCZYK:INFLUENCEOFPREPARATIONCONDITIONSONIONICCONDUCTIVITYIN(LiNH 2)X(LiBH4)1 ( =0.50,0.75)

47

P13:JunCHEN:MgCl 2PROMOTEDHYDROLYSISOFMgH2NANOPARTICLESFORHIGHLYEFFICIENTH 2GENERATION

48

P14:ShigeyukiTAKAGI:EXPLORATIONOFHYDROGENRICHMATERIALS
P15:GuanqiaoLI:DehydridingPropertiesofLiBH 4CombinedwithMg2FeH6

䇲21:30

73
49

P16:KazutakaIKEDA:STRUCTURALANALYSISOFHYDRIDESBYHIGHINTENSITYNEUTRONTOTALDIFFRACTOMETER(NOVA)

50

P17:MarianaSPODARYK:ELECTROCHEMICALCO2REDUCTIONTOSPECIFICHYDROCARBONS

51

P18:DaijuMATSUMURA:HYDROGENETIONREACTIONOFPRECIOUSMETALNANOPARTICLESSTUDIEDBYTIMERESOLVEDXRAYABSORPTIONSPECTROSCOPY52

P19:JiuyiZHU:RECYCLABLEHYROGENSTORAGEINLiBH 4COMPOSITEWITH BN

53

P20:TamioIKESYOJI:HOWCATIONSMOVEINBORONHYDRIDEELECTROLYTES:FIRSTPRINCIPLESMOLECULARDYNAMICS

54

P21:ShinichiORIMO:COMPLEXHYDRIDEELECTRODESFORHIGHENERGYDENSITYALLSOLIDSTATELITHIUMSULFURBATTERY55

P22:DhaneshCHANDRA:LOCALATOMICORDERINTHENiBASEDAMORPHOUS
HYDROGENPERMEATIONMEMBRANES

56

P23:TessuiNAKAGAWA:DEHYDROGENATIONANDREGENERATIONOFAMMONIABORANEINIONICLIQUIDS

57

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

WEDNESDAYmorning Chair:CraigBUCKLEY
09:0009:40

I8:MinZHU:MgBASETERNARYALLOYSWITHIMPROVEDHYDROGENSTORAGE
PROPERTIES

58

09:4010:20

I9:KatsutoshiAOKI:STRUCTURALANDTHERMODYNAMICPROPERTIESOFHYDROGENRICHSOLIDSOLUTIONSOFIRON

59

10:2010:40

CoffeeBreak

10:4011:00

T17:MartinOwenJONES:NEUTRONSTUDIESOFUNCONVENTIONALHYDROGEN
STORAGEMATERIALSANDCATALYSTS

60

11:0011:20

T18:SabrinaSARTORI:LONGRANGEORDERINGOFDEUTERIUMATOMSIN
SUPERLATTICEALLOYSWITHPARTIALAl/SiSUBSTITUTION

61

11:2011:40

T19:KoujiSAKAKI:DEGRADATIONUPONHYDROGENATIONANDLOCALSTRUCTUREANALYSIS

62

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

THURSDAYmorning Chair:PingCHEN
09:0009:40

I10:YoungWhanCHO:INTERPHASEBOUNDARYANDSIZECONFINEMENTEFFECT
ONREVERSIBLEHYDROGENSORPTIONREACTIONANDIONTRANSPORTOFMETAL
BOROHYDRIDES/NANOSCAFFOLDCOMPOSITES

63

09:4010:20

I11:TorbenR.JENSEN:MULTIFUNCTIONALENERGYSTORAGEMATERIALS

64

10:2010:40

CoffeeBreak

10:4011:00

T20:DidierBLANCHARD:LITHIUMSULFURALLSOLIDSTATEBATTERIES

65

11:0011:20

T21:MotoakiMATSUO:DEVELOPMENTOFCOMPLEXHYDRIDESFORFASTIONICCONDUCTION

66

11:2011:40

T22:DanielePONTIROLI:GRAPHENEBASEDLiANDNaIONBATTERIES

67

THURSDAYafternoon Chair:YoungWhanCHO
14:0014:40

I12:MartinDORNHEIM:NOVELHYDROGENSTORAGEMATERIALSANDSYSTEMSDEVELOPMENT

68

14:4015:00

T23:XinJU:TherelevanceofstructureandpropertiesonTidopedMg 2Ni,TiVCrMn
alloyandNaAlH4duringhydrogenabsorptiondesorptioncycles

69

15:0015:20

T24:ElsaCALLINI:DEHYDROGENATIONREACTIONS:TRANSIENTSPECIESAND
PHASES70

15:2016:00

CoffeeBreak

16:0016:20

T25:YaroslavFILINCHUK:TOWARDSNANOPOROUSHYBRIDHYDRIDES

71

16:2016:40

T26:MauroRICCÒ:MUONSPECTROSCOPYFORTHESTUDYOFHYDROGEN
STORAGEMATERIALS

72

16:4017:00

T27:ShigeyukiTAKAGI:EXPLORATIONOFHYDROGENRICHMATERIALS

73

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

FRIDAYmorning

Chair:MartinDORNHEIM

09:0009:40

I13:EtsuoAKIBA:NITROGENBASEDCOMPOSITEMATERIALSFORHYDROGEN
STORAGE74

09:4010:20

I14:TomAUTREY:RESEARCHANDDEVELOPMENTOFADVANCEDHYDROGEN
STORAGECORECHARACTERIZATIONTECHNIQUESANDMATERIALS

75

10:2011:00

I15:CraigJENSEN:REVERSIBLEHYDROGENATIONOFBORANESTOBOROHYDRIDESUNDERMODERATECONDITIONS76

SCIENCEOFHYDROGEN&ENERGYAWARD
ListofParticipants
Information
Note

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

TIMETABLE㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫㸫㸫

20:00-21:30

Dinner

18:00-20:00

opening: Shin-ichi ORIMO

1: Andreas ZÜTTEL

Registration

21.02.16
Sunday14:00-14:20
14:20-14:40
14:40-15:00
15:00-15:20
15:20-16:00
16:00-16:20
16:20-16:40
16:40-17:00
17:00-17:20
17:20-17:40
17:40-18:00

12:00-14:00

09:00-09:20
09:20-09:40
09:40-10:00
10:00-10:20
10:20-10:40
10:40-11:00
11:00-11:20
11:20-11:40

Time/Day

Coffee Break
9: Mark D. ALLENDORF
10: Jean-Claude CRIVELLO
11: Marcello BARICCO

Coffee Break
1: Bill DAVID
2: Michel LATROCHE
3: Mattia GABOARDI

Chair: Michael HIRSCHER

Dinner

12: Satya Shekhar BHOGILLA
13: Asunción FERNÁNDEZ
Coffee Break
14: Shunsuke KATO
15: Teng HE
16: Ryota KONDO

7: Craig BUCKLEY

Chair: Xingguo LI

1: Efi HADJIXENOPHONTOS
2: Hao ZHONG
3: Jianwen LIU
4: Klaus TAUBE
5: Hiroyuki SAITOH
6: Toyoto SATO
7: Junxian ZHANG
8: Han WANG
9: Katherin HURST
10: Toshiya OTOMO
11: Philippe MAURON

12: Anna WOLCZYK
13: Jun CHEN
14: Shigeyuki TAKAGI
15: Guanqiao LI
16: Kazutaka IKEDA
17: Mariana SPODARYK
18: Daiju MATSUMURA
19: Jiuyi ZHU
20: Tamio IKESHOJI
21: Shin-ichi ORIMO
22: Dhanesh CHANDRA
23: Tessui NAKAGAWAPOSTER Chair: Anna-Lisa CHAUDHARY POSTER Chair: Shunsuke KATO

Dinner4: Chiara MILANESE
5: Anna-Lisa CHAUDHARY
Coffee Break
6: Stefano DELEDDA
7: Hai-Wen LI
8: Liuzhang OUYANG

4: Bjørn C. HAUBACKLunch

6: Tejs VEGGE

3: Ping CHEN

Lunch

5: Xhingguo LI

23.02.16
Tuesday
Chair: Bjorn C. HAUBACK

2: Michael HIRSCHER

22.02.16
MondayChair: Etsuo AKIBA

Dinner (Zao, Cheese House)

Social Event

Chair: Shigeyuki TAKAGILunch (Lunch Box)

Coffee Break
17: Martin Owen JONES
18: Sabrina SARTORI
19: Kouji SAKAKI

9: Katsutoshi AOKI

8: Min ZHU

24.02.16
Wednesday
Chair: Craig BUCKLEY

Conference Banquet

23: Xin JU
24: Elsa CALLINI
Coffee Break
25: Yaroslav FILINCHUK
26: Mauro RICCÒ
27: Shigeyuki TAKAGI

12: Martin DORNHEIM

Chair: Young Whan CHO

Lunch

Coffee Break
20: Didier BLANCHARD
21: Motoaki MATSUO
22: Daniele PONTIROLI

11: Torben R. JENSEN

10: Young Whan CHO

25.02.16
Thursday
Chair: Ping CHEN

Departure

Closing & Lunch

15: Craig JENSEN

14: Tom AUTREY

13: Etsuo AKIBA

26.02.16
FridayChair: Martin DORNHEIM

20:00-21:30

18:00-20:00

14:00-14:20
14:20-14:40
14:40-15:00
15:00-15:20
15:20-16:00
16:00-16:20
16:20-16:40
16:40-17:00
17:00-17:20
17:20-17:40
17:40-18:00

12:00-14:00

09:00-09:20
09:20-09:40
09:40-10:00
10:00-10:20
10:20-10:40
10:40-11:00
11:00-11:20
11:20-11:40

Time/Day

10th Int. Symposium "Hydrogen & Energy"
Sendai, JAPAN 2016

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

ABSTRACTS㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016    
Andreas ZÜTTEL
Affiliation LMER, ISIC, SB, École polytechnique fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Rue del’Industrie 17, CP 440, CH-1951 Sion, Switzerland
Abstract
The storage of renewable energy for mobility and stationary is a key challenge for the near future. While the conversionof solar energy into high temperature heat and electricity is technologically feasible, the storage of energy with a highgravimetric and volumetric density as well as in large quantities remains a challenge. Our energy demand per capita isaround 0.2 kWh/km for mobility (car, airplane), 2 kW of electricity and 2 kW of heat (Switzerland). The storage of large
quantities of energy as well as the need for high energy density energy carrier for mobility requires the synthesis ofhydrocarbons from water and CO2 with renewable energy.


An energy economy solely based on renewable energy
requires the seasonal storage of half of the annual
energy consumption (25'000 kWh/capita) with a time
constant of half a year and the storage of 100 kWh/capita
with a high energy density and a time constant of half a
day for mobility. The latter corresponds to > 500 kg ofbatteries or 5 kg of hydrogen used in a fuel cell with 50%
efficiency. The seasonal storage requires 250 t ofbatteries or 2.5 t of hydrogen. The storage of hydrogen ina metal hydride (1 mass%) leads to 250 t of metal
hydride, which cost today at least 5 Mio. Euros. This is
more than most Europeans earn during there whole life.
In case of batteries the cost is approx. 75 Mio.
Euros/capita. Therefore, seasonal energy storage inbatteries or hydrides is more expensive than building ahouse and economically not affordable for a large part ofthe population in the industrialized world. Furthermore,
for mobility the storage of the energy is roughly ten times
the weight and volume of the transported person andsince the energy consumption is proportional to theweight of the vehicle, the efficiency drops below 10%.

the atmosphere (50 kg/capita and day) and the synthesisof 15 kg liquid hydrocarbon per capita and day. The
seasonal storage of 2500 kg/capita of hydrocarbons is
economically negligible.

! "#
Hydrogen is the energy carrier, i.e. the renewable energy
is stored in hydrogen. The reaction of hydrogen with CO2
to hydrocarbons is an exothermal reaction, which leads
to a stable and easy to store liquid, e.g. C8H18, that
contains 76% of the energy in hydrogen (thermodynamic
limit).


As a consequence, the storage has to be simplified by anefficient and economically feasible process. Hydrocarbons are a high energy density storage material,
which is easy to store. Furthermore hydrocarbons are
based on CO2 and H2O, both are abundant on earth. The
storage of renewable energy in hydrocarbons requires tosolve three technical challenges. Water electrolysis inlarge scale e.g. >10 kW/capita, extraction of CO2 fromA. ZÜTTEL

Fig. 1 Water is reduced with renewable energy to hydrogen andthe hydrogen reduces CO2 from the atmosphere to form
synthetic hydrocarbons.The number indicate the quantities per
capita in Switzerland in case the energy demand is completely
covered by renewable energy.

Short CV Born 22. 8. $%&' in Bern, Switzerland. $%() Engineering Degree in Chemistry, Burgdorf,
Switzerland. $%%* Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. $%%' Dr.
rer. nat. from the science faculty UniFR. $%%+ Post Doc with AT&T Bell Labs in Murray Hill, New
Jersey, USA. $%%, Lecturer at the Physics Department UniFR. -**' External professor at the Vrije
Universiteit Amsterdam, Netherlands. -**+ Habilitation in experimental physics at the sciencefaculty UniFR. President of the Swiss Hydrogen Association „HYDROPOLE“. -**& Head of thesection “Hydrogen & Energy” at EMPA and Prof. tit. in the Physics department UniFR. -**% Guest
Professor at IMR, Tohoku University in Sendai, Japan. -*$- Visiting Professor at Delft Technical
University, The Netherlands, -*$+ Full Professor for Physical Chemsitry, Institut des Sciences etIngénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland

Corresponding author: Andreas. ZÜETTEL, andreas.zuettel@epfl.ch, Tel. +41 79 484 2553

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYDROGEN ADSORPTION IN POROUS MATERIALS
Michael Hirscher, Maurice Schlichtenmayer, Ingrid Weinrauch, and Rafael BalderasXicohténcatl
Max Planck Institute for Intelligent Systems, Stuttgart, Germany
Highly porous materials can be utilized for hydrogen storage in cryo-adsorption tank systems. The presentation will focus
on important technological aspects as gravimetric and volumetric storage density, usable capacity, and operating
temperature. Additionally, fundamental investigations on the density of the adsorbed hydrogen layer and differences in
the heat of adsorption of hydrogen isotopes will be addressed.

Introduction
Besides high hydrogen storage density, one important
prerequisite for automotive application is short refuelingtime without evolving a large amount of heat. Owing to
the low heat of adsorption involved in physisorption ofhydrogen molecules, cryo-adsorption systems based onmaterials, possessing large specific surface area andhigh micropore density, fulfil these requirements. The
field of cryoadsorption gained new momentum when anovel class of crystalline lightweight materials withextremely high porosity, the so-called metal-organic
frameworks (MOFs) has been developed. These
coordination polymers consist of inorganic sub-units,
such as metal ions or metal–oxide clusters, connected toeach other by rigid organic ligands in a three-dimensionalframework. Recently specific surface areas up to 5000
m2 g–1, i.e. more than five times the specific surface areaof the best zeolites, were obtained for several novel
MOFs [1]. Surface areas of 5000 m2 g-1 maybe theultimate maximum achievable and higher areas reported
are still under discussion.

Results and Discussion
For the maximum hydrogen uptake at high pressure and77 K an almost linear correlation with the specific surface
area determined by nitrogen adsorption is found for manydifferent nanoporous materials [1-3]. In contrast, theadsorption at low pressure depends on the pore size or
the chemical composition of the materials. Several
experimental techniques have been applied to correlate
the hydrogen uptake properties to the nanostructure ofthese novel materials. The newly developed technique of
low-temperature thermal desorption spectroscopy
enables a quick analysis of different adsorption sites andtheir strength [4]. Generally MOF structures possessing

M. Hirscher

smaller pores show higher desorption temperatures forhydrogen [5]. By measuring adsorption isotherms over awide range of pressure and temperature, the isostericheat of adsorption can be accurately determined over awide regime of hydrogen uptake which is important fortechnologically applications [6]. Typically structurespossessing smaller pores show a higher heat ofadsorption. Both, maximum hydrogen storage capacity
and heat of adsorption have to be considered to optimize
the materials for their potential application [7,8].
Another cruicial point is the density of the adsorbed layer,
which ultimately limits the volumetric storage capacity.
The pesentation will give first results for measurments onreference materials.

References[1] M. Hirscher, Angew. Chem. Int. Ed. 50, 581 (2011)[2] R. Chahine, T. K. Bose, Int. J. Hydrogen Energy 19,
161 (1994)[3] B. Panella, M. Hirscher, S. Roth, Carbon 43, 2209
(2005)[4] B. Panella, M. Hirscher, B. Ludescher, Microporous
Mesoporous Mat. 103, 230 (2007)[5] B. Panella, K. Hönes, U. Müller, N. Trukhan, M.
Schubert, H. Pütter, M. Hirscher, Angew. Chem. Int.
Ed. 47, 2138 (2008)[6] B. Schmitz, U. Müller, N. Trukhan, M. Schubert, G.
Férey, M. Hirscher, ChemPhysChem 9, 2181 (2008)[7] M. Schlichtenmayer, B. Streppel, M. Hirscher, Int. J.
Hydrogen Energy 36, 586 (2011)[8] M. Schlichtenmayer, M. Hirscher, Journal of
Materials Chemistry, 22, 10134 (2012)

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. Prior to taking his position in Stuttgart, hespent a post-doctoral fellowship at the University of Pennsylvania, Philadelphia, USA. Recently, heedited the “Handbook of Hydrogen Storage”. Since 2013 he is Operating Agent of Task 32“Hydrogen-based Energy Storage” in the Hydrogen Implementation Agreement of the IEA. Last year
he received Hydrogen & Energy Award 2015 in Switzerland. His current research interests focus on
nanoporous materials for gas storage and separation.

Corresponding author: Michael Hirscher, hirscher@is.mpg.de, Tel. +49-711-689-1808㸫㸫

10th Int. Symposium "Hydrogen & Energy"

TITLE

Sendai, JAPAN 2016

AMIDES AND AMMONIA AS HYDROGEN CARRIERS

Name(s) Ping Chen,* Jianping Guo, hujun Cao, Juner Chen, Zhitao Xiong, Guotao Wu
Affiliation

Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Abstract
N combines with H, C and/or alkalis forming NH3, amines and amides etc., those substances are potential hydrogen
carriers. The thermal treatment of amines or amides usually leads to decomposition rather than dehydrogenation.
Ammonia, on the other hands, has to overcome sever kinetic barrier to give off H2. The selective and efficientdehydrogenation of those compounds depends largely on the compositional alteration and catalytic modification.

Results and Discussion

HGThe thermodynamic properties of hydrogen releasefrom those materials may be altered through theintroduction of additives that can either stabilize reactantsor products. Comparatively, catalytic modification ischallenging with a few successful examples.
NH3, having a hydrogen content of 17.6 wt%, is an
attractive hydrogen carrier. The key issue in the catalytic
decomposition of NH3 is the development of non-noble
metal based, highly active and stable catalysts. With theunderstanding on the electronic promotion of alkali
amide/imide to 3d metal nitrides, a novel catalyst systemhaving activity surpassing Ru was identified recently. The
characterization of intermediate phase of catalyst and thestep-wise reaction pathway allows the elucidation of
catalytic mechanism.

References[1] Chen P, Xiong ZT, Luo JZ, Lin JY, Tan KL. Nature.
420, 302 (2002)[2] Xiong ZT, Yong CK, Wu GT, and Chen P et al.
Nature Mater. 7(2), 138(2008)

HG       

H2

  

  





 





18

Reversibility: full ۖ partial

AmountofH2 desorbed(wt%)

The strategy in materials design for hydrogenstorage is via compositing NH-containing compoundswith those containing hydridic H. As shown in Fig. 1,
amides can composite with hydrides to facilitatehydrogen desorption under moderate condition. LiNH2, as
an example, reacts with LiH giving off ~10.5 wt% in a
stepwise manner.[1] Mg(NH2)2-LiH composite, on theother hand, reversibly stores ca. 5.5 wt% hydrogen at
180 °C. Amides can also compound with –BH3 or –CH2R
group forming amidoboranes or metalated amines (suchas dilithiated ethylediamine).[2,3] Those compounds
release large amount of H2 selectively via redox of H(N)and H(B) or H(C) under given condition.

null
NH 3

16
14

LiBH 4NH2NH 2

12LiNH 2BH 3

2LiNH 2LiBH 4

10

Ca(NH2BH 3)2864

LiNH2LiH
Li2EDAۖ
Mg(NH2)22LiH
Kcatalyzed
Mg(NH 2)22LiH 2LiNH2CaH2

Li2NHLiH

2
100

200

300

400

500

Temperature(eC)

Figure 1 The strategy of materials design forhydrogen storage (upper) and the performancesof selected systems (bottom).
[3] Chen JE, Wu H, and Chen P et al. Chem Eur J.
20(22), 6632 (2014)[4] Guo JP, Wang PK, Wu GT, Wu AA, Hu DQ, Xiong ZT,
Wang JH, Yu P, Chang F, Chen Z, Chen P *, Angew.
Chem. Int. Ed. 54, 2950 (2015)

Short CV 㸪            ǡ   ȋ Ȍǡ   ȋȌǤ ǡͳͻͻͳǡͳͻͻͶͳͻͻ͹ǡ ǡǡǤ
  ʹͲͲͺǤ 
         ǦǦ       Ǥ
Ping Chen
Corresponding author: Ping Chen, pchen@dicp.ac.cn, 86-411-84379905.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

EXPLORING THE ENERGY STORAGE VERSATILITY OF THE LITHIUM
IMIDE/ AMIDE 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 solid-solution system is not only attractive as a reversible lightweight hydrogen store but is also an effective
catalyst in the decomposition of ammonia. This presentation highlights the significant and related roles of ammonia, nitrogen andhydrogen both in maintaining the hydrogenation capacity of lithium imide/ amide over hundreds of cycles and also effecting ammonia
decomposition at moderate temperatures. The presence of ammonia in the input gas stream is a concern for PEM fuel cell operationand is an important issue to resolve for using lithium imide/ amide or ammonia as a hydrogen store. This presentation will briefly
describe the successful demonstration of PEM fuel cell operation with hydrogen that is produced from ammonia that has beencatalytically decomposed by lithium imide.

Introduction
The lithium imide and amide system is among the mostreversible lightweight physisorbed hydrogen storage materials.
With a 6.5wt% H2 gravimetric capacity, it has been successfully
cycled, with essentially no loss of capacity, many hundreds oftimes through the addition of nitrogen to the hydrogen gas
stream. In this presentation, we examine the hydrogen
reversibility of the lithium imide/ amide system and confirm theefficacy of a mixed gas stream of hydrogen andnitrogen using[1]
in-situ high resolution X-ray powder diffraction . The versatilityof lithium imide/ amide as an energy storage material goesbeyond its reversible hydrogen storage properties to its
consideration as an ammonia cracking catalyst. Ammonia has
many attractive properties as a potential hydrogen storage
material. It is a liquid at room temperature under modest
pressure (<10bar) and has a 17.6wt% H2 gravimetric capacity.
[2]
The discovery that the sodium / sodium amide is an effective
and inexpensive ammonia cracking catalyst has led to thesearch for other amide/imide based systems. Non-stoichiometric[3]lithium imide, in particular, is an efficient catalyst with superior
performance to sodium amide. In-situ neutron powder diffraction
analysis has provided insights into the nature of the lithium imide
catalyst under operating conditions.

reaction under different conditions emphasises the crucial role ofionic mobility in determining the practical use of this material.
Non-stoichiometric Li2-xNH1+x is a highly active catalyst for the
production of high-purity hydrogen from ammonia. Neutron
powder diffraction measurements reveal that the catalyst
deviates from pure imide stoichiometry under ammonia flow,
with active catalytic behaviour observed across a range of
stoichiometry values near the imide. These measurements also
show that hydrogen from the ammonia is exchanged with, andincorporated into, the bulk catalyst material, in a significant
departure from traditional NH3 decomposition catalysts. The
efficacy of the lithium imide–amide system not only represents a
more promising catalyst system, but also broadens the range ofcandidates for amide-based ammonia decomposition to include
those that form imides.

Experimental
Synchrotron X-ray diffraction data were collected on the ID22
high resolution powder diffractometer at the ESRF, Grenoble,
from a sample of lithium nitride placed inside a single crystal
1mm. sapphire capillary housed within a custom-built highpressure sample environment, allowing gas pressures of up to
100 bar. Diffraction data collected over the first 26 cycles areshown in Figure 1. Neutron powder diffraction patterns of nonstoichiometric lithium imide, in combination with in-situ mass
spectrometry, were collected on the POLARIS diffractometer at
the ISIS neutron source under flowing ND3 and NH3.

Results and Discussion
In-situ X-ray powder diffraction confirms that hydrogen capacity
reduction in the lithium imide/ amide system may be mitigatedagainst through the addition of up to 20% N2 to the hydrogengas stream. The interplay between kinetically stabilised nonstoichiometric Li2-xNH1+x and the thermodynamic tendency todisproportionation to imide and amide is evident from analysis of
the diffraction data. Examination of the rates and endpoints ofFig. 1 Synchrotron X-ray powder diffraction data for 26 hydrogenation cycles of lithium
imide/ amide.

References[1] J. W. Makepeace, M. O. Jones, S. K. Callear and W. I. F. David, Phys.
Chem. Chem. Phys., 16, 4061 (2014)[2] W. I. F. David, J. W. Makepeace, S. K. Callear, H. M. A. Hunter, J. D.
Taylor, T. J. Wood, and M. O. Jones, J. Am. Chem. Soc.136 13082(2014)[3] J. W. Makepeace, T. J. Wood, H. M. A. Hunter, M. O. Jones and W. I.
F. David, Chem. Sci., 6, 3805 (2015).

Bill David is STFC Senior Fellow at the ISIS Neutron Source at the Rutherford Appleton Laboratory, Oxfordshire, UK, Professorof Materials 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 Institute of Physics, a Fellow of the Royal Society of Chemistry and an Honorary Life
Member of the British Crystallography Association.
Bill’s research has focused on the development of neutron and X-ray diffraction techniques for the study of the atomic andmolecular structure of materials. His particular emphasis on energy storage materials began with his postdoctoral research in thegroup led Prof. J B Goodenough that discovered the lithium battery. Over the past decade, Bill’s research has focused on the
discovery and characterisation of lightweight hydrogen storage systems with a growing emphasis on ammonia for energy storage
applications.

Bill DavidBill has received a number of national and international awards that most recently include one of three Bragg Lecture Awards(2013) to mark the Bragg Centenary of the discovery of X-ray diffraction and the 2015 Royal Society of Chemistry John B
Goodenough Award recognising exceptional and sustained contributions to the area of materials chemistry. He has publishedover 240 papers (h-index 56: Web of Science), edited two books and filed five patents.

Corresponding author: W I F David, bill.david@stfc.ac.uk +44 1235 445179 / +44 1865 272689

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

MECHANOCHEMICALSYNTHESISAND
CRYSTALLOGRAPHICPROPERTIES OF THE Li-Mg-N-H SYSTEM UNDER HYDROGEN GAS
Fermin Cuevas1, Zhinian Li1,2, Junxian Zhang1 and Michel Latroche1
1

ICMPE/CNRS-UPEC UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais, France 2 GRINM, 2 Xinjiekou Wai Street, Beijing
100088, China

Abstract: Efficient storage of hydrogen is widely recognized as a key challenge in the transition towards a hydrogenbased energy economy [1, 2]. In the present work, the mechanochemistry under H gas of the light-weight system Li-MgN-H is investigated. Synthesis path, gas sorption properties and crystallographic properties of the intermediate phases
are described allowing to propose a mechanistic reaction scheme for this complex hydride system.

Mechanochemistry under hydrogen gas is an efficientmethod for fast synthesis of light-weight hydrides leading
to the formation of new metastable phases with unknown
properties. Presently, the Li-Mg-N-H system has been
investigated following first the synthesis at short milling
time of metastable Li3MgN2H phase and then that ofamorphous Mg(NH2)2 phase at long milling time.
Structural analysis by X-ray (XRD) and Neutron (ND)
diffraction of intermediate and end phases wereaccomplished.

first absorption step entails the formation of a metastable
mixed-cation imide according to reaction 2Li3N + Mg +2H2 o Li3MgN2H + 3LiH. The structural andhydrogenation properties of the metastable Li3MgN2H
and amorphous Mg(NH2)2 phases are further studied byin-situ neutron diffraction at 200 °C using deuterated
samples (Fig. 1).

Phase content (wt.%)

.030
Synthesis was performed by reactive ball milling in aclosed-tighthighpressure
millingcellfromEvicomagnetics. Ball-to-powder weight ratio was set to80:1; 40 steel balls  12 mm; : = 350 rpm, Z = -350 rpm.
Reactants were 2Li3N, Mg and 8 MPa H2. In-situ
hydrogen (or deuterium for neutron studies) absorption
curves were monitored during mechanochemical
synthesis. The reaction paths during mechanochemistrywere elucidated by means of ex-situ X-ray (XRD) and
Neutron Diffraction (ND) at RT. Reactivity of theintermediate Li3MgN2D phase towards deuterium gas
was studied during PCT measurements by in situ ND at
200°C. *

60

Li3-xMgN2D1+x

40

LiD





Li2Mg2N3D3Mg(ND2)2
LiND2

20

0




4

5

6

7

8

9

D-content (D/(2Li3N+Mg))

Fig. 1 The reaction mechanism during PCT (D2absorption isotherm at 200 °C) can be divided in threedomains: I) a solid solution Li3MgN2D o Li2Mg(ND)2; II) aphase transition Li2Mg(ND)2 o Li2Mg2(ND)3+ LiND2; III) aphase transition Li2Mg2(ND)3+ LiND2 o Mg (ND2)2"


Starting from 2Li3N+Mg powder mixture under H2, ex situ
XRD shows the formation of LiH and an amorphous
phase. Further heat treatment leads to the crystallizationof the Mg amide (I41/acd) at 160 °C. The overall reactionof the mechanochemical process is thus described by
2Li3N + Mg + 5H2 o amph-Mg(NH2)2 + 6LiH. However
the absorption curve indicates two reactions steps of 3.9
and 4.7 wt.% at 1 and 4 h of milling, respectively. The80[1] Palumbo, O.; Paolone, A.; Cantelli, R.; Chandra, D. Int.
J. Hydrog. Energy, 33 (2008) 3107.
[2] Chen, P.; Xiong, Z.; Luo, J.; Lin, J.; Tan, K. L. Nature,420 (2002) 302.

Dr. Fermín Cuevas obtained his PhD in Physics at Autonoma University of Madrid (Spain) in 1996.
After a postdoctoral position at the Max-Planck-Institute of Metals Research (Germany) he moved to
the Est Paris Institute of Chemistry and Materials Science (France) where he got a CNRS
permanent research position in 2002. His main research interest deals with hydrogen storage insolids, intermetallic compounds for Ni-MH batteries and nanostructured intermetallic compounds,
composites and hydrides for Li-ion batteries*

Fermin Cuevas
Corresponding author: Fermin Cuevas, cuevas@icmpe.cnrs.fr, +00 33 1 49 78 12 25

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYDROGEN IN NOVEL CARBON NANOSTRUCTURES
M. Gaboardi,1 C. Milanese,2 G. Magnani,1 P. Mauron,3 S. Duyker,4 V. K. Peterson,4 I.
Saldan,2 D. Pontiroli,1 P. Galinetto,5 M. Riccò.1
1 Department of Physics and Earth Sciences, University of Parma (Italy), 2 Department of Chemistry, University of Pavia(Italy), 3 École Polytechnique Fédérale de Lausanne (EPFL), Sion (Switzerland), 4 Australian Nuclear Science andTechnology Organisation (ANSTO) Sydney (Australia), 5 Department of Physics, University of Pavia (Italy).
A new class of hydrogen storage materials has taken hold in the last years: the so-called alkali-cluster intercalated
fullerides (AxC60n-, x  6, n < x). These compounds are able to uptake high amounts of hydrogen via a reversible
chemisorption mechanism at modest temperatures and dehydrogenation enthalpies. The hydrogen-sorption mechanism
investigation and the performance improvement are hereby presented.

Introduction
Finding new materials able to store hydrogen for mobile
and stationary applications is a challenge for the future
development of a hydrogen economy. Besides complex
hydrides, MOFs, or chemical hydrides, carbon basedmaterials are often studied, although their tendency tointeract with hydrogen is confined to weak van der Waals
forces. Otherwise, when carbon chemisorbs hydrogen,the generated covalent bond is too strong to guarantee
any reversibility. Not all this occurs in the case of alkalicluster
intercalated
fullerides(ACIFs),whereinmetastable C60-H covalent bonds can be reversibly
exploited to store high amounts of hydrogen with modest
dehydrogenation enthalpy. In this work, the synthesis, thestructural investigation and the hydrogen storage
mechanism of LiyC60, NayC60 and NaxLiy-xC60 mixed
phases will be discussed.

Experimental
ACIF compounds were synthesized by a 2-steps solidstate reaction between C60 and metal azides at 350450 °C. The hydrogen uptake studies were carried out ina manometric apparatus up to 100 bar H2 and 350 °C.
Thermodynamic features were investigated by DSC
analysis during hydrogen discharge under 1 bar H2. The
samples’ structural properties and the absorption
processes were investigated by means of  neutron
diffraction under 60 bar D2.

Results and Discussion
These materials were proved to reversibly absorb up to 5
wt% H2 at moderate temperature and pressure [1,2]through the catalytic effect of the intercalated
clusters.[3,4] We also identified some strategies to further
improve the absorption performance. On one hand, theaddition of catalysts (  Pt or Pd) improves the catalytic

activity towards hydrogen dissociation and allows toincrease the hydrogen absorption of Li6C60 up to 6 wt%
H2.[5] On the other hand, the destabilizing effect of Na inthe co-intercalated NaxLiy-xC60 compounds (where y = 6,
12; and 0.5  x  y) improves the hydrogen absorption
rate of about 67%, lowering at the same time thedesorption enthalpy from 66 to 49 kJ/mol,[6] making
these materials attracting for mobile applications.

Fig. 1: Hydrogenation process of Li6C60.[7]References[1] P. Mauron, M. Gaboardi,       37, 14307 (2012).
[2] P. Mauron, M. Gaboardi,     117,
22598 (2013).
[3] M. Aramini, M. Gaboardi,    67, 92 (2014).
[4] M. Gaboardi, C. Cavallari,    90, 130(2015).
[5] M. Aramini, M. Gaboardi,      39, 2124 (2014).
[6] M. Gaboardi, C. Milanese,   Manuscript in
preparation[7] M. Gaboardi, S. Duyker,     119,
19715 (2015).

Short CV:
Since 2011, first as Ph.D. student and later as a Post Doc, I worked at the Carbon Nanostructures
Laboratory at the Physical Department of Parma’s University. I gained the M.Sc. in Material Scienceand the Ph.D. in Physics at the same University in 2010 and 2014 respectively. My main research
activity is focused on the chemical and physical synthesis of metal decorated and intercalated
carbon nanostructures for energy storage and their structural and physical study.
Mattia Gaboardi
Corresponding author: Mattia Gaboardi, mattiagianandrea.gaboardi@fis.unipr.it, Tel. +39 0521 905209

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th

10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

Mg(BH4)2 – STUDIES OF ADDITIVES AND ISOTOPIC EXCHANGE
Bjørn C. Hauback, Olena Zavorotynska, Stefano Deledda
Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway
This work presents the effect of additives in magnesium borohydride, Mg(BH4)2. Different Ni-, Co-, Ti- and Mo-based
compounds have been ball-milled with J-Mg(BH4)2. By partial decomposition of Mg(BH4)2 it was found that it is possible
to re-absorb hydrogen at around 12 MPa and 250-280 qC. Gas-solid HoD exchange studies has indicated the ratelimiting steps for hydrogen desorption and absorption in Mg(BH 4)2.

2-

Introduction
Magnesium borohydride, Mg(BH4)2, is one of the mostpromising complex hydrides for energy related
applications. It has a high gravimetric hydrogen capacity(14.9 wt%), but hydrogen desorption kinetics
andreversibility present a challenge. There exists several
polymorphs, including the dense - and porous JMg(BH4)2 that irreversibly transform to the hightemperature -modification. The decomposition occurs
via several steps [1], and the resulting products andintermediates depend on the experimental conditions.
This work presents cycling studies with different additives
and in-situ studies of isotopic exchange in Mg(BH4)2.

absorption reaction rates. With Ni-additives, [B10H10]
seems to contribute to the reversibility. XAS experiments
clarified the changes in the Co-additives during thesorption process. In-situ Raman spectroscopy was used
to study gas-solid HoD exchange in Mg(BH4)2, and it
occurs already at 100 qC [6]. These results indicate thatthe solid-state H diffusion is the rate-limiting step forhydrogen desorption and absorption.

Acknowledgements
The Research Council of Norway, EU FP7 and ERA-NET
CONCERT-Japan are acknowledged for financial
support.

References

Experimental
Commercial J-Mg(BH4)2 was used as received The
composites of Mg(BH4)2 with additives were prepared byplanetary ball milling. All sample handling were carriedout in a glove box under purified Ar atmosphere. The
materials were characterized with a number of methods:
hydrogen desorption and absorption and kinetics studies
with a Sieverts-type apparatus, DSC-TGA, TPD, powder
X-ray diffraction both with laboratory source (PXD) andsynchrotron radiation at ESRF in Grenoble, France (SRPXD), X-ray absorption spectroscopy (XAS) including
XANES and EXAFS, in-situ Raman spectroscopy, ATR
1
11
FT-IR, and solid state H and B NMR.

Results
The decomposition and rehydrogenation of J-Mg(BH4)2ball milled with 2 mol% of different Ni-, Co-, Ti- and Mobased additives were investigated in details [2-5]. With Ni
additives it was found that partially decomposed material
is partial reversible with formation of crystalline Mg(BH4)2 at 10-15 MPa and around 250 qC, and with Co
the conditions for hydrogen absorption wereapproximately 12 MPa and 280 qC. The main effects of
the additives are to increase the desorption and[1] M.D. Riktor, M.H. Sørby, K. Chlopek, M. Fichtner, F.
Buchter, A. Züttel, B.C. Hauback, J. Mater. Chem. 17,4939 (2007)[2] I. Saldan, S. Hino, T.D. Humphries, O. Zavorotynska,
M. Chong, C.M. Jensen, S. Deledda, B.C. Hauback, J.
Phys. Chem. C 118, 23376 (2014)[3] O. Zavorotynska, I. Saldan, S. Hino, T.D. Humphries,
S. Deledda, B.C. Hauback, J. Mater. Chem. A 3, 6592
(2015)[4] O. Zavorotynska, S. Deledda, J.G. Vitillo, I. Saldan,
M.N. Guzik, M. Baricco, J.C. Walmsley, J. Muller, B.C.
Hauback, Energies 8, 9173 (2015)[5] I. Salan, C. Frommen, I. Llamas-Jansa, G.N.
Kalantzopoulos, S. Hino, B. Arstad, R.H. Heyn, O.
Zavorotynska, S. Deledda, M.H. Sørby, H. Fjellvåg, B.C.
Hauback, Int. J. Hydrogen Energy 40, 12286 (2015)[6] O. Zavorotynska, S. Deledda, G. Li, M. Matsuo, S.-I.
Orimo, B.C. Hauback, Angew. Chem. Int. Ed. 54, 10592(2015)

Bjørn C. Hauback is Department Head and Chief Scientist of the Physics Department, Institute forEnergy Technology 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 structureproperty relationships of hydrogen storage materials and neutron diffraction. He is a member ofNorwegian 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.
B.C. Hauback
Corresponding author: Bjørn C. Hauback, bjorn.hauback@ife.no, tel: +47 97 40 88 44.

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10thInt. Symposium "Hydrogen &Energy"

Sendai, JAPAN2016

REVERSIBLE HYDROGEN SORPTION FOR THE INFILTRATEDMAGNESIUM BOROHYDRIDE
C. Milanese1, I. Saldan1, A. Girella1, G. Valsecchi1, E. Cabrini1, P. Pallavicini1, P.
Galinetto2, M. RuedaNoriega3, A. Martin3, D. Pontiroli4, M. Gaboardi4, G. Magnani4, M.
Riccò4, A. Marini1
1 Pavia Hydrogen Lab&inLab, Chemistry Dept., University of Pavia, Italy,2 Physics Dept., University of Pavia, Italy, 3High Pressure Processes Group, Chemical Engineering and Environmental Technology Dept., University of Valladolid,
Spain, 4 Carbon Nanostructures Lab, Physics and Earth Science Dept., University of Parma, Italy
Abstract
In this work, we summarize our findings on magnesium borohydride nanoconfinement as a way to improve thereversibility and the kinetics of the H2 sorption reactions of this complex hydride. Both solid-statehigh-pressure and wet
chemistrymethods are tested as samples preparative procedures. Pure and transition metals decorated silica and C
based materials (graphene; CMK; MWCNT) are used as suitable matrices. Different preparation methods for thescaffolds and different matrices– active phases’ ratios are explored in the attempt to find the most performing system
concerning H2 storage. Silica matrices give the best results in terms of gravimetric capacity and reversibility.

Introduction
Magnesium borohydride is a very high-capacity hydrogencomplex hydrides (14.84wt% of H2) althoughits H2
sorptionreversibility
remainsachallenge.
Thermodynamics of Mg(BH4)2 dehydrogenation is
calculated to be near ideal for effective hydrogen storage,
but experiments reveal competing decomposition
pathways with the formation of very stable intermediates
limitingthe lifecycle. In practice, 11 wt% H2reversibilitywas
demonstrated forvery high pressures and temperatures[1], while only 2.5 wt% H2 at reasonable conditions [2].
Solid-state synthesis of Mg(BH4)2 has been developed [3]and decomposition products have been identified, as wellas methods to improve hydrogen sorption performance,
including catalysts addition [4,5]. It is known that both thereversibility and the kinetics of the complex
hydridessorption reactions can be improved by nanoencapsulation. Therefore, nano-engineering to introduce
Mg(BH4)2 as nanoparticles in highly porous materials andavoid their aggregation during hydrogen cycling might asolution [6,7].

Experimental
Solid statehigh-pressure encapsulation is attained byheating the silica matrices, produced as in [8],and theborohydride within a manometric apparatus up to 300 °C
at 110 bar of H2 for 6 h.Impregnation is performed bywetting the matrices and dissolving the borohydride in
THF under N2 flux and subsequently removing thesolvent by heating at 70 °C. The ex-situ BET, XRPD and
Raman spectroscopy help to understandthe success andextent of the used encapsulation. The thermodynamic
features of the systems are explored by high pressure bycycling the samples in the manometric apparatus undervacuum/up to 110 bar for des/absorption at thecharacteristic temperatures, previously found by the DSC
measurements.

Results and Discussion
The silica – borohydride systems are quite promising,showing gravimetric capacity close to the theoreticalvalues and improvedreversibility to our best knowledge.
The desorption kinetics still needs improvement: work isin progress to decorate the silica matrices with a suitable
catalyst for reversible hydrogen sorption. C-basedmaterials seem not suitable as scaffolds due to evident
reactions with the borohydride already at the firsthydrogen cycle, even at around 200°C.

References[1] G. Severa, E. Rönnebrow and C.M. Jensen, Chem.
Commun., 46, 421 (2010).
[2] M. Chong, A. Karkamkar, et. al., Chem. Commun., 47,
1330 (2011).
[3] C. Pistidda, S. Garroni, et. al.,J. Alloys and Comp.,
508, pp.212–215, (2010).
[4] I. Saldan, S. Hino, et al., J. Phys. Chem. C 118,
23376 (2014).
[5] O. Zavorotynska, I. Saldan, et al., J. Mater. Chem. A
3, 6592 (2015).
[6] M. Fichtner, Nanotechnology, 20, 204009(2009).
[7] S. Sartori, K.D. Knudsen, et al., Nanotechnology, 20,505702 (2009).
[8] M.Rueda, L.M.Sanz-Moral, et al., J.of Supercritical
Fluids 92, 299 (2014).

Chiara Milanese is Associate Professor at the Chemistry Department of the Pavia University andscientific responsible for the Pavia Hydrogen Lab, that is active since 2006 in the ideation,
preparation and characterization of innovative materials for solid state hydrogen storage. Her main
research activities concern the physico-chemical characterization of materials for energy storage, i.e.
in H2fuel cell, Li – ion batteries and photovoltaic applications. She is author of more than 100 papers
on highly specialist journals on the above quoted topics and she collaborates in more than 150
presentations at national and international conferences. She is member of national and international
associations having as the main topic the study of materials for solid state hydrogen storage.

Chiara MilaneseCorresponding author: Chiara Milanese, chiara.milanese@unipv.it, Tel. +39 0382 987557

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

# !7 "  8-9&:8;<+=- # 
#0
Anna-Lisa Chaudhary1, Magnus SØrby2, Fahim Karimi1, Stefan Börries1, , Guanqiao Li3,
Mokoto Matsuo3, Shin-ichi Orimo3,4, Stefano Deledda2, BjØrn Hauback2, Claudio Pistidda1,
Thomas Klassen1, Martin Dornheim1
Affiliations: 1 Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Germany; 2 Institute for Energy Technology,
Norway, 3 Institute for Materials Research, Tohoku University, 4WPI-Advanced Institute for Materials Research, Tohoku
University
Abstract
Complex hydrides are very promising hydrogen-storage materials, due to their high gravimetric and volumetriccapacities. Presented here is a reactive hydride composite of Mg2FeH6 combined with the light metalborohydride Mg(BH4)2 characterised by different synchrotron techniques. Several photon sources were used toinvestigate this system in detail, including  powder X-Ray diffraction (PXRD) (SNBL, ESRF, France), X-ray
Absorption Near Edge Structure (XANES), Extended X-Ray Absorption Fine Structure (EXAFS) (Diamond Light
Source, UK) and X-ray micro-tomography (DESY, Petra III, Germany). Due to the sensitive nature of hydrogenstorage materials to both oxygen and moisture, each of these techniques had limitations and required specificadaptations to accurately measure physical and chemical properties of the Mg2FeH6 / Mg(BH4)2 composite
system. An overview of each technique with relation to the measurement of hydrogen storage materials as wellas the analysis for the specific example of Mg2FeH6 / Mg(BH4)2 is given.





Reactive hydride composite (RHC) systems areinteresting to study as the interaction between the twophases can result in improved physical properties forhydrogen storage applications compared to theirindividual counterparts. One such system is Mg2FeH6
combined with Mg(BH4)2. The desorption behaviour of
this system, at a specific anionic ratio, showed
simultaneous desorption of the two hydrides, which
resulted in a single event of hydrogen release1. To gain
an in depth understanding of the reaction pathway for this
RHC, several photon source techniques were used toinvestigate the Mg(BH4)2-Mg2FeH6 in detail. The results
are presented here.

The results showed interesting behaviour for the
Mg2FeH6 / Mg(BH4)2 system before and after desorption
including the details regarding the reaction pathway
during heating, the existence of Fe-B complexes and thespatial distribution of the element Fe within the RHC
system.

.0Firstly,   PXRD measurements were done at the
Swiss-Norwegian Beam Line (SNBL, BM01A ESRF,
France). A range of samples were also measured at theK-edge of Fe (7.112 keV) at the B18 beamline at the
Diamond Light Source (Oxfordshire, UK) for XANES and
EXAFS. Finally, the P.05 beamline was used at PETRA
III, DESY (Hamburg, Germany) for 3-D synchrotron
radiation tomography. Each of the techniques used
specialised sample holders to ensure there was nocontamination from neither oxygen nor water.

Dr. Anna-Lisa
ChaudharyFig. 1: In situ PXRD of Mg2FeH6 / Mg(BH4)2 results from the
SNBL, ESRF,  = 0.80607 Å.

"
[1] Chaudhary et. al. Appl. Phys. Lett. $*, (7), 073905(2015).

Anna-Lisa has a background in chemical engineering including a Master’s degree from the
University of Queensland, Australia. After working for the international company, Plantic
Technologies Limited as a product development engineer, she then went on to complete a Ph.D. in
the Physics Department at Curtin University, Australia. Since 2013, she has been working as a
research scientist at the Helmholz Zentrum Geesthacht in Germany with strong collaborations with
Tohoku University, Japan, Institute for Energy Technology, Norway and Aarhus University,
Denmark. Anna-Lisa has a number of peer reviewed publications in the area of solid state hydrogenstorage and more recently attended international conferences for oral presentations as an invited
speaker (SMEC 2015, EMRS 2015).

Corresponding author: Dr. Anna-Lisa Chaudhary, anna-lisa.chaudhary@hzg.de, +49 4152 87 2647

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

QUATERNARY MG-BASED TRANSITION-METAL COMPLEX HYDRIDESPRODUCED BY REACTIVE MILLING
S. Deledda1, O. Zavorotynska1, B.C. Hauback1
1 Physics Department, Institute for Energy Technology, Kjeller, Norway
In this work, we employed ball milling in a reactive H2 or D2 atmosphere to explore the possibility of producing quaternary
Mg-based transition-metal complex hydrides. The results focus on Mg-Fe-Co, Mg-Mn-Fe, and Mg-Fe-Ni systems andwere compared with data for ball milled Mg-Co-Ni. The aim is exploring if: i) different transition-metal complex anions,such as [FeH6]4 - and [CoH5]4 -, can coexist in the same crystalline structure and ii) the presence of [FeH6]4 -, [CoH5]4 -, or[NiH4]4 -anions can stabilize the [MnH6]5 – complex.

Introduction

Results and Discussion

Ball milling techniques are considered beneficial forprocessing potential hydrogen storage materials. This is
due
to
the
possibility
tomechanicallymixelements/compounds at an atomic scale, extend the solid
solubility of metals and, in turn, obtain novel materials
that might show interesting hydrogen storage properties.
In this work, we employed ball milling in a reactive H2 (orD2) atmosphere with the aim of exploring if: i) different
4transition-metal complex anions, such as [FeH6] and4[CoH5] , can coexist in the same crystalline structure and444ii) the presence of [FeH6] , [CoH5] , or [NiH4] anions
5–
can stabilize the [MnH6] complex, which is observed in
Mg3MnH7 prepared at high pressure (2 GPa) andtemperature (800 K) [1].

Quaternary Mg-based transition-metal complex hydrides
phases with different transition-metal complex anions cancoexist in the same crystalline structure and areobserved when elemental powder mixtures MgTM’TM’’(TM’, TM’’ = Fe, Co, Ni, Mn) are ball milled in a reactivehydrogen atmosphere.

Experimental methods and Results
Elemental powder mixtures MgTM’TM’’ (TM’, TM’’ = Fe,
Co, Ni, Mn) were ball milled in H2 or D2 at about 50 bar.
The structural characterization of the powders was
carried out by X-ray and neutron powder diffraction
analysis and vibrational spectroscopy (i.e. IR). The
thermal stability and the hydrogen sorption behaviour
were investigated by differential scanning calorimetry andthermal programmed desorption. In-situ powder
diffraction was carried out to follow the structural changes
upon heating and hydrogen desorption.

StefanoDeleddaThe quaternary hydrides generally adopt a K2PtCl6-type
structure (space group 3) [2]. Strong changes in thelattice parameters of the cubic quaternary hydrides areobserved depending on the starting elemental powder
mixture. Experimental data suggest that the disorderedsolid solutions of the transition-metal complex anions in2+
the Mg sub-lattice display large solubility gaps, except
when Mn is among the starting materials
The relative content of the complex anions could be used
to tune the properties of the quaternary Mg-basedtransition-metal complex hydrides, e.g. with respect totheir hydrogen desorption temperature

References[1] M. Bortz, B. Bertheville, K. Yvon, E.A. Movlaev, V.N.
Verbetsky, F. Fauth, J. Alloys Comp. 279 (1998), L8-L10[2] S. Deledda, B.C. Hauback, Nanotechnology, 20(2009) 204010

Dr. Stefano Deledda received his Master in Chemistry from the University of Sassari, Italy, and his
PhD in Chemistry from the Dresden Technical University, Germany. He has a 15-year-longexperience in the synthesis and characterization of metastable and nanocrystalline alloys andcompounds processed by non-equilibrium techniques. At IFE since 2005, his research activities
include the synthesis of complex hydrides, multicomponent alloys and composites by ball milling andtheir structural and thermodynamic characterization. He has authored and co-authored more than 50
publications. He is now project responsible for the construction of the new high-resolution neutron
powder diffractometer, work-package leader in an EU Project on hydrogen storage materials(BOR4STORE) and scientific contact for one on advanced magnetic materials (NANOPYME).

Corresponding author: Stefano Deledda, email: Stefano.deledda@ife.no, Tel.: +47 407 26 921

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SOLVENT-FREE SYNTHESES OF METAL DODECABORATES FOR
ENERGY APPLICATIONS
Hai-Wen Li1,2, Liqing He3, Son-Jong Hwang4, Yaroslav Filinchuk5, 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 Division of Chemistry and Chemical Engineering, California Institute of Technology, 5 Institute of Condensed Matterand Nanosciences, Université catholique de Louvain
Systematic investigation of the thermal decomposition behavior for metal dodecaborate M2/nB12H12 is of great importanceto understand its role in the dehydrogenation of metal borohydride M1/nBH4. Anhydrous M2/nB12H12 has been successfully
synthesized via a novel solvent-free process, i.e. sintering of M1/nBH4 and B10H14. Thermal decomposition of M2/nB12H12
tends to experience multistep pathways with the formation of H-deficient monomers M2/nB12H12-x containing icosahedral
B12 skeletons and followed by the formation of (M2/nB12Hz)n polymers.

Introduction
Metal borohydrides M1/nBH4 with approximately 10
mass% of hydrogen capacity, generally show stepwise
decomposition accompanied with the formation of
2intermediates containing polyanions, like [B2H6] , [B3H8]
and/or [B12H12]2- [1]. The [B12H12]2- intermediate, having
strong B-B bonds in a stable icosahedral boron cage, hasbeen widely regarded as an obstacle for therehydrogenation to borohydrides [1]. Fundamental
investigation on the thermal decomposition of M2/nB12H12,
therefore, is in great need to elucidate its role in thedehydrogenation of borohydrides.

polymers (see an example of MgB12H12 in Fig. 1). This isfairly different with those in situ formed M2/nB12H12 during
the dehydrogenation of corresponding borohydrides [3,5].

11

Results and Discussion
Several anhydrous M2/nB12H12 (M = Li, Na, K, Mg, Ca,
LiNa) have been successfully synthesized by sintering of
M1/nBH4 and B10H14 with the stoichiometric chemicalcompositions [2-4]. The thermal decomposition ofanhydrous M2/nB12H12 proceeds in two steps: (1)dehydrogenate to produce H-deficient M2/nB12H12xcontaining the icosahedral B12 skeletons and (2)polymerization of M2/nB12H12x to form (M2/nB12Hz)nPolymers(MgB12Hz)n700 ºC
800 ºC30 20 10

Starting materials of M1/nBH4 and B10H14 were firstly
mechanically milled for 5 h at room temperature and thenwere sintered in order to synthesize anhydrous
M2/nB12H12. Decomposition pathway was examined bythermogravimetry, mass spectrometry, X-ray diffraction,
Raman and nuclear magnetic resonance (NMR).

H-deficientmonomers
MgB12H12-x
200 ºC
400 ºC

Experimental

Hai-Wen LI

MgB12H12B MAS NMR
Z = 16kHz

0 -10 -20 -30
ppm

Amorphous B

Fig. 1 Thermal decomposition of MgB12H12 forms Hdeficient monomers MgB12H12-x and then (MgB12Hz)n11
polymers examined by solid B MAS NMR.

References[1] H.-W. Li et al.,    4, 185 (2011)[2] L. He et al.,   118, 6084 (2014)[3] L. He et al.,   44, 15882 (2015)
[4] L. He et al.,    27, 5483 (2015)[5] L. He et al.,   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

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10thInt. Symposium "Hydrogen & Energy"

Sendai, JAPAN2016

##"8-:<#
Liuzhang Ouyang* Miaolian Ma, Min Zhu
School of Materials Science and Engineering and Key Laboratory of Advanced Energy Storage Materials of Guangdong
Province, South China University of Technology, Guangzhou, 510641, People’s Republic of China
Abstract
MgH2 appears to be an attractive candidate for hydrogen generation due to the advantages of low cost, abundant in thecrust, high theoretical H2 generation yield, and hydrolysis byproduct friendly to environment. While the hydrolysis reaction
rate of pure MgH2 with water declines quickly due to the formation of passivation layer Mg(OH)2. To improve thehydrolysis properties of MgH2-based hydrides, ball milling, synthesis of MgH2-based composites, and tuning of thesolution composition are applied. The formation of a composite system, such as the MgH2/LaH3 composite, through ball
milling and in situ synthesis, can improve the hydrolysis properties of MgH2 in pure water. Furthermore, the addition of Ni,
Co or Al to the MgH2/LaH3 composite resulted in the development of LaH3/MgH2/(NiCoAl) composites. Moreover, theyield rate for the hydrolysis of MgH2 was controlled by manipulation of the particle size via ball milling and by optimizing
the solution. The hydrogenation yield of MgH2 reached 1711.2 mL/g of H2 in 10 min at 298 K in the 27.1% ammonium
chloride solution with hydrolytic conversion rate being 99.5%..


In recent years, more and more attention has been
paid to hydrogen generation by hydrolysis of metals or
metal hydrides for their high theoretical hydrogen yieldand the generated high purity hydrogen can be passed
directly into the cells as fuel [1]. MgH2 appears to be an
attractive candidate for hydrogen generation due to theadvantages of low cost, abundant in the crust, hightheoretical H2 generation yield, and hydrolysis byproductfriendly to environment. However, the hydrolysis reactionof MgH2 is rapidly interrupted because of the formation ofa passive magnesium hydroxide layer.

at 298 K in the 27.1% ammonium chloride solution, andthe hydrolytic conversion rate reached the value of 99.5%.
Furthermore, the hydrolysis of ball-milled MgH2 produced
1,137 mL/g in 90 min at 298 K in the 0.05 mol/L MgCl2
solution, whereas the hydrolysis in pure water wasinterrupted.

.030
The starting materials of Mg-RE alloys were preparedby induction melting. The hydrolysis reactions of the
MgH2 based composite were carried out in a 250 mL
Pyrex glass reactor with three openings according to apreviously described method [2]. The hydrogengeneration rate and yield can be calculated from thereaction time and hydrogen volume, which wasmeasured and analyzed by the computer. Eachexperiment test was repeated at least two times in order
to confirm its reproducibility.


Fig.1 shows The hydrolysis kinetics of MgH2 indifferent concentrations of ammonium chloride solution.
This result confirms that the hydrolysis speed can becontrolled by adjusting the solution concentration. The
hydrolysis of MgH2 produced 1,711 mL/g of H2 in 10 min

Fig. 1 ! ## ? " 8-  ""
"000@"
[1]M. Matsuo, S. Orimo, Adv. Energy Mater.1, 161 (2011)[2]L.Z. Ouyang et al, Int. J. Hydrog. Energy.24, 34(2009)

Short CV: Liuzhang Ouyang is Professor and Head of department of metallic materials science andtechnology at South China University of Technology. He received his B.S. in Metallic Materials from
Yanshan University at Hebei province in 1994. Professor Ouyang received his Ph.D. from South
China University of Technology (SCUT) in 2001 and joined SCUT faculty in 1987. Current research
projects focus on hydrogen storage and hydrogen generation materials of light metal hydrides, lightmetal complex hydrides and their composites, La-Mg-Ni-based hydrogen storage, nickel/metal
hydrides (Ni/MH) secondary batteries electrode alloys etc.. Prof. Ouyang has already publishedmore than 100 papers in important journals such as APL,
JPCC, Acta Materialia etc..
Liuzhang Ouyang

Corresponding author: Liuzhang Ouyang, email:meouyang@scut.edu.cn, Tel: 86-20-87114253

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYDROGEN SORPTION KINETICS IN MAGNESIUM AND TITANIUMHYDRIDE THIN FILMS
Efi Hadjixenophontos, Lukas Michalek, Guido Schmitz
Institute of Material Physics, University of Stuttgart, Heisenbergstrasse 3, 70569 Stuttgart, GERMANY
Abstract Magnesium hydride (MgH2) has been extensively studied over the last decades because of its great potential forhydrogen storage. Recent studies have focused on improving this property by mechano-chemical treatment, addition oftransition metals (TM) and reduction of the crystallite size. However, hydrogen diffusion remains a challenging fundamental
problem. In this work, we compared the H-sorption behaviour at low temperatures for MgH 2 and titanium hydride (TiH2),
and study the influence of TM additives. Pd and Ti were exploited to improve both dissociation of H2 molecules anddiffusion of H atoms in the material. Thin films were deposited in order to quantitatively determine diffusion coefficients andmeasure kinetic barriers at the interfaces. A main focus here is the comparison of these properties between TiH 2 and MgH2.

Introduction
Magnesium and titanium hydrides are of great interest in
the context of hydrogen storage [1]. Mg, in addition to its
abundance and low cost, can reversibl
    hydrogen (H). Nevertheless, it suffers from slow kinetics,
which impedes performance and makes it functional atonly high temperatures. The use of transition metals isknown to improve kinetic properties. In thin film geometry,these materials are also interesting as optical switches.
Despite the extensive work on hydrogen materials vis-avis diffusion, there is still a lack of reliable experimental
data on these important systems. Therefore, we focus on
H-absorption and desorption mechanisms in low
temperatures and quantify important transport parameters.

vaporize upon hydrogenation [3] at a lower thickness.
Complete hydrogenation of the Mg films can be observed
after annealing at 300°C, 10 bar of H-atmosphere and240min if a Pd layer is catalysing the process. Then the
MgH2 (110) plane appears parallel to the basal plane ofMg (fig1-       !-TiH2 phase (111)thin film [2] up to 600°C shows the decrease of the c lattice
parameter towards lower values (fig1-right) as expected
when hydrogen atoms leave the structure. Quantitative
measurements and evaluation at different temperatures
will be presented that allow determination of diffusivity andsurface reaction coefficients.

Experimental / Computational
Both materials were deposited using ion beam sputtering
at a pressure of 10-4 mbar on Si and SiO2 substrates, witha thickness of 50-400 nm. Hydrogenation of these layers
followed at temperatures up to 300°C under 1-10 bar of H
atmosphere for different durations. Dehydrogenation was
done in a fast annealing oven step of 5s. Microstructuralchanges were studied by TEM (PHILIPS CM200) andhydrogen sorption was quantified by XRD (SIEMENS
D5000).

Results and Discussion

References[1] L.Schlapbach, A.Zuttel, Naturl 414 (2001) 535[2] Mingwang Ma et al. Intern. Journal of H energy (2015)  -Ti epitaxial thin films have a pronounced texture
with the dense packed planes of the hcp structure, and the(002) plane parallel to the substrate. Experiments with Mg
focus on thicknesses over 200nm, since Mg seems to

Efi
Hadjixenophontos

Fig. 1 Left: Mg thin films as deposited and hydrogenated. Right:
Dehydrogenation of TiH2 from RT to 600°C and change in the lattice
parameter over dehydrogenation[3] Yi-Kui Liu et al. Appk. Phys. Lett 78 (2001)[4] A. Pundt Acta Materialia 82 (2015) 279-289

I grew up in Cyprus and after high school, I moved to France to start my studies in physicalchemistry in Montpellier. After French, I added English to my science skills through MESC, an   " # $    % &% '( )  '( ) )"   "  science, while working at various European universities. During my " # *  )  )
president for my teamwork skills and ability to manage and coordinate the multi-lingual/multi-culturalgroup.  )" ) +  % %   (   " " # (,) 
created for me in Montreal, Canada, working on modified carbons and ionic liquids forelectrochemical 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.

Corresponding author: efi.hadjixenophontos@mp.imw.uni-stuttgart.de +49 711 685 61984 http://www.ecostore-itn.eu㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

ENERGY EFFICIENCY OF MGH2-BASE HYDRIDE AND NaBH4HYDROLYSIS CYCLE
Hao Zhong1, Liuzhang Ouyang1, 2 *, Min Zhu1, 2
1 School of Materials Science and Engineering and Key Laboratory of Advanced Energy Storage Materials of
Guangdong Province, South China University of Technology, Guangzhou, 510641, People’s Republic of China
2 China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology,
Guangzhou, 510641, People’s Republic of China
Abstract
In this work, the energy efficiency of the hydrolysis and regenerating process is determined through thermodynamics
calculations method and the value is 45.3%, 40.1%, 41.1% and 53.7% for MgH2, H-Mg3La, H-La2Mg17 and NaBH4,
respectively. In addition, NaBH4 was regenerated successfully by a convenient method of ball milling NaBO2 with HMg3La. On the other side, the enhanced hydrolysis performance of La2Mg17-Ni hydrides produced by ball milling La2Mg17
and Ni under H2 at room temperature was also discussed.

Introduction
The previous studies have proposed that NaBH4 [1],Mg3La hydrides and La2Mg17 hydrides [2] are excellent
hydrolysis materials. To further confirm their energy
efficiency, we calculated their energy efficiency of thehydrolysis cycles according to thermodynamics
calculation method. The convenient regenerating processof NaBH4 hydrolysis was developed through the reactionof NaBO2 ball milled with hydrogenated Mg3La (H-Mg3La)
or hydrogenated La2Mg17 (H-La2Mg17).

Experimental / Computational
Enthalpy change of endothermic reaction in the cycle isregarded as the input energy and Gibbs free energy ofwater is regarded as the output energy. Energy efficiency
is the ratio of these two values. The reaction of NaBO2
and H–Mg3La was achieved by ball milling 20h andLa2Mg17 and Ni was ball milled under 7MPa H2. The
products were investigated by XRD and FTIR.

Results and Discussion
Fig. 1 shows the hydrolysis and regenerating cycle of H–
La2Mg17 and NaBH4. The energy input in and output fromthese cycles is 722.67 kJ and 237.1 kJ, 475.05 kJ and
237.1 kJ, while the energy efficiency of such cycles is
41.1% and 53.7%, respectively. Judging from the XRD
pattern of the NaBH4 regeneration reaction as shown in
Fig.2, MgH2 reacted completely with NaBO2 for the firststep and then part of LaH3 reacted with the remaining
NaBO2 to form NaBH4, and the left part transformed to
LaH2. After 20h ball milling, the peak belonging to NaBH4
is found in the XRD pattern. On the other hand, the ballmilled La2Mg17 and Ni is almost hydrogenated and the
products show excellent hydrolysis performance withhydrogen yield being 1208 ml g1 hydrogen in 40 min at
25°C. The enhanced hydrolysis may be resulted from theparticle refinement during the ball milling process andcatalysis of LaH3 and Ni.

Fig. 1 The path of (a) H–La2Mg17 hydrolysis cycle(b) NaBH4 hydrolysis cycle

Fig. 2 XRD patterns ofFig. 3 Curves of La2Mg17–(a) the NaBO2-Mg3La hydride Ni hydrides hydrolysis
mixture and the product afterball milling the NaBO2-Mg3La
hydride mixture for (b) 0.5h(c) 3h (d) 5h (e) 10h (f) 20h

References[1] W.Y. Chang, P.J. Carroll, L.G. Sneddon, J. Am. Chem.
Soc. 131, 855-864 (2009).
[2] L.Z. Ouyang, Y.J. Xu, H.W. Dong, L.X. Sun, M. Zhu.
Int. J. Hydrogen Energy. 34, 9671-6(2009).

Hao zhong was born on April 1991 in Guangzhou, China. 2013 Bachelor in Department of Materials,
South China University of Technology, Guangzhou, China. His major is Metallic Materials Scienceand Engineering. Currrently he is a D.S candidate at the Key Laboratory of Advanced Energy
Storage Materials of Guangdong Province.
His research interest is focused on regeneration of NaBH4.

Hao ZhongCorresponding author: Liuzhang Ouyang, meouyang@scut.edu.cn..

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

PREPARATION AND HYDROGEN STORAGE PROPERTIES OF Mg/
(=Ti,Nb) THIN FILMS BY MAGNETRON SPUTTERING
Jiangwen Liu, Wencheng Huang, Jun Yuan, Hui Wang, Liuzhang Ouyang, Min Zhu
School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong
Province, South China University of Technology, Guangzhou 510640, China
Abstract
The transition metals(TM) and their oxides can catalyze the Mg/MgH2 reaction effectively. We designed and fabricateddifferent Mg/TMs or their oxides (TMOx,TM=Ti, Nb) multilayer Mg/TMOx films by means of magnetron sputtering, andstudied the effects of the TMOx catalytic layer features and variable multi-valence on the dehydrogenation kinetics of MgTMOx-H films, then discussed TMOx multi-valence catalytic mechanism.

Introduction
Magnesium is a type of promising hydrogen storage alloy
with high hydrogen capacity and reversibility. However,the Mg hydride is thermodynamically stable and difficult
to be dehydrogenated under moderate conditions. In thiswork we intend to prepare the different and controllable
Mg/TMOx(TM=Ti, Nb) multilayer films using magnetron
sputtering, and to study the effects of the structure andcomposition of film, TMOx catalytic layer, and TMOx multivalence on the desorption kinetics of Mg-based film.

hybrid type (Nb2O5+Nb)/Mg/(Nb2O5+Nb) catalyst layers
presented better dehydrogenation properties than that ofmultilayer films with pure Nb or with pure Nb2O5 catalyst
layer. These results are related to not only the special
nanostructure of the multilayer films but also the catalysis
of Ti and Nb with variable multi-valences which promoted
the electron transfer thus speeded up the MgH2/Mg
reaction.

Experimental
A serial of Mg/TMOx multilayer nanofilms were preparedusing magnetic sputtering methods. The deposition
processes, microstructures and dehydrogenation kinetic
properties of Mg/TiOx (X=0~2) and Mg/NbOx (X=0~2.5)
films were studied.

Results and Discussion
The results indicated that the thickness, surface
morphology, and grain size, density of Mg/TMOx
multilayer films varied with sputtering power. The
preferred growth orientations of Mg and Ti were [001]and <100>, respectively.The TiO2/Mg/Ti type film
presented lower dehydrogenation temperature than the
TiO2/Mg/TiO2 and Ti/Mg/Ti films (Fig.1). Also the multivalence (TiO2+Ti)/Mg/(TiO2+Ti) film prepared by (TiO2+Ti)
hybrid target showed more excellent dehydrogenation
kinetics and lower dehydrogenation temperature than the
TiO2/Mg/TiO2 and Ti/Mg/Ti films with only pure Ti or pureTiO2 single valence catalyst layer.
The dehydrogenation kinetics properties of Mg/NbOx
multilayer films were similar to that of Mg/TiOx films. The
Mg/NbOx films with sandwich type Nb2O5/Mg/Nb or with

Fig.1 TPD-MS curves of Mg/TiOx-H multi-layer films

Acknowledgements
The authors are grateful to the NSFC(5157010144) andGNSF(2014A030313222).

References[1] J. Cui, H. Wang, J. Liu, L. Ouyang, Q. Zhang, D. Sun,
X. Yao, M. Zhu, J. Mater. Chem. A1, 5603(2013)[2] G. Xin, J. Yang, C. Wang, J. Zheng, X.Li, Dalton
Trans. 41,6783(2012)

Dr. Jiangwen LIU is a professor at School of Materials Science and Engineering, South China
University of Technology. He received BEng and MEng degree from Shanghai Jiaotong University,and completed his PhD at School of Mechanical Engineering of SCUT in 1998. His current research
is focused on Mg-based hydrogen storage materials and electron microscopy analysis of energy
materials.
Jiangwen LIU

Corresponding author: Jiangwen LIU, Email: mejwliu@scut.edu.cn Tel:+86-20-39380575

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

BOR4STORE – BORON BASED METAL HYDRIDES FOR HYDROGEN
SUPPLY OF SOFC
1
K. Taube1, C. Pistidda, G. Capurso1, J. M. Bellosta v. Colbe1, M. Dornheim1, T. Guerrero Cervera2, D.
Márquez Gómez2, I. Castellano2, H. Zoz3, D. Yigit3, R. Keder4, M. Krovácek4, T. R. Jensen5, B. Richter5,5
B. R. S. Hansen, P. Javadian5, S. Deledda6, B. Hauback6, O. Zavorotynska6, M. Baricco7, E. Albanese7,
E. Pinatel7, A. Züttel8, A. Borgschulte8, N. Stadie8, G. Charalambopoulou9, A. Stubos9, T. Steriotis9, A.
Yiotis9, M. Kainourgakis9

Affiliation 1Helmholtz-Zentrum Geesthacht, Geesthacht, Germany; 2 Abengoa Hidrógeno, Sevilla, Spain; 3Zoz GmbH,
Wenden, Germany; 4Katchem spol, Prague, Czech Republic; 5Aarhus University, Denmark; 6IFE, Kjeller, Norway;
7
University of Turin, Italy; 8Empa, Dübendorf, Switzerland; 9NCSR “Demokritos”, Athens, Greece
In the frame of the FCH JU project BOR4STORE – “Fast, reliable and cost effective boron hydride based high capacity
solid state hydrogen storage materials” (grant 303428), a broad range of metal borohydrides and composites were
investigated, with the target of developing a metal hydride tank to be thermally integrated with a high temperature solidoxide fuel cell (SOFC). The hydrogen sorption properties and reaction pathways of these materials were characterised,accompanied by   and thermodynamic calculations, to achieve a fundamental understanding of reaction
mechanisms, structural changes, thermodynamics and kinetics. After screening various types of materials, one boron
based hydride system was selected for the tank. The tank integrated with an SOFC will be tested in early 2016. .

Introduction
BOR4STORE (www.bor4store.eu) was a European
project with the target of a) investigating various kinds ofhigh capacity boron hydride based hydrogen storage
materials and b) selecting the most suitable for a metal
hydride tank to be thermally integrated with a SOFC. A
prototype of such an integrated system was constructed.

application in this materials class. Selected results fromthe different materials systems will be presented.
*****************************************************************

Experimental
In a broad approach, several single and multi-cation
borohydrides, both stable and unstable at RT,
Eutectically Melting and Reactive Hydride Composites(EMC, RHC) and materials infiltrated in nanoscaffolds,
were synthesised and characterised. This was supportedby  and thermodynamic modelling.
The selection criteria of the “best” material were basedon (i) a hydrogen capacity of t 8 wt.%, t 80 kg H2/m3, (ii)a hydrogen release temperature of < 450°C, (iii) a
reaction enthalpy of < 40 kJ/(mol H2), (iv) loadable to full
capacity in less than 1 hour with (v) a high stability ofcapacity over several tens of loading and unloading
cycles, and with (vi) the potential for reaching competitive
cost benefits compared to compressed hydrogen stores
under mass production conditions.
Among all boron based storage materials investigated in
BOR4STORE, only the Lithium based Reactive HydrideComposite 2LiBH4-MgH2 (Li-RHC) exhibited the required
combination of properties. For this material, a reactive
ball milling process for synthesis was established on an
8l-vial-mill (CM08, ZOZ), operating with inert atmospherein the milling vial only, but not in a glove box.
A test tank and a suitable heat transfer system with gas
as the transfer medium was constructed, to be tested inearly 2016.

Results and Discussion
The experimental data showed that currently the Li-RHC
system, Mg(BH4)2 and EMCs infiltrated into nanosized
scaffolds have the highest potential for practical    !"  ! !   # 
 !$ $   %   "  &'

Outlook
BOR4STORE has shown, that borohydride basedhydrogen storage materials have the potential to be used
for supply of SOFCs and in SOEC/SOFC P2P systems,
needing only the off-heat of the SOCs for heat supply tothe tank during hydrogen release. Still, for future practicalapplications, especially issues of, the cost of raw
materials (currently ca. 4000 €/kg of stored hydrogen),the cost of steel for tank construction (focus on lowering
temperature of operation and loading pressure forcheaper steel), significantly improving system capacity(currently < 1 wt.%, < 20 kg H2/m3) and establishing an
industrial process chain from raw materials to integrated
tank, have to be addressed.

References[1] Javadian, P.  ,(  , 11, 2015, 96-103

1979-1986: Study of physics at the University of Hamburg, 1987-1991: PhD Thesis at the Philips
Research Laboratory Hamburg, Dept. Thin Films, 1991-2000: Scientist at the Fraunhofer Institutefor Surface Technology and Thin Films, Braunschweig, 2000-2001: Head of Dept. Forming
Technology at IFU Institute for Forming Technology, Lüdenscheid, since 2002:Scientist at theInstitute of Material Science at Helmholtz-Zentrum Geesthacht Research Centre
Coordinator of the FCH JU Collaborative Project "BOR4STORE" (2012 – 2015, www.bor4store.eu/)
and of the Marie Curie ITN ECOSTORE (2013 – 2017, www.ecostore.eu)
Dr. Klaus Taube㸫㸫

10th Int. Symposium "Hydrogen & Energy" !9~ 

Sendai, JAPAN 2016   

Hiroyuki Saitoh1, Shigeyuki Takagi2, Katsutoshi Aoki3, and Shin-ichi Orimo2
1 Japan Atomic Energy Agency, 2 Tohoku University, 3 The University of Tokyo
Novel hydrides have been synthesized under high pressure and high temperature. In situ synchrotron radiation x-ray
diffraction technique is effectively used to find reaction conditions and to optimize them. Theoretical calculations predict
thermodynamical stabilities of target materials before high-pressure experiments. Novel hydrides have been successfully
synthesized by combining these techniques.


At high pressures of several gigapascals, hydrogen
becomes chemically active and reacts with metals andalloys to form hydrides which cannot be obtained aroundambient pressure. We have carried out high-pressure
syntheses of novel hydrides with the aid of synchrotron
radiation X-ray diffraction measurement and theoretical
calculations. Synchrotron radiation X-ray diffraction
measurement enables us to find synthetic conditions oftarget materials, to optimize these conditions, and toclarifythesereactionmechanisms.
Theoretical
calculations predict thermodynamical stabilities of target
materials before high-pressure experiment.

hydrogenation reaction completely proceeded above
900°C, whereas a part of the powdered mixture washydrogenated below 900°C. High pressure above 6 GPa
is necessary to stabilize the hydride above 900°C
This work was supported by JSPS KAKENHI (grant
numbers 25420725, 25220911, 26820312) and the
Photon and Quantum Basic Research Coordinated
Development Program by MEXT.

.0
A sample, which was subject to hydrogenation, waspressurized to a target pressure at room temperature andthen was heated up to a target in hydrogen fluid. Highpressure and high-temperature conditions weregenerated using a cubic-type multi-anvil high-pressure
apparatus. Structural changes of the sample weremonitored by in-situ synchrotron radiation X-ray
diffraction technique at BL14B1 at SPring-8 [1].


Al2CuH)[2]: Al2Cu alloy first decomposed into Al2Cu3 andpure aluminum at 880°C and 10 GPa. A hydrogenation
reaction started upon lowering the temperature to 800°C.
The formed hydride was recovered at ambient conditions
and characterized by powder X-ray diffraction
measurement. The interstitial nature of the hydride wasconfirmed based on its crystal and electronic structures.
Li4FeH6[3]: Iron-containing complex hydride, Li4FeH6 has
been synthesized by hydrogenation reaction of apowdered mixture of LiH and Fe. In situ synchrotron
radiation x-ray diffraction measurement revealed that theFig. 1 Crystal structures of synthesized hydrides underhigh pressure.

"
[1] H. Saitoh, A. Machida, and K. Aoki, Chinese Sci. Bull.
59, 5290 (2014).
[2] H. Saitoh, S. Takagi, N. Endo, A. Machida, K. Aoki, S.
Orimo, and Y. Katayama, APL Mater. 1, 032113 (2013).
[3] [1] H. Saitoh, S. Takagi, M. Matsuo, Y. Iijima, N. Endo,
K. Aoki, and S. Orimo, APL Mater. 2, 076103 (2014).

Hiroyuki Saitoh is currently a principal scientist at Quantum Beam Science Center, Japan Atomic
Energy Agency (JAEA). He received his PhD degree in material science from Tsukuba University in
2003, where he investigated structural phase transitions of macromolecules using X-ray diffraction
technique. He joined Japan Atomic Energy Research Institute, the former organization of JAEA, as a
postdoc. He became a tenured scientist at JAEA in 2011. His research interests focus on highpressure synthesis of functional materials, especially metal hydrides, with the aid of synchrotron
radiation X-ray diffraction techniques.

Hiroyuki Saitoh
Corresponding author: Hiroyuki Saitoh, cyto@spring8.or.jp, +81-791-58-2632.

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

CRYSTAL STRUCTURE INDICATOR: THE IONIC FILLING FRACTION OF
HYDRIDES WITH ARBITRARY ARRANGED IONIC COMPONENTS
Toyoto Sato1, Shigeyuki Takagi1, Stefano Deledda2, Bjørn C. Hauback2, Shin-ichi Orimo1, 3
1 Institute for Materials Research, Tohoku University, 2 Physics Department, Institute for Energy Technology, Norway
3 WPI-Advanced Institute for Materials Research, Tohoku University
Abstract
Crystal structure investigation is essential for material characterization and understanding of material properties. Here,
we propose a new indicator for crystal structural identification by organizing various ionic compounds with arbitrary
crystal structure and composition, thus tackling the main obstacle for determining unknown crystal structures. The
indicator represents ionic filling fraction (IFF) which is the occupancy of constituent ions within the crystal structures. The
IFF shows a linear trend between volume of crystal structure and composition, and thus the IFF is expected to become anew indicator for comprehensive crystal structure identification.

Introduction
Every compound is identified by a unique crystal
structure that aids the understanding of the atomic
positions, compositional ratios and unique material
properties. Although crystal structural determination isessential in crystallography, materials science, chemistry,
physics etc., it is complicated due to many factors forrepresentation of arbitrary crystal structures.
We therefore propose a new indicator for structure
identification on various ionic compounds including
hydrides. The indicator allows us to organize ioniccompounds with arbitrary crystal structures andcomposition ratios by using the Ionic Filling Fraction (IFF).

plot represents the IFF of spherical ions in the crystal
structure. The data for many ionic compounds are
distributed near the line of best fit at *unit/+ = 1.45*ion,
corresponding to IFF of 0.69. Since ionic compounds arein general locates along *unit/+ = 1.45*ion, the IFF is
expected to become a new indicator for comprehensive
crystal structure identification.

MethodWe define the assessment standard for comparison of
the different crystal structures of complex hydrides,
binary hydrides, perovskite hydrides, oxides and halides.
The relative sizes of crystal structures are compared withthe volume of the unit cell (*unit) normalized by the
number of formula units (+): *unit/+. Each ion is assumed
to be spherical and their volumes are determined using
their Shannon radii [1]. The total volume of spherical ions
*ion is calculated using the stoichiometric ratio of the ioniccompounds as shown in Fig. 1. In this study, 1.40 Å wasused as the radius of the H ion. The thermochemical
radius [2], which is estimated from Glasser generalizationof Kapustinskii equation for lattice energy of ioniccompounds, is used for complex anions.

Fig. 1 Schematic crystal structure of a complex hydride(red: cation; blue: complex anion, + = 2) and *unit/+ vs.
*ion for complex hydrides, binary hydrides, perovskite
hydrides, oxides and halides (total: 136 compounds).
This research was supported by the JSPS KAKENHI(grant numbers 25220911, 26820312, and 26820313),
and Integrated Project of ICC-IMR of Tohoku University,
and Collaborative Research Center on Energy Materials
in IMR (E-IMR), Tohoku University.

Results and Discussion

References

Fig. 1 shows a plot of *unit/+ vs. *ion. The inverse of theslope of straight lines that pass through the origin in each[1] R. D. Shannon, Acta Crystallogr. A 32, 751 (1976).
[2] L. Glasser, Inorg. Chem. 34, 4935 (1995).

2006:
2006 – 2007:
2007 – 2009:2009 – 2012:
Toyoto Sato

Ph.D, Stockholm University, Sweden
Research Scientist, Arizona State University, USA
Research Scientist, Institute for Materials Research, Tohoku University, Japan
Assistant Professor, WPI-Advanced Institute for Materials Research,
Tohoku University, Japan
2012 – Present: Assistant Professor, Institute for Materials Research, Tohoku University, Japan

Corresponding author: Toyoto Sato, toyoto@imr.tohoku.ac.jp, +81-22-215-2094

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

STRUCTURE AND HYDROGEN SORPTION PROPERTIES OF (A,Mg)2Ni7(A = La, Sm, Gd OR Y) COMPOUNDS*J. Zhang1, V. Charbonnier1, J. Monnier1, L. Goulbault2, P. Bernard2, M. Latroche1
1

ICMPE/CNRS-UPEC UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais, France, 2 SAFT Direction de la Recherche 111113 boulevard Alfred Daney 33074 BORDEAUX, France

Unlike La2Ni7, Gd2Ni7 or Nd2Ni7, Y2Ni7 can absorb or desorb hydrogen reversibly at room temperature. The PCI curve
exhibits three plateau pressures forming three hydrides. The maximum hydrogen capacity reaches 8.9 H/f.u. at 10 MPa.
The structural properties of Y2Ni7Dx have been studied by neutron diffraction. Due to higher pressure of the second andthird plateau, this alloy cannot be used for electrochemical application. Partial substitution of Y by La and Mg will be
studied to optimise the PCI curve for electrochemical application.

Introduction
To improve the properties of Nickel-Metal Hydride
batteries, new promising A2Ni7-type alloys are developed(A = mixture of rare earths). These A2Ni7 alloys can reach-1
400 mAh.g by partially substituting the rare earth withMg [1]. The La-Mg-Ni system has been largely studied,but A2Ni7 systems with other rare earths have beenbarely reported [2].In this study, model binary A2Ni7 alloys
were synthesized, for A = La, Sm, Gd or Y using
induction melting and powder metallurgy.

Experimental
The compounds were synthesized by induction melting or
powder metallurgy, the crystal structure were studied by
X-ray (or neutron) diffraction, the hydrogen sorption
properties were studied by the Sievert’s method. The
electrochemical properties were characterized by using
VMP3 (biologic) galvanostatic measurements.

Fig. 1: Crystal structures for Y2Ni7Dx (x= 2.1 (E), 4.1 (J)and 8.8 (G)) from bottom to top (RJm). Stacking subunits[A2B4] and [AB5] are also represented.

Results and Discussion
Single phase A2Ni7 compounds have been synthesized
successfully. Surprisingly, unlike other binary A2Ni7
compounds, Y2Ni7 absorb and desorb hydrogen
reversibly. The cycling stability has been studied by solidgas and electrochemical methods. The crystal structureof the three deuterides have been studied by neutron
diffraction. The correlation of the cycling stability and thehydride structures will be discussed. Partial substitutionof Y by La and Mg leads to a large and flat plateau
located in the electrochemical application window, theelectrochemical properties of the substituted compound
will be presented.

References[1] Kohno, T.; Yoshida, H.; Kawashima, F.; Inaba, T.;
Sakai, I.; Yamamoto, M.; Kanda, M. Journal of Alloys andCompounds 2000, 311, L5-L7.
[2] Zhang, J.; Latrohe, M, Magén, C.; Serin, V.; Hÿtch, M.
J.; Knosp, B.; Bernard, P. J. Phys. Chem. C, 2014, 118,
27808

Junxian Zhang received her PhD degree from Stuttgart University (Germany) in 2000. She was
postdoc researcher in the Laboratory of Chemistry and Metallurgy of Rare Earths, CNRS, before
joining the Institute of Chemistry and Materials Paris East, France. She has first worked on hardmagnetic materials, her current research field is now devoted to materials for hydrogen storage. She
is interested in the application of hydrides as negative electrode materials in Ni-MH and Li-ion
batteries. She has published ~60 scientific papers.

Junxian Zhang

Corresponding author: Junxian Zhang, Email: junxian@icmpe.cnrs.fr, Tel: +33149781342.

㸫㸫

10thInt. Symposium "Hydrogen & Energy"

Sendai, JAPAN2016!! 0#"0"8:00-8;-=-'<+0;=$-$ $!$$Affiliation 1 Dalian National Laboratory for Clean Energy,Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, 2 University of Chinese Academy of Sciences
Abstract 2Mg(NH2)2–3LiH–LiBH4 composite exhibits an improved kinetic and thermodynamic properties in hydrogenstorage in comparison with 2Mg(NH2)2–3LiH. The peak temperature of hydrogen desorption drops about 10 K and thepeak width shrinks about 50 K compared with the neat 2Mg(NH2)2–3LiH. Its isothermal dehydrogenation and rehydrogenation rates are respectively 2 times and 18 times as fast as those of 2Mg(NH2)2–3LiH. A slope desorption
region with higher equilibrium pressure is observed. By means of X-ray diffraction (XRD), Fourier transform infrared
spectroscopy (FTIR) and nuclear magnetic resonance (NMR) analyses, the existence of Li2BNH6 is identified and its
roles in kinetic and thermodynamic enhancement are discussed.


Li-Mg-N-H system is regarded as a promising hydrogenstorage material because of its relatively high storage
capacity and reversibility. However, slow kinetics andstable thermodynamics hinder its practical application.[1]In contrast to the substantial progress in theenhancement of kinetics,[2] thermodynamic tuning is still a[3]
great challenge for the Li-Mg-N-H system. Hu et alreported thermodynamic properties could be altered bymechanically ball-milling Mg(NH2)2-LiH with LiBH4. An
interesting phenomenon was observed that there was ahigher pressure slope in pressure composition isotherm(PCI)
measurementsof
2Mg(NH2)2–3LiH–LiBH4
composite, which reveals the change of thermodynamic
properties.

significantly improved in comparison with pristine
2Mg(NH2)2–3LiH sample. Especially, it desorbs ca. 80%
hydrogen in 100 min and re-hydrogenates 80% hydrogenin 50 min isothermally at 416 K, which is ca. 2 times and18 times as fast as those of 2Mg(NH2)2–3LiH composite.

.030
The composites were prepared by ball-milling for 24 h a
mixture of self-produced Mg(NH2)2 (yield >95%),
commercially available LiH and LiBH4 in a mole ratio of 23, 2-3-1 and 2-3-1/3 in an inert gas (Ar) environment.*
The structural evolution of the crystalline phases bydecomposition was studied by X-ray diffraction (XRD).
The dehydrogenation thermodynamics of the composite
was studied by the pressure composition isotherm (PCI).*
Increasing LiBH4 amount in the 2Mg(NH2)2–3LiH
composite leads to a higher dehydrogenation pressure in
the slope region. The reason for this change may be dueto the melted reaction of LiNH2–LiBH4. Moreover, thekinetics of 2Mg(NH2)2–3LiH–LiBH4 composite are

Fig. 1 Dehydrogenation Pressure-Composition-Isotherm(PCI) curves of 2Mg(NH2)2–3LiH (Tp), 2Mg(NH2)2–3LiH–
LiBH4(T2) and 2Mg(NH2)2–3LiH–1/3LiBH4(T4) composite
at 473 K. The inset is the PCI curves at H/(mol of T2 andT4): 0 to 2. "
[1] M. Zhu, P. Chen, Mater. Today. 11, 36 (2008)[2] J. H. Wang, Angew. Chem.-Int. Edit.48, 5828(2009)[3] J. J. Hu, P. Chen, Chem. Mater. 20, 7089(2008)

Short CV: Han Wang received her BSc degree in Chemical Engineering from Tianjin University in2011. Now She is a PhD candidate in Dalian Institute of Chemical Physics, Chinese Academy of
Sciences (tutored from Ping Chen). Her research is focused on improving the dehydrogenation/ rehydrogenation properties of solid-state hydrogen storage materials of lithium-magnesium-nitrogenhydrogen system.


Han Wang
Corresponding author: Name: Ping Chen, Email: pchen@dicp.ac.cn, Tel.:+0411-8437-9583.

㸫㸫

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

STRUCTURAL ANALYSIS DURING THE DISPROPORTIONATIONPROCESS OF NaAlH4 BY ELEMENT-SELECTIVE METHODS
Toshiya Otomo1, 2, Fumika Fujisaki2, Kazutaka Ikeda1, Hidetoshi Ohshita1, Hitoshi Abe1,
Hiroshi Arima3, Kazumasa Sugiyama3, Motoaki Matsuo3, Toyoto Sato3, Kouji Sakaki4,
Yumiko Nakamura4 and Shinichi Orimo3, 5
1 Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), 2 Department ofMaterials Structure Science, The Graduate University for Advanced Studies (SOKENDAI), 3 Institute for Materials
Research, Tohoku Univ., 4 National Institute of Advanced Industrial Science and Technology, 5 WPI-AIMR, Tohoku Univ.
Abstract
The atomic scale mechanism of the disproportionation process of NaAlH4 with TiCl3 was investigated by elementselective methods such as neutron diffraction, X-ray diffraction, anomalous X-ray scattering and X-ray absorption finestructure. Important structural information of Al-H correlation and position of Ti were obtained.

The hydrogen desorption and absorption of NaAlH4 isa disproportionation process between NaAlH4 and NaH +Al as follows;
NaAlH4 п 1/3Na3AlH6 + 2/3Al + H2
Na3AlH6 п 3NaH + Al +3/2H2
Additives of TiCl3 affects the process kinetically andmakes the reaction to reversible. It was found in 1996
and it has not been revealed because the analysis of theatomic structure is complicate: the sample isn’t stable atroom temperature and the process includes 5 elements(Na, Al, H, Ti, Cl).
In this study, we aimed to reveal the mechanism in
atomic-scale by neutron diffraction (ND), X-ray diffraction(XRD), anomalous X-ray scattering (AXS) and X-ray
absorption fine structure (XAFS). Combination of thesetechnique realizes element-selective analysis of thedisproportionation process of NaAlH4 with TiCl3.

These results show that Ti atom replaced with Al
atom in the as-synthesized sample and then Ti atom
forms Al-Ti alloy in the hydrogen desorption process. The
replacement helps to form highly dispersed Al-Ti alloy inthe first desorption process. The dispersion of Ti is
supposed to be the reason of the effectiveness of TiCl3
as an additive.
This work was partially supported by JSPS KAKENHI
Grant Numbers 23686101, 24241034, 15K13810, theInter-University Cooperative Research Program of theInstitute for Materials Research, Tohoku University(Proposal No. 15K0110), the Neutron Scattering Program
Advisory Committee of IMSS, KEK (Proposal No.
2009S06, 2014S06) and the Photon Factory Program
Advisory Committee (Proposal No. 2014T001).

In case of as-synthesized sample, it was found thatthe coordination number of H atom around Al atom isinvariance by the addition of TiCl3 by ND of NaAlD4. AXS
at around Ti K-edge shows that Ti atom replaced with Al
atom. The replacement was also supported by Rietveld
refinements with ND and XRD data. In case of firsthydrogen desorption and absorption samples, XRD and
XAFS results suggest that Ti atom forms Al-Ti alloy ofnano-meter order particle.

Born 5. 9. 1965 in Japan. 1993 Dr. of Engineering from Tohoku University and Post Doctoral fellow
at Institute for Material Research, Tohoku Univ. 1994 Research associate, High Energy Physics
Laboratory (former name of High Energy Accelerator Research organization, KEK). 2003 Associate
Professor, KEK. 2008 Professor, Institute of Materials Structure Science, KEK.

Toshiya Otomo
Corresponding author: Toshiya Otomo, toshiya.otomo@j-parc.jp, +81-29-284-4333

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYDROGEN DOSORPTION OF C60H33/LiD INVESTIGATED BY MASS
SPECTROMETRY
Philippe Mauron, Andreas Züttel
Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC),
École polytechnique fédérale de Lausanne (EPFL), Rue de l’Industrie 17, 1950 Sion, Switzerland
Abstract
Lithium and sodium intercalated fullerides can reversibly absorbe up to 5.1 and 3.5 mass% hydrogen, respectively.
During hydrogenation of the metal intercalated fullerides a phase separation into hydrofullenes and the corresponding
metal hydride occurs. In order to investigate in detail de dehydrogenation mechanism, hydrogen desorption of C60H33/LiD
was investigated by mass spectrometry.

Introduction
Lithium and sodium intercalated fullerides, so called
charge transfer salts, can reversibly absorbe up to 5.1
and 3.5 mass% hydrogen [1, 2], respectively. The
hydrogen absorption/desorption temperature are up to
200/150 °C lower than for pure C60. The kinetics forhydrogen sorption is also much increased [3].

Experimental
C60H33 was purchased form MER Corp. and LiD from
SigmaAldrich. A stoichiometric mixture of 1:33 of C60H33
and LiD was grinded with a mortar in order to get ahomogenous mixture. As a reference sample unmixed
C60H33 and LiD was measured.
Fig. 1: Reaction mechanism of the dehydrogenation of
C60H33/LiD

Results and Discussion
The appearance of HD already at low temperature for thegrinded sample, starting at 130 °C, suggests that thenegatively charged deuterium from the LiD reacts withthe hydrofullerene by forming HD and by transferring
charge to the hydrofullerene and direct reintercalation of+
the Li ion (see Figure 1). This reaction mechanism can
explain the reaction of very stable LiD already at low
temperature, below the melting point and decomposition
temperature of LiD.

References[1] Ph. Mauron, A. Remhof, A. Bliersbach, A. Borgschulte,
A. Züttel et al.     37, 14307 (2012)[2] Ph. Mauron, M. Gaboardi, A. Remhof, A. Bliersbach,D. Sheptyakov et al.   117, 22598 (2013)[3] Ph. Mauron, M. Gaboardi, D. Pontiroli, A. Remhof, M.
Riccò, A. Züttel.   119, 1714 (2015)

1973 born 6. October in Fribourg, Switzerland.
1999 Diploma in experimental physics (solid state physics), University of Fribourg,
Switzerland.
2003 PhD at University of Fribourg, Switzerland.
2005 Postdoc at Vrije Universiteit Amsterdam, The Netherlands.
2007 Project leader at Empa. Swiss Federal Laboratories for Materials Science andTechnology, Dübendorf, Switzerland
2015 Scientist at École polytechnique fédérale de Lausanne EPFL, Sion, Switzerland
Philippe Mauron
Corresponding author: Philippe Mauron, philippe.mauron@epfl.ch, Tel. +41 21 695 8211

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SYNTHESIS AND PROPERTIES OF NANOSTRUCTURED MATERIALSFOR HYDROGEN STORAGE AND LITHIUM BATTERY BY HOT AND
COLD PLASMAS
Chen Jun1, He Fu1, Yong Wu, Zheng Jie2, Li Xingguo3
1 PhD candidate, 2 Associate Professor, 3 Professor
The plasma processing techniques utilized this study include low temperature plasma and arc thermal plasma, which
exhibits distinct characteristics. Due to the unique plasma chemistry processes and plasma-surface interaction, plasma
exhibits special effects in controlling the nanoscale structure. Our results suggest that plasma assisted techniques arevery versatile in preparing nanostructures for energy storage applications.

Introduction
Nanostructured materials have been an important
subject since the late 1980s. There are many methods
developed for synthesis of nanomaterials such as ballmilling, precipitation, hydrothermal method, chemical
vapor deposition and so on. Different from theseconventional methods, we study synthesis of nanostructured materials by DC arc plasma and RF plasmaand expect nanostructure can enhence their properties
for hydrogen storage and lithium battery.

Experimental / Computational

Fig. 1. (a) SEM pattern, (b) TEM pattern (inset: magnified
TEM pattern) of the as-prepared Li2NH hollow
nanospheres

A shematic figure of the experiment equipment, which
is used to produce the metal nanoparticles by hydrogenplasma-metal reaction, was described previously[1] .
The intercalated metal/C multilayer films are preparedin a home designed dual plasma reactor, which consistsof a stainless high vacuum chamber equipped with two
plasma sources: a radio frequency magnetron sputtering
source and an inductively coupled plasma source.

Results and Discussion
Figure 1a and 1b show that the product is in hollow
nanostructure and the diameters range from 100 to 400
nm with more than 90% in the range of 100-200 nm,
produced by DC arc plasma.
The cycling performance of the intercalated Si/C
multilayer film electrodes was tested up to 100 cycles(Fig.2).The capacity of the first discharge of every sample
was found to be much larger than silicon theoretical
capacity (4200 mAh/g). This large irreversible capacity
can be attributed to the formation of the SEI layer. The
capacity of the silicon in the electrode is calculated bysubtracting the contribution of the carbon layer.

Fig. 2. Cycling performance of the intercalated Si/C
multilayer film electrode. The solid and hollow symbols
correspond to the charge and discharge curves,
respectively.

References[1] Li X G, et al. J. Magn. Magn. Mater. 170, 339 (1997)[2] X.G. Li et al. Chem. Mater., 20, 282 (2008)[3] X.G. Li et al. Adv. Mater., 22, 1451 (2010)

Xingguo Li received his bachelor’s degree from Huazhong University of Science and Technology in1982 and was awarded the PhD diploma in 1990 from Tohoku University. Since 1999, he works as aprofessor in the College of Chemistry and Molecular Engineering at Peking University. His researchinterest includes energy-related materials, intermetallic and rare earth compounds, and nanomaterial
fabrication techniques.

Xingguo Li
Corresponding author: Li Xingguo, xgli@pku.edu.cn, 86-10-62765930.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

COMPUTATIONAL DESIGN OF MATERIALS FOR ELECTROCHEMCIAL
ENERGY CONVERSION AND STORAGE
Tejs Vegge
Department of Energy Conversion and Storage, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark
Emerging technologies for conversion and storage of energy from renewable and intermittent sources like wind and solar
power remain non-competitive on commercial terms, due to poor activity, selectivity, efficiency, stability or cost. The
ability to improve and ultimately design superior materials is paramount in the development of more efficient sustainableenergy technologies. Density functional theory (DFT) calculations can provide predictive accuracy in the design of new
eletrocatalysts for sustainable production of synthetic fuels and chemicals, as well as new materials for energy storage

Materials Predictors for Catalyst Design
Model structures and materials predictors can link thecomplex functionality of materials to simple atomic
properties, e.g. the binding energy of nitrogen on nanoparticle catalysts for electroreduction of N2 into NH3 [1],which can then be used to design better electrocatalysts.

Fig. 2 0  !     $ !    ! / ! 123 /( $ ! &4'
DFT-GA can also be used to optimize materials for, e.g.,ammonia storage, by calculating only a few percent of
the number of possible compositions and structures [4].

References[1] J. G. Howalt, T. Bligaard, J. Rossmeisl and T. Vegge,  . 15, 7785 (2013).

Fig. 1  $   !! !   $!    /!  %$    !    &'[2]S. Lysgaard, D. D. Landis, T. Bligaard, T. Vegge%$!  57, 33(2014).

Optimization by DFT & Genetic Algorithms[3]S. Lysgaard, J. S. G. Myrdal, H. A. Hansen, T. Vegge%
  17,28270 (2015).

Here, we also combine such DFT-level, predictor-based
approaches with evolutionary algorithms (DFT-GA) to
optimize electrocatalysts, e.g. Cu-Ni [2] and Au-Cu
nanoalloys [3] for electroreduction of CO2 into fuels andchemicals.

Tejs Vegge[3]P.B. Jensen, A. Bialy, D. Blanchard, S. Lysgaard, A.
Reumert, U. J. Quaade, T. Vegge,     27,4552 (2015).

Professor Tejs Vegge is Head of Section for ‘Atomic Scale Modeling and Materials’ at DTU Energy,
Technical University of Denmark (DTU). He is an elected member of the Danish Academy ofTechnical Sciences and his research activities are centered round integrated computational andexperimental design, development and characterization of novel materials for energy conversion andstorage. His work combines density functional theory (DFT) level calculations with large-scalecomputational screening and he has developed and applied a number of new computational
approaches using template-based screening, materials predictors and genetic algorithms toaccelerate the materials design process. The activities include the design of novel materials forstorage of hydrogen and ammonia, battery electrodes and electrolytes, and electrocatalysts.

Corresponding author: Prof. Tejs Vegge, teve@dtu.dk, +45 5164 1787㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYMARC: A CONSORTIUM FOR ADVANCING SOLID-STATE HYDROGEN
STORAGE MATERIALSMark D. Allendorf,1 Brandon C. Wood,2 Jeffrey J. Urban,3 Jinghua Guo,3 Tae Wook Heo,2Leonard E. Klebanoff 1 Robert Kolasinski,1 Vitalie Stavila1
1Sandia National Laboratories, Livermore, CA 94551-0969; 2 Lawrence Livermore National Laboratory, Livermore, CA
3394550, Lawrence Berkeley National Laboratory, Berkeley, CA 94720; Lawrence Berkeley National Laboratory,
Berkeley, CA 94720
Abstract. The Hydrogen Materials Advanced Research Consortium (HyMARC), recently initiated by the DOE Fuel Cell
Technologies Office (FCTO), seeks to address the critical scientific gaps blocking the development of solid-statematerials that meet DOE targets for on-board vehicular storage. By leveraging recent advances in predictive multiscalemodeling, high-resolution in-situ characterization, and material synthesis, HyMARC will develop new capabilities toenable accelerated development of all types of advanced storage materials, including sorbents, metal hydrides, andliquid carriers.

Introduction
Although fuel cell vehicles are now a commercial reality,
the hydrogen fuel is stored as high-pressure gas (700bar) in costly carbon fiber-reinforced tanks. This storage
format cannot meet U.S. DOE targets for cost andvolumetric capacity. Consequently, solid-state storage
materials, including novel sorbents and high-density
hydrides, remain of interest because of their potential todeliver hydrogen at lower pressures and higher on-board
densities. Unfortunately, although materials meetingsome DOE targets are known, progress is hindered by alack of fundamental understanding of the kinetics andthermodynamics governing the uptake and release ofhydrogen. Consequently,
the DOE Fuel Cell
Technologies Office initiated the Hydrogen Advanced
Materials Research Consortium (HyMARC), a teamcomprised of researchers at three national laboratories(Sandia, Lawrence Livermore, and Lawrence Berkeley
Laboratory), with the objective of addressing the scientificgaps blocking the advancement of solid-state storage
materials.
HyMARC research activities will focus on thethermodynamic and kinetic limitations of storage
materials, including mass transport, surface chemistry,and processes at solid-solid interfaces. The resulting
fundamental understanding, when combined withmaterials informatics, will embody the approachdescribed in the recent Materials Genome Initiative
Strategic Plan for accelerated materials development.
HyMARC will employ the large-scale parallel computing
resources, innovative synthetic approaches, and high-Mark D. Allendorf

resolution in-situ characterization tools available at thethree laboratories to develop new capabilities that will
accelerate development of storage materials that meet
DOE targets. These capabilities will be made available tothe hydrogen storage research community through future
joint projects and collaborations. Examples include: multiphysics software, methods, and models optimized forhigh-throughput material screening; a sustainable,
extensible database framework for measured andcomputed material properties; protocols for synthesizing
storage materials in bulk and nanoscale formats; ultra
high-pressure synthesis and characterization facilities(700 bar); and characterization methods tailored forhydrogen storage and facile use of advanced X-ray
probes.

Fig. 1. Potential rate-limiting physiochemical processes
during uptake and release of H2 by storage materials

Dr. Mark D. Allendorf is Director of 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 hydrogen-related research activities incude lead
investigator for theory and modeling in the Metal Hydride Center of Excellence and principal
investigator for research focused on nanoconfinement effects on metal hydrides. Currently, his
research team at Sandia is leading efforts to develop the fundamental science and applications ofmetal-organic frameworks (MOFs), including chemical sensing, gas separations, electronic devices,
photovoltaics, and catalysts for biofuels production. Dr. Allendorf is also President Emeritus andFellow of The Electrochemical Society.

Corresponding author: Mark D. Allendorf, mdallen@sandia.gov, Tel. (925)294-2895.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

GROUND STATE MAPS OF BINARY METAL HYDROGEN SYSTEMS
J.-C. Crivello1,2, N. Bourgeois1, T. Mohri2, J.-M. Joubert1
12Affiliation: CMTR-ICMPE-CNRS, UMR7182, Thiais, France, CMRI-IMR, Tohoku university, Sendai, Japan
Abstract: For 30 different binary metal-hydrogen systems, with 5H such as  = Mg, V, Pd,…, the heat of formation, 'f,of about 20 different hydride structures, among the classical interstitial hydrides, has been calculated with first principles
calculations (DFT + phonon). By joining the 'f values of all the most stable structures, one may obtain the convex hull,or ground state map, of a given system. The results present a good agreement with the experimental behavior. Besides,
not only the expected stable hydride structures are found, but also our calculation predicts the formation of new hydrides,
which could be obtained at high pressure.

Introduction

Results and Discussion

Among the emerging areas of materials science, thehigh-throughput computational materials design is one of
the most exciting [1]. By combining first principles
calculations and advanced thermodynamic approacheswith the power of current supercomputer architectures, it
is possible to build reliable databases and to discovernovel materials.

Fig. 1 shows a sample of results for 6 systems. On the
one hand, the expected stable hydride structures appear
with the good range of heat of formation values; on theother hand, our calculation predicts the formation of new
hydrides, including some which could be obtained at highpressure.

In the frame of the density functional theory (DFT),
systematic investigation has become a routine. However,the coupling with vibrational computation, like phonon
calculations is more complex, but still a necessity to
express the zero point energy (ZPE), a contribution which
is not negligible for hydrides.
The present paper shows a systematic review of 30
different 5H systems. For each system, the heat offormation of about 20 hydride structures has been
investigated and a ground state map has been
determined.

Fig. 1 Ground state map of 6 different -Hsystems (=Li, Mg, Ti, Fe, Ca, V)

Computational methodology
The DFT calculations were done using the PAW method
implemented in the VASP code. The GGA using the PBE
exchange-correlation functional has been consideredwith cut-off energy for pseudo-potentials set to 800 eV.
Phonon calculations were performed by a supercell
approach with the finite displacement method within theharmonic approximation and using the Phonopy code.
For a selection of hydrides, quasi-harmonic calculation
was done to describe the free energy, (,*), as afunction of the volume and the temperature.

Phonon calculation provides several vibrational
properties (ZPE, *, …). The overall result leads tobuild a reliable hydride database, usable for thethermodynamic modeling. Following this multiscale
approach, a full thermodynamic assessment of the Ni-H
system has been recently carried out in our group [2].

References[1] S. Curtarolo  , (   . 12, 191 (2013)[2] N. Bourgeois  ,  . (2015) $ 

J.-C. CrivelloSince his PhD study (University Paris XI, 2005), Jean-Claude Crivello has been working with firstprinciples calculation of materials for hydrogen storage application. He spent 2.5 years in Tokai
University (Japan) for a postdoctoral position. In 2008, he was recruited as a permanent researcher
at the French National Center of Scientific Research (CNRS) in the ICMPE institute. Since 2015, hehas been habilitated and is in sabbatical leave (~1 year), working in CMRI-IMR (Tohoku university).
With the help of DFT, his research is mainly focused on the description of chemical and physicalproperties of intermetallic and hydride compounds. His recent interest is combining DFT + phonon
calculations with thermodynamic modeling (Calphad, CVM,…) to describe phase equilibria.

J.-C. Crivello: crivello@icmpe.cnrs.fr

list of publications: http://scholar.google.fr/citations?user=YJT62kQAAAAJ㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

ASSESSMENT OF PHASE DIAGRAMS IN COMPLEX HYDRIDES
E. R. Pinatel, E. Dematteis, A. Wolczyk, F. Paruzzo, M. Corno, P. Ugliengo,
B. Civalleri, M. Baricco
Department of Chemistry and NIS, University of Turin, via P. Giuria 9, I-10126 Torino, Italy
Results of assessments of thermodynamic properties and phase diagrams for complex hydrides (borohydrides andamides) of alkali and alkaline-earth metal (e.g. Na, Li, Mg, Ca) will be reported, evidencing the challenges for developing
databases.

Introduction
Complex hydrides [1] are studied for various applications,
including hydrogen storage, electrochemical energy
storage, heat storage and, more recently, CO2
capture/conversion [2]. In all cases, thermodynamic
properties and phase diagrams have to be known indetails.
The Calphad approach is a useful tool for theinvestigation of complex hydrides, being able to provide
thermodynamic properties at different temperatures andpressures. However, the lack of reliable databases for
hydrides [3] is still a bottleneck toward a reliable use ofthis approach.

Experimental / Computational
Experimental data on temperature and enthalpy of phasetransformation have been obtained for various complex
hydrides by HPDSC under hydrogen pressure.
Ab initio DFT calculations have been performed by the
CRYSTAL program [4]. In order to compute an enthalpyof reaction at T = 298.15 K and P = 1 atm, the computed
electronic energy has been corrected for the zero point
energy. Thermodynamic modelling has been carried out
according to the Calphad approach [11].

Results and Discussion
Assessed phase diagrams have been obtained for pureborohydrides (i.e. NaBH4, LiBH4, Mg(BH4)2 and Ca(BH4)2).
In several cases, it is observed that stable phases cannot
be obtained experimentally during phase transformations,so that metastable phase diagrams have to beconsidered. From available database, the effect of anion
and cation substitution in borohydrides has been
considered and an estimation of interaction parameters

Marcello BARICCO

has been obtained. Examples will be provided for LiBH4LiCl and Mg(BH4)2-Zn(BH4)2 systems.
The description of thermodynamic properties of the liquid
phase in borohydride systems remains a big challenge,
because of lacking of experimental data. Examples ofphase diagrams will be provided for eutectic mixtures(e.g LiBH4-NaBH4), often infiltrated into porous scaffolds
to enhance hydrogen sorption properties
The combination of different complex hydrides (e.g.
LiBH4 and LiNH2) brings to the development ofcompounds with new crystal structures, characterized byopen channels for fast Li-ion mobility. A description ofthermodynamic properties has been obtained forLi4(NH2)3(BH4) and Li2(NH2)(BH4) compounds, allowing
the assessment of the LiBH4-LiNH2 phase diagram.
Developed assessments underlined inconsistencies
among experimental results, driving the selection of themost reliable data.

References[1] M. B. Ley et al.,      17, 122 (2014)[2] J.G. Vitillo et al.,    16, 22482(2014)[3] J.M Joubert et al., 6 64, 1438 (2012)[4] R.Dovesi et al.,  7   114, 1287
(2014)[5] H.L. Lukas et al., $    !,Cambridge University Press, 2007

Marcello BARICCO obtained the PhD in Chemistry in 1987. From 2004 he is full professor in
Metallurgy at the University of Turin. He is now vicerector of the University of Turin. He has been
responsible for the University of Torino in several national and international research projects withresearch institutions and industrial partners. He coordinated several European project on hydrogenstorage materials (COSY, FLYHY, BOR4STORE, SSH2S, ECOSTORE). He is an expert in the Task
32 of the IEA HIA, coordinator of JU-FCH project SSH2S and coordinator of the Working Group on
Hydrogen Storage at FCH-JU-N.ERGHY. The scientific contributions have been presented in about
300 papers, published in international and national journals, and in several invited talk ininternational and national meetings.

Corresponding author: Marcello Baricco, E.mail: marcello.baricco@unito.it, Tel. +39 366 7877 947

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th
10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 20168#"!0#
Craig Buckley, Drew Sheppard, Terry Humphries
Department of Physics, Astronomy and Medical Radiation Sciences, 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 themost important renewable energy resource to focus our attention upon. The International Energy Agency roadmap forsolar 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 or for integration with domestic power grids. Solar mirror collection fields can collect thermal energy during
the day and run a heat engine to convert it into electricity, but cannot provide power at night unless integrated with anenergy storage system. At the present time Concentrated Solar Thermal (CST) systems with heat storage use the heat
capacity (sensible heat) of binary liquid molten salt mixtures (40% NaNO3; 60% KNO3) to produce electricity during nonsun hours. A fundamental problem is the large quantity, volume and cost of the molten salts required to store sufficientheat to operate the plant for several hours during periods when the sun does not shine. The cost of solar thermal heatstorage 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 overall solar to electricity conversion efficiencies.
Reversible thermochemical reactions have the potential for substantially higher heat storage capacities than sensible
heat or 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
chemically by 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) from solar 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 – 8].

"
[1] D.N. Harries, M. Paskevicius, D.A. Sheppard, T.E.C. Price, C.E. Buckley. Proc. of the IEEE, $** (2012) 539.
[2] M. Fellet, Feature Editors: C.E. Buckley, M. Paskevicius, D.A. Sheppard. MRS Bulletin '( (2013) 1012.
[3] D.A. Sheppard, T.D. Humphries, C.E. Buckley. Materials Today $( (2015) 414.
[4] M. Paskevicius, D.A. Sheppard, K. Williamson, C.E. Buckley.Energy, (( (2015) 469 - 477. I.F. 4.159.
[5] Q. Lai, M. Paskevicius, D.A. Sheppard, C.E. Buckley, A.W. Thornton, M.R. Hill, Q. Gu, J. Mao, Z. Huang, H.K. Liu, Z.
Guo, A. Banerjee, S. Chakraborty, R. Ahuja, K.F Aguey-Zinsou. ChemSusChem, ( (2015) 2789.
[6] D.A. Sheppard, , C. Corgnale, B. Hardy, T. Motyka, R. Zidan, M. Paskevicius, C.E. Buckley. RSC Advances, + (2014)
26552.
[7] D.A. Sheppard, M. Paskevicius, T.D. Humphries, M. Felderhoff, G. Capurso, J. Bellosta von Colbe, M. Dornheim, T.
Klassen, P.A. Ward, J.A. Teprovich Jr., C. Corgnale, R. Zidan, D.M. Grant, C.E. Buckley. Accepted in Applied Physics A,
November 2, 2015.
[8] D.A. Sheppard*, T.D. Humphries, C.E. Buckley. Accepted in Applied Physics A, November 9, 2015.

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 andAustralia prior to being awarded tenure at Curtin University. His research is
focussed on hydrogen storage materials and the investigation of the structuralproperties of a wide range of materials. Craig has published 117 scientificpapers in peer reviewed journals.
Professor Craig Buckley
Corresponding author: Professor Craig Buckley, c.buckley@curtin.edu.au, +61401103602

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10th Int. Symposium Hydrogen & Energy

Sendai, JAPAN 2016

EXPERIMENTAL STUDY ON TOTALIZED HYDROGENUTILIZATION SYSTEM USING PV POWER DATAENERGY

Satya Shekhar Bhogillaa, Hiroshi Itoa, Atsushi Katob, Akihiro Nakanoa,*ab

National Institute of Advanced Industrial Science and Technology (AIST)
R and D Center, Takasago Engineering Co., Ltd, Japan

Abstract
Most of the countries have increased the production of renewable energy to reduce pollution and their dependency on oil
and natural gas. In case of Japan, solar power is increased rapidly, especially after the Fukushima Nuclear Accident. The
load leveling and fluctuation absorption are the main bottlenecks to the integration of PV power into the future electricity
system. This paper evaluate the Totalized Hydrogen Energy Utilization System (THEUS) operation and performance.

Introduction
Renewable energy sources such as solar and windenergy are clean and abundant but both are intermittent
power sources. Hydrogen based energy storage system
can store energy for long periods and thus allowing load
levelling in supply and demand for hourly to seasonalvariations. THEUS consists of a Unitized Reversible Fuel
Cell (URFC) and a Metal Hydride based Hydrogen
Storage Tank (MHT). THEUS can store intermittent
renewable energy and supply electric power, hydrogen,and thermal energy1. The URFC combines the Water
Electrolyzer (WE) and Fuel Cell (FC) functions in a single
unit, which lowers the capital cost of total system. THEUS
was tested at different load conditions of solar irradiation
profiles and discussed the performance of the wholesystem.

PV power data of a partly cloudy day. The URFC wasoperated in WE mode operation for 9 h 50 min and in FC
mode operation for 14 h. The total amount of hydrogenproduced by the WE was 5314 NL and 5099 NL ofhydrogen supplied from the MHT to the URFC in FC
mode operation. Fig. 1(a) shows the hydrogen production
rate and power input in WE mode operation and Fig. 1(b)shows the hydrogen flow rate from the MHT to the URFC
and power output in FC mode operationFrom Fig. 1(a),it
can be seen that the URFC responded rapidly to the load
variations of the PV power and performed reliable
operation. Total efficiency of the URFC was 49% andtotal efficiency of the THEUS (including metal hydride
heat output) was 62%, respectively.

Experimental set-up
The URFC can produce 2.56 kg/day of hydrogen andmaximum hydrogen flow rate was 17.8 NL/min with the
maximum DC stack power supply of 4.4 kW and able toproduce 0.68 kW DC stack power with the averagehydrogen supply rate of 7 NL/min in fuel cell mode.  The
URFC stack is made of ten electrochemical cells (2502cm active area each). The MHT was filled with 50 kg of
MmNi5 (AB5) type metal hydride alloy. A double coil typeheat exchanger, made of copper, was used to recover
the reaction heat of the MHT.

Results and Discussion
The irradiance data was measured at the Savannah
1River National Laboratory (SRNL) , which was used totest the THEUS. The URFC was operated based on theSatya Sekhar
Bhogilla(a)(b)

Fig. 1 Power and hydrogen flow rate. (a) WE operation(b) FC operation.

Acknowledgements
This study was supported by the NEDO, the contract
administration number 14103078-0.

References[1] Nakano A, Ito H, Bhogilla SS, Motyka T, et. al. Int. J.
Hydrogen Energy 40, 2663–2672 (2015).

Dr. Bhogilla Satya Sekhar received M. Tech in 2010 with specialization in Fluid & Thermal Sciencefrom Mechanical Engineering at Indian Institute of Technology Guwahati, India working in the area ofthermal energy storage systems. Following this, he started his Ph. D at the same Institute, where he
was involved in the development of metal hydride thermal machines. He joined Research Institutefor Energy Conservation, National Institute of Advanced Industrial Science and Technology (AIST),
Japan as a Postdoctoral Research Fellow in August 2014 to continue his research on hydrogenenergy. His area of interests are hydrogen energy, solid state hydrogen storage, fuel cells, sorption
systems and thermal energy storage.

Corresponding author: Akihiro Nakano, email a.nakano@aist.go.jp, Tel. +81-29-861-7250

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th

10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

Pt-Cu CATALYTIC COATINGS FOR HYDROGENNANOSTRUCTURE AND DEALLOYING EFFECTSCOMBUSTION:

V. Godinho, G.M. Arzac, A.M. Beltrán, M. C. Jiménez de Haro, F. Giarratano, A.
Fernández
Instituto de Ciencia de Materiales de Sevilla (CSIC - Univ.Sevilla), Avda. Américo Vespucio 49, 41092-Sevilla, Spain
Pt-Cu thin films have been deposited onto SiC-foam substrates by magnetron sputtering. The selection of the processgas (Ar and/or He) and deposition conditions allowed the control of nanostructure, porosity, and composition in the as
prepared films. A chemical dealloying treatment has been applied for analyzing its combined effect with the initial
nanostructuration of the coatings. The catalytic activity of the films has been investigated for the catalytic combustion ofhydrogen under conditions of excess of oxygen. Improved catalytic behavior has been demonstrated. *Introduction
Nanostructured Pt-Cu alloy particles [1], and otherrelated materials [2] are currently investigated due to theformation of very active catalytic phases after chemical,
or electrochemical, dealloying processes. Dealloyed PtCu core-shell nanoparticles have been proposed as costeffective electrocatalysts in oxygen reduction reactions[1]. Our aim is to investigate the dealloying process in PtCu thin films. The magnetron sputtering technology has
been selected for fabrication of coatings in order toinvestigate the effect of introducing novel porous
nanostructures in the as prepared films [3]. The effect of
both, nanostructure and dealloying, in the catalytic
activity was investigated in the catalytic hydrogen
combustion (CHC) [4]; an important reaction in the“hydrogen economy”, which can be employed as ameans of heat production as well as for safety purposes.

Experimental / Computational
The magnetron sputtering fabrication of coatings was
carried out in a one target chamber using a 2 inch Cu
target covered radially with Pt strips. Highly porous SiC
foam was used as support. The chemical dealloying
process was done by acid treatments. The Materials
were characterized by XRD, XPS, TEM and SEM
electron microscopy. The test CHC reaction was carriedout passing lean (1% v/v) H2/air mixtures through thecatalysts in a fixed bed reactor. Percentages of
conversion were determined by GC analysis.

Results and Discussion
Cost effective deposition of Pt-Cu alloys was possible by
the one target strategy. This considers the Pt/Cu
exposed area ratio at the sputtering track for controllingthe composition of the as prepared alloys. Composition of
the process gas (Ar and/or He) and deposition
parameters (DC/RF power, geometry, etc.) were also

ASUNCIÓN FERNÁNDEZ

controlled. Fig. 1a shows a Pt6Cu94 coating with columnar
microstructure prepared under Ar plasma. The effect ofdealloying is presented in Fig. 1b showing the induced
nanostructuration and porosity in the obtained Pt 34Cu66
alloy.

Fig. 1 STEM/HAADF images of a Pt-Cu catalytic coating
before and after dealloying
Catalytic activity measurements included activationenergy and evaluation of the T50 temperature(temperature for the 50% conversion). Improved catalytic
temperatures
wherebehavior
and
lower
T50
demonstrated in this work as the first time for the CHC
reaction with these materials. Data on the possiblesynergistic effects with the presence of novel porous
nanostructures will be also presented.

References[1] P.Strasser et al., Nature Chemistry 2, 454 (2010).
[2] A.-A.El Mel et al., ACS Applied Materials & Interfaces
7, 2310 (2015).
[3] V.Godinho, A.Fernández et al., Nanotechnology 2,
454 (2010).
[4] A.Fernández et al., Appl.Catal. B: Environ. 180, 336(2016)

Born May 1958 in Vigo, Spain, Prof. Asunción Fernández graduated in Chemistry at the University ofCádiz (Spain) (1980) and in Physics at UNED (Spanish Open University) (1984). She carried out her
PhD work at Max-Planck Institut für Strahlenchemie in Mülheim a.d. Ruhr (Germany) obtaining theDr. rer. nat. degree at the University of Dortmund (Germany) in June 1983 on the subject ofphotocatalytic H2 production from water solutions. In 1984 she joined the Materials Science Instituteof Seville (Spain), where she is leading the “Nanostructured Materials & Microstructure” group andthe “Advanced Laboratory for Nanoscopies and Spectroscopies”. Her actual research is devoted to
the fabrication and characterization of nanostructured coatings by PVD and the study of materials forH2 technologies in portable applications.

*Corresponding author: Asunción Fernández, asuncion@icmse.csic.es, +34-954489531

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

CO2 REDUCTION VIA A METAL HYDRIDE CATALYST
Shunsuke Kato,1 Santhosh Matam,2 Philipp Kerger,3 Laetitia Bernard,2 Corsin Battaglia,2Dirk Vogel,3 Michael Rohwerder,3 Andreas Züttel1
1. École Polytechnique Fédérale de Lausanne (EPFL), 1951 Sion, Switzerland
2. Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland
3. Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Str. 1, 40237 Düsseldorf, Germany
Abstract
To store renewable energy in synthetic hydrocarbons, reduction of carbon dioxide is a major challenge. The aim was toelucidate the origin of the catalytic activity of a metal hydride catalyst.

Introduction

Results and Discussion

To secure future energy supplies and stabilize
anthropogenic carbon dioxide emissions, a sustainableenergy society is to be based on a closed energy
material cycle. To store renewable energy in synthetichydrocarbons, with the energy density comparable tofossil fuels (e.g. petrol), reduction of carbon dioxide, as
well as the capture of carbon dioxide, is the major
challenge.[1]Carbon dioxide can be reduced to hydrocarbons bybinding hydrogen via heterogeneous catalysis reactions.
The direct and indirect hydrogenation of carbon dioxide
and carbon monoxide leads to several reactions,depending on the kinetics and thermodynamics, toward
the production of hydrocarbons. In view of the change inthermodynamic potential for reduction of carbon dioxide,
we focus on the catalytic properties of metal hydrides.
The aim was to elucidate the origin of the catalytic activity
for reduction of carbon dioxide.

Methane was markedly formed on the hydride, not on
the pristine intermetallic, in our experimental conditions,and the hydrogen desorption from the metal hydride
leads to the formation of methane (Figure 1). The activity
of hydrogen at the surface is a key factor in the reductionof carbon dioxide and increases the rate of the formationof methane.[2]Experimental
The catalytic activity of cobalt intermetallic hydrides
was investigated by using a fixed-bed tubular flow reactor,
and the products were analysed by mass spectrometry
and gas chromatography. The surface analysis was
performed by means of time-of-flight secondary ion mass
spectroscopy (ToF-SIMS) and near-ambient pressure Xray photoelectron spectroscopy (NAP-XPS), for the insitu analysis.

Shunsuke KATO

Figure 1 (Left) A metal hydride catalyst: Formation of anintermetallic hydride. Metal A is catalytically active in CO2
reduction. (Right) The formation of CH4 in the flow of CO2,++
H2 (H2/CO2 = 5), and He. Ion current ratio CH3 /He vs.
temperature: The pristine intermetallic (ʊ) and the hydride(ʊ).

References[1][2]

A. Züttel, P. Mauron, S. Kato, E. Callini, M. Holzer, J.
Huang,  , 2015, 69, 264.
S. Kato, S. Matam, P. Kerger, L. Bernard, C.
Battaglia, D. Vogel, M. Rohwerder, A. Züttel, to besubmitted, in 2015.

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, andat 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 theLaboratory of Radio- and Environmental Chemistry, Paul Scherrer Institute, Switzerland. 2014
Postdoc at the Laboratory for Hydrogen & Energy, Empa. Since 2015 Scientist at the Laboratory ofMaterials for Renewable Energy, École Polytechnique Fédérale de Lausanne (EPFL), and academic
guest at the Laboratory Materials for Energy Conversion, Empa.

Corresponding author: Shunsuke KATO, Email: shunsuke.kato@epfl.ch, Tel.: +41 21 695 82 13㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

COVALENT TRIAZINE FRAMEWORK SUPPORTED PALLADIUM
NANOPARTICLES FOR CATALYTIC HYDROGENATION OF HETEROCYCLES
Teng He, Lin Liu, Guotao Wu and Ping Chen
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.
Abstract
The as-prepared 4% Pd/CTF-1 catalyst showed a markedly improved activity in hydrogenation of (-heterocyclic
compounds as compared to the active carbon (AC) supported catalyst,  % Pd/CTF-1 catalyst exhibits !  3.6 times
faster than that of Pd/AC on the hydrogenation of (-methylpyrrole. Characterizations on Pd/CTF indicated the electron
donation from N in CTF to metallic Pd NPs, showing the intensified electronic interaction between the Pd NPs and CTF
support, which is responsible for the enhanced activities on the catalytic hydrogenation of (-heterocycles.

There are growing interests in employing hydrocarbons asliquid organic hydrogen store and carriers in recent years dueto the compatibleness with existing gasoline infrastructure andthe reduction in the economical impact of switching tohydrogen as an energy carrier.1-3 It has been demonstrated
theoretically and experimentally that incorporation ofheteroatoms, such as N or O, into liquid organic hydrogen
carriers (LOHCs) is in favor of their thermodynamic properties
in de/hydrogenation. However the de/hydrogenation stillencounter kinetic barriers. It is clear, from previous
investigations, that materials with high surface area allowing
high dispersion of noble metals and basicity to enhance activity
are potential catalyst supports in the hydrogenation ofheteroatomic LOHCs.
A covalent triazine framework (CTF) with high surface area,
high amount nitrogen functionalities, porosity and basicity has
the merits to meet the requirements mentioned above.
Therefore, it is of great interests to investigate the behavior of
CTF as a support in the catalytic hydrogenation of heterocycles as mentioned above. In the presence study, we
entrapped Pd nanoparticles (NPs) in CTF and used it as thecatalyst in the hydrogenation of heterocycles, including methylpyrrole and 1,10-phenanthroline (phen for short) .
*heterocyclic compounds (-methylpyrrole (see Fig. 1) and1,10-phenanthroline) as compared to the AC supported catalyst.
The improved activity of Pd/CTF-1 in the hydrogenation canbe explained by the electron donation from N group on CTF-1
to Pd. However, a slight deactivation in the catalytichydrogenation was observed. Therefore, more investigations
are still needed to improve the stability of Pd/CTF catalyst in
the future. [1]100oComversion (%)

Introduction

120 C 4% Pd/CTF-1

80
60

o

100 C 4% Pd/CTF-1

40o

120 C 4% Pd/AC

20o

120 C CTF-1

0
0

2

4
Time (h)68Fig. 1 Hydrogenation of (/methylpyrrole at 120 °C and 100 °C
by using pristine CTF-1, 4% Pd/CTF-1 and 4% Pd/AC under 20
bar H2.

References[1] T. He, L. Liu, G. Wu, P. Chen, J. Mater. Chem. A, 3,
13265(2015)

Results and Discussion
By using of basic support CTF-1, Pd NPs with well dispersion
and narrow distribution was successfully synthesized thanks tothe anchoring effect of N functionalities in CTF-1. The catalyst
exhibits a markedly improved activity in hydrogenation of -Teng HE pursued his PhD degree in Prof. Ping Chen’s group from 2006 to 2012 in Dalian Institute ofChemical Physics, Chinese Academy of Science (DICP, CAS). During his PhD, he mainly focusedon synthesis, characterization and dehydrogenation of solid state materials for hydrogen storage.
After graduation, he joined Prof. Ping Chen’s group directly and devoted himself to the research of
liquid organic hydrogen carrier. Now, he is a Associate Professor in DICP with the research interestsof materials chemistry and catalysis.
Teng HE
Corresponding author: Teng He, Email: heteng@dicp.ac.cn, Tel. +86-411-84379583

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

INITIAL ACTIVATION MECHANISMS OF PALLADIUM ADDED Ti ALLOYUSING CROSS COUPLING REACTION
Ryota Kondo1, Seiya Nakamichi2, Yasushi Obora1, Hiroyuki T. Takeshita1
1 Faculty of Chemistry, Materials and Bioengineering, Kansai University, 2 Graduate School of Science and Engineering
Abstract
Several initial activation mechanisms of Ti based hydrogen storage materials were proposed. Because Pd is well-known as a catalyst,
tiny content of Pd added Ti alloy (Ti(Pd)) would dominantly work the catalytic active site in/on Ti oxide film for molecular hydrogendissociation. Conventional surface analysis method, especially XPS analysis was commonly selected the chemical state of Pd in/on
oxide film. However XPS analysis could not outermost surface information. In this study cross coupling reaction with Ti(Pd) alloys
was applied as a probe reaction on the oxide film surface. Pd in/on oxide film existed as valence state of 0 (Pd0). The cross coupling
reaction progressed with using Ti(Pd) alloys, however pure Ti didn’t served as a catalyst for the reaction between 4methylphenylboronic acid and iodobenzene. The reaction efficiently progressed with using hydrogenated Ti(Pd) alloys. Therefore asa result of Pd0 on the oxide film dominantly served as a catalyst for dissociation of molecular hydrogen, condition of initial activation
was moderated in Ti(Pd) comparing with that in pure Ti.

Introduction
Ti based hydrogen storage materials are a low price and canabsorb and desorb hydrogen at low pressure and temperature.
Concerning the advantages of the Ti based hydrogen storage
materials, they could be practical and affordable for stationary
applications. In general, Ti based hydrogen storage materials
need initial activation at high temperature in hydrogen or avacuum due to their stable passive oxide film which wasformed after exposing in air. Focusing on catalytically active
element, Pd was effective for mitigation of initial activation
despite the tiny concentration1). Concerning about proposed
initial activation mechanism, formation of catalytically active
site for dissociation of molecular hydrogen, the catalytically
active site in/on oxide film should also work for external
reaction. Thus in this study, surface property of Ti alloys with atiny amount of Pd was investigated by using XPS and crosscoupling reactions.

Experimental Methods
Ti(1-x)Pdx (x = 0.002, 0.005, 0.010) alloys were arc-melted toform buttons from the pure Ti buttons and Pd sheet(99.95mass%) in an Ar atmosphere on a water-cooled cupper
hearth. Initial activation property was evaluated with a
Sieverts-type apparatus under conditions of initial hydrogenpressure of 3.0 MPa at R.T., heating at 5 K min-1 to 673 K, and
500 mg of sample quantity in a stainless steel reactor. XPS was
performed using AlK radiation. Cross coupling reaction
between iodobenzene and 4-methylphenylboronic acid was

conducted with before and after hydrogenated Ti or Ti0.99Pd0.01
as a catalyst.

Results and Discussion
Hydrogenation time was shown a trend of decrease withincrease of Pd concentration. From XPS analysis, Pd0 was
detected in the oxide film on Ti0.99Pd0.01. Conversion rate ofiodobenzene and yield rate of 4-methylbiphenyl using metallic
and hydrogenated Ti0.99Pd0.01 as a catalyst was shown in highyield. However the cross coupling reaction was not proceed in
the mixture with pure Ti. It should be noted that thecatalytically active site could account for the less than 1% of
Ti0.99Pd0.01. Therefore extremely small amount of Pd would
work for active site for the cross coupling reaction because thecatalytically active site was equivalent to less than 1% for thatof iodobenzene. Concerning the mechanism of cross coupling
reaction with Pd2), the cross coupling reaction could proceedwith the Pd0 species. Therefore, the valence state of Pd0 inoxide film could work for external reaction. Therefore it could
be considered that the Ti0.99Pd0.01 rapidly transformed into Ti
hydride because valence state of Pd0 could dominantly work as
catalyst for dissociation of molecular hydrogen.

References[1] R. Jeng, S. Lee, C. Hsu, Y. Wu, J.C. Lin, J. Alloy. Compd.,
464, 467 (2008)[2] A Braga, G. Ujaque, F. Maseras, Organometallics, 25, 3647
(2006)***

PhD with the thesis “Relationship between microstructure and mechanical properties of Zr-Nb alloys for
applying medical device” and M. Sc with the dissertation “Relationship between microstructure and magnetic
susceptibility of Zr alloys for applying medical device” were done at Tokyo Medical and Dental University.
After PhD was done in 2013, he has been working at Materials for Hydrogen Energy Systems Laboratory
which is affiliated with Department of Chemistry and Materials Engineering Faculty of Chemistry, Materials
and Bioengineering of Kansai University. The main topic of his research is mechanisms of initial activation of
catalytically effective element added Ti alloys and applying of the alloys for molecular transformation andhydrogen related devices using their advantages. His area of expertise is surface and interface science.
Ryota KONDOCorresponding author: Ryota KONDO rkondo@kansai-u.ac.jp (e-mail), +81-(0)6-6368-1690 (tel).

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10thInt. Symposium "Hydrogen & Energy"

Sendai, JAPAN2016

INFLUENCE OF PREPARATION CONDITIONS ON IONIC CONDUCTIVITY
IN (LiNH2)(LiBH4)1- (=0.50, 0.75)
A.Wolczyk1, M.Brighi2, E.Hadjixenophontos3, R.erný2, G.Schmitz3, C.Nervi1, M.Baricco1
1
Department of Chemistry and NIS, University of Turin, Via P.Giuria 9, I-10125 Torino, Italy, 2Laboratoire de Cristallographie, DQMP, Université de Genève,
24, quai Ernest-Ansermet, CH-1211 Geneva 4, Switzerland, 3Institut of Materials Science (IMW), University of Stuttgart, Heisenberstrasse 3, 70569
Stuttgart, Germany.

Abstract
The aim of this work is to investigate the relationship between microstructure and Li-ion conductivity in complex hydrides to be used assolid-state electrolytes for Li-ion batteries. Studied materials are combinations of (LiNH2)x(LiBH4)1-x, where x=0.50 (Li2BH4NH2) and 0.75
(Li4BH4(NH2)3) prepared by different methods (QU-quenching and BM-ball milling). SEM and TEM characterization have been
performed in order to investigate the microstructure. Rietveld refinement of XRD patterns was used to obtain strain and coherent
domain size. QU sample turns out with a coarser microstructure with respect to BM sample. Electrochemical characterisation by cycling
voltammetry and ion-conductivity measurements provided insights on the role of defects on the Li-ion mobility.

Introduction
One of the challenges toward Li-ion batteries is to develop
materials that possess high volumetric and gravimetric energy
density [1], combined with a fast ionic conductor and safe
electrolyte. Complex hydrides are of special interest forelectrochemical energy storage as novel solid state ion
conductors and anode conversion materials. They exhibit
superior electrochemical energy storage capacities as well as
high ionic conductivities at ambient temperatures. Li-ion
conductivity is the key issue. 6   [2] have reported alithium fast-ion conductions in Li2(BH4)(NH2) and Li4(BH4)(NH2)3,
making them candidates for solid-state electrolytes. Aim of thiswork is the analysis of the effect of preparation conditions on
microstructure and ion conductivity in (LiNH2)x(LiBH4)1-x (x=0.50,0.75) complex hydrides. In particular, the role of thermal cycling
on morphology, grain size and strain will be investigated.

than bulk diffusion through the grains. From the line broadening
observed in X-ray diffraction peak profiles - crystallite size andmicrostrain information have been obtained. Grain size havebeen estimated from TEM images, coupled with SAD. In case of
1:1, DSC traces show a sharp endothermic signal at around 4050°C in both synthesis, followed by a broad peak at 60-80°C,
related to melting of the compound. In case of 1:3 composition,
melting occurred at about 220 °C. Correlations between
microstructural features and ion conductivity has been
established and will be discussed.

Experimental
Mixtures of LiBH4 and LiNH2 from commercially available
powders were handled in inert atmosphere in glovebox. Samples
with ratios 1:1 and 1:3 were prepared by quenching (QU) andball milling (BM). QU samples were obtained by annealing
starting powders in a furnace at 190 °C for 3 h for composition
1:1 and 110 °C for composition 1:3, followed by quenching incold water with presence of ice and finally grounded manually inagate mortar to improve homogeneity. For BM samples, about
500 mg of reagents were milled with a Fritsch Pulverisette 7 with
5 balls of 10 mm diameter. Samples have been characterized by
XRD, DSC, TEM, SEM as well as through electrochemical
characterisation and ion-conductivity measurements, using
analogous conditions for sample preparation (e.g. compaction
pressure, diameter of pellet).

Results and Discussion
From SEM images shown in Fig. 1, variations in morphology anddimension of particles can be evidenced. Protruding surfaces
were observed in 1:1 QU sample, where sharp, long needle
parts can be identified. It is well established that ion mobility
along the grain boundaries can be orders of magnitude fasterFig. 1 SEM images of quenched (QU) and ball milled (BM) samples of 1:1(Li2(BH4)(NH2)) and 1:3 (Li4(BH4)(NH2)3) compounds.

References[1] C. Wang, S. Wang, Y-B He, L. Tang, C. Han, C. Yang, M.
Wagemaker, B. Li, Q.-H. Yang, J.-K. Kim and F. Kang    27, 56475656 (2015)[2] Y. Zhou, M. Matsuo, Y. Miura, H. Takamura, H. Maekawa, A.
Remhof, A. Borgschulte, A. Zuttel, T. Otomo and S. Orimo     !%52, 654-657 (2011)

Short CV

Anna Wolczyk

Born in Kielce, Poland, 31/03/1989. Graduated from AGH University of Science and Technology in Krakow, Poland.
Faculty of Materials Science and Ceramics, Discipline Chemical Technology, Specialization Technology of Building
Materials. Currently PhD student in ECOSTORE ITN Project “Novel Complex Metal Hydrides for Efficient and Compact
Storage Renewable Energy as Hydrogen and Electricity” as an Early Stage Researcher at the University of Turin, Italy.
Internships: September 2013 - February 2014, Graz/Austria at the TU GRAZ; field: electrochemistry. October 2012 –December 2012, Caparica/Portugal in CENIMAT; field: transistors.

Corresponding author: Anna Wolczyk, email: annnaroza.wolczyk@unito.it, tel: +393453615562.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

MgCl2 PROMOTED HYDROLYSIS OF MgH2 NANOPARTICLES FORHIGHLY EFFICIENT H2 GENERATION
Jun Chen 1, Jie Zheng 2, Xingguo Li 3
1 PhD candidate, 2 Associate Professor, 3 Professor
In our previous work, it’s found that MgCl2 can significantly promote the hydrolysis of Mg[1]. In this work, we found that
MgCl2 can also significantly promote the hydrolysis of MgH2. Compared with Mg, MgH2 has higher capacity of H2generation. Using 100-500 nm MgH2 particles, near theoretical amount of H2 (1723.8 ml/g) was released in 20 min in 1 M
MgCl2 solution. The most notable advantage of this system is the constant composition of the solution, which allows
continuous H2 generation without changing the solution.

Introduction
It remains highly challenging to develop reversiblehydrogen storage systems meeting all the requirements[2]
for on broad applications . An alternative approach isusing disposable hydrogen carriers to generate hydrogenand recover the hydrogen carriers from the spent fuel )
[3]. This approach may have impact in the near term,
which is particularly attractive for portable, onsitehydrogen generation. The hydrolysis reaction of Mg or
MgH2 is very convenient for on site hydrogen generation.
However, the reaction of Mg or MgH2 with H2O is very
slow at room temperature, due to the formation of thesurface passivation Mg(OH)2 layer.

A reasonable explanation for the promotion effects
illustrated in Fig 1c. In deionized water, hydrolysis of
MgH2 leads to an increase of the OH concentration near
the MgH2 surface. The insoluble Mg(OH)2 layer is formed
when the OH- anions attached to the MgH2 surface. In2+
MgCl2 solution, the Mg cations in the solution willcompete OH with the surface of MgH2 particles. In thiscase, the formed Mg(OH)2 will be dispersed in thesolution rather than forming a passivation layer coated on
the MgH2 particles.

Experimental / Computational
Mg nanoparticles are prepared by the hydrogenplasma metal reaction (HPMR) as described in ourprevious publications. MgH2 nanoparticles are preparedby direct hydrogenation of Mg nanoparticles. Hydrogengeneration kinetics is measured by H2 collection processwith displacement.

Results and Discussion
Fig. 1a shows the H2 generation kinetics fromhydrolysis of the MgH2 nanoparticles in deionized waterand in 1 M MgCl2 solution at 295 K. The hydrolysis of
MgH2 is quite slow in deionized water. After 40 min, only-1
23% (418.6 mL g ) theoretical H2 is released. The
incomplete hydrolysis is attributed to the formation of the
Mg(OH)2 passivation layer. Presence of MgCl2 in thesolution significantly promotes the hydrolysis reaction. In
the first 5 min, 59% (1073.8 mL g-1) theoretical H2 wasreleased. Near 100% (1820 mL g-1) theoretical H2 wasreleased within 20 min.

Fig. 1 a) H2 generation kinetics from thereaction of MgH2 nanoparticles with
deionized water and 1 M MgCl2 solution.
b)SEM image of MgH2 nanoparticles. c)
Schematic illustration of the mechanism forthe hydrolysis of MgH2 in MgCl2 solution
References[1] X. Li, et al.  , 49, 9437 (2013)[2] J. Yang, et al.  8!9 ", 39, 656 (2010)[3] J. Graetz,  8!9 ", 38,73 (2009)

Jun Chen received B.S. degree in Chemistry from Wuhan University, China in 2013. He is currently
a direct promoted PhD student in Prof. Xingguo Li’s group. His research is focused on materials forhydrogen storage and hydrogen generation.

Jun Chen
Corresponding author: Xingguo Li, xgli@pku.edu.cn, Jie Zheng, zhengjie@pku.edu.cn, 86-10-62765930.

㸫㸫

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

STRUCTURAL ANALYSIS OF HYDRIDES BY HIGH INTENSITY NEUTRONTOTAL DIFFRACTOMETER (NOVA)
Kazutaka Ikeda1, Toshiya Otomo1, 2, Hidetoshi Ohshita1, Naokatsu Kaneko1, Tomohiro
Seya1, Fumika Fujisaki2, Kentaro Suzuya3
1 Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), 2 Department
Materials Structure Science, The Graduate University for Advanced Studies (SOKENDAI), 3 J-PARC Center, Japan
Atomic Energy Agency
Abstract
A high intensity neutron total diffractometer (NOVA) was constructed to study atomic distribution in various materials
including liquids, amorphous and crystals. Short time and small sample measurements are feasible for averaged
structure analysis, and the real space resolution is enough for local structure analysis. The time-divided neutron
diffraction profiles of Pd powder during the deuterium absorption reaction was investigated on the second time scale.

A high intensity neutron total diffractometer, NOVA, at
BL21 of J-PARC (Japan Proton Accelerator ResearchComplex)/MLF (Materials and Life Science Experimental
Facility) provides an effective opportunity to study atomic
distribution in various materials. Short time and small
sample measurements are feasible for averaged
structure analysis, and the real space resolution isenough for local structure (Pair Distribution Function)
analysis. Crystalline structure as well as amorphous andliquid structure was investigated by NOVA for AlD3 [1],LaDx and
LiAl(ND2)4
[2].
Also,
time-transient
measurement during hydrogen absorption and desorption
process under hydrogen/deuterium gas atmosphere (max
10 MPa) is performed on NOVA, using a tight cell madefrom single crystal sapphire. The diffraction profiles ofpowder samples in the tight cell are obtained byremoving the Bragg peaks of the single crystal sapphire.
Absorption was carried out by submitting Pd powder to adeuterium pressure of 2 MPa at 393 K and letting it
absorb with its own kinetics in quasi-equilibrium
conditions. The time-divided neutron diffraction profiles
during the deuterium absorption reaction revealed thatthe phase continuously transforms from metal Pd through
D-PdDx to E-PdD~0.7 in a few seconds (Fig. 1).
This work was partially supported by the New Energy
and Industrial Technology Development Organization(NEDO) under “Advanced Fundamental Research
Project on Hydrogen Storage Materials (HydroStar)” and“Feasibility Study on Advanced Hydrogen Storage
Materials for Automotive Applications (2012)”, JSPS

2006

KAKENHI Grant Numbers 23686101, 24241034,
15K13810 and the Neutron Scattering Program Advisory
Committee of IMSS, KEK (Proposal No. 2009S06,
2014S06).

Fig. 1 Time-transient for neutron diffraction profiles of PdD2 system.
[1] K. Ikeda, H. Ohshita, N. Kaneko, J. Zhang, M.
Yonemura, T. Otomo, K. Suzuya, H. Yukawa, M.
Morinaga, H.-W. Li, S. Semboshi, S. Orimo,    , 52, 598 (2011)[2] K. Ikeda, T. Otomo, H. Ohshita, N. Kaneko, M.
Tsubota, K. Suzuya, F. Fujisaki, T. Ono, T. Yamanaka, K.
Shimoda, T. Ichikawa, Y. Kojima,    , 55, 1129
(2014)

Ph.D, Tohoku University, Japan

2006 – 2007

JSPS Fellow, Japan

2007 – 2010

Assistant Professor, IMR, Tohoku University, Japan

2010 – present Associate Professor , IMSS, KEK, Japan

Kazutaka Ikeda
Corresponding author: Kazutaka Ikeda, kikeda@post.j-parc.jp, +81-29-284-4639

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

ELECTROCHEMICAL CO2 REDUCTION TO SPECIFIC HYDROCARBONSMariana 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, CH-1951 Sion, Switzerland
Abstract
The simultaneous electrochemical reduction of CO2 and H2O allows the direct production of hydrocarbons, which have thesame energy density as fossil fuels, from electricity. The key factor in determining the product distribution in CO2 reductionis the cathode material. The new concept of present work is designing new catalytic materials for CO2 reduction whichallows to obtain the surface which will play role of electrode, catalyst and H-donor for creating hydrocarbons at the sametime.

Carbon dioxide concentration in theatmosphere is continuously increasing. The
reduction of CO2 with hydrogen to hydrocarbons(synthetic fuels) allows storing renewable energy
with the same energy density as fossil fuels.
Therefore, electrochemical CO2 reduction to specifichydrocarbon after its extraction from the air is ofgreat importance for the future energy economy
based on renewable energy.
The advantage of the simultaneouselectrochemical reduction of CO2 and H2O allows the
direct production of hydrocarbons from electricity,
compare to other reactions, e.g. Sabatier, reversed
water gas shift reaction and Fischer-Tropsch
synthesis, which are based on the availability ofhydrogen (obtained from electrolysis) and the
reduction reaction in a heterogeneously catalyzed
reaction.
The product distribution in CO2 reduction
varies widely, depending primarily on the electrodemetals and the electrolyte solutions used for theprocess [1]. The key factor in determining the
product distribution in CO2 reduction is the cathodematerial. Copper is a unique electrode, which canelectro-catalytically convert CO2 and water intohydrocarbons and alcohols at atmospherictemperature and pressure. Such products as CH4,
C2H4, EtOH, and PrOH, as well as CO, are produced
from CO2 at Cu electrode according to the one of theearly work of Hori [1].
The new concept of present work is tocombine on the electrode surface H2 and CO2
simultaneously and continuously.

Mariana Spodaryk

The aim of our work is designing a new
catalytic copper-containing materials for CO2
reduction which allows to obtain the surface which
will play role of electrode, catalyst and H-donor for
creating hydrocarbons at the same time (Fig.1). First
experimental results in this direction seem to be very
promising [2, 3].

Fig.1. Schematic representation of electrochemical CO2
reduction to synthetic fuels (SF).

The successful development of such acatalytic material for the electrochemical CO2
reduction will enable the efficient production of
specific hydrocarbons substituting fossil fuels by
renewable energy.

References[1] Y. Hori, Modern Aspects of Electrochemistry, 42, ch. 3,
89–189, Springer, New York (2008).
[2] K.Ohkawa et al., J. Electroanal. Chem., 367, 165–173(1994).
[3] S. Kato, A. Züttel et al., Phys. Chem. Chem. Phys.,
14, 5518–5526 (2012)

Short CV of Mariana Spodaryk
Born 17th of October 1988 in Ivano-Frankivsk, Ukraine
2011 Master Degree in Technical Electrochemistry in Kyiv National University of Technology and
Design, Ukraine
2011 - 14 PhD student, Ukraine National Academy of Science in Kyiv, Ukraine2013 - 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 - LMER in Sion, Switzerland

Corresponding author: Mariana Spodaryk, email: mariana.spodaryk@epfl.ch, Tel. +41 78 810 7516

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HYDROGENETION REACTION OF PRECIOUS METAL NANOPARTICLESSTUDIED BY TIME-RESOLVED X-RAY ABSORPTION SPECTROSCOPY
D. Matsumura1, Y. Okajima2, Y. Nishihata1, J. Mizuki3
1 Japan Atomic Energy Agency, Japan, 2 SPring-8 Service Co. Ltd., Japan, 3 Kwansei Gakuin University, Japan
Abstract
Nanoparticles often show different hydrogenation and dehydrogenation properties from bulk materials. We haveobserved hydrogenation and dehydrogenation reactions of Pd, Rh and Pt metal nanoparticles by using real-timeresolved X-ray absorption fine structure spectroscopy. For Pd nanoparticle, the intermediate state was detected byobserving increase of Debye-Waller factor during hydrogenation process. For Rh case, surface and interface hydrogen
adsorption processes were separately detected.

Introduction
Precious metal nanoparticles have been widely used aspractical catalysts of hydrogenation reaction and often
show different hydrogen adsorption, absorption anddesorption properties from bulk materials. It is typicallyobserved in an ambiguous - transition in the case of
Pd nanoparticles. We have developed the real-timeresolved X-ray absorption fine structure (XAFS)
spectroscopy system with the dispersive optics in order tounderstand the dynamic structural change of the Pd andother precious metal nanoparticles during hydrogenation
reaction. It was succeeded to obtain the spectra with 5
ms exposure time in the real-time-resolved mode anddetermine the reaction time below 10 ms [1]. In thispresentation, we show the dynamic structure of the Pd
nanoparticles during hydrogenation reaction besideshydrogen adsorption reaction of Rh and Pt metal
nanoparticles.

distances exist at the middle stage of the reaction. This
may not be consistent with the result that the limiting-rate
process of the reaction is the surface dissociative
adsorption of the hydrogen molecule [1]. We want tostate that the hydrogen atoms move very quickly withmaking the distortion of Pd local bonds at the middle
stage of the hydrogenation reaction.

Experimental
XAFS spectra were observed at BL14B1 and BL28B2 ofSPring-8 by dispersive mode. The local structuraltransformation of metal nanoparticles on Al2O3 duringhydrogenation reaction was investigated with the realtime-resolved mode.

Results and Discussion
Figure 1 shows the temporal variations of the interatomic
distance and the Debye-Waller factor of the Pd
nanoparticles of Al2O3 during hydrogenation reaction.
Sudden increase of the interatomic distance shows thePd nanoparticles was transformed to the  phase in
about 0.5 s. The positive peak of the Debye-Waller factor
is observed during the interatomic distance increases,
which indicates that both the long and short interatomic

Fig. 1 Temporal variations of interatomic distance andDebye-Waller factor for Pd nanoparticles duringhydrogenation reaction.

References[1] D. Matsumura, et al., 8  430, 012024(2013)

Short CV
D.Sc., The University of Tokyo, 2004
Researcher, Japan Atomic Energy Agency, 2005Research topics: X-ray absorption fine structure, real-time-resolved measurement, metal
nanoparticle catalyst
D. Matsumura
Corresponding author: Daiju Matsumura, daiju@spring8.or.jp, +81-791-58-2637

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

RECYCLABLE HYROGEN STORAGE IN LiBH4 COMPOSITE WITH h-BN
Jiuyi Zhu, Weitong Cai, Hui Wang, Min Zhu㸨
School of Materials Science and Engineering, South China University of Technology, Key Laboratory of Advanced
Energy Storage Materials of Guangdong Province, Guangzhou, 510641, PR China.
Abstract
The -BN-LiBH4 composite has excellent hydrogen storage properties. The high-energy ball-milled -BN could not only
act as catalyst to the dehydrogenation of LiBH4, which made the on-set temperature at ~200 °C, but also react to LiBH4,
which formed a broadened intercalating space and non-crystallization structure. These results suggests that -BN may
store hydrogen with B-H and N-H bonds.

Introduction
Lithium borohydride has been extensively investigated
due to its highest gravimetric and volumetric hydrogendensity of 18.4 wt.% and 121 kgm-3, respectively [1].
However, owing to the thermodynamic stability andkinetic
restrictions,themain-dehydrogenation
temperature of LiBH4 is as high as above 400 °C. What’smore, the re-hydrogenation of LiBH4 requires extremely
harsh conditions [2]. In order to solve the problem, manystudies have been done with such as nano-confinement,
destabilization and catalysts. In this study, -BN-LiBH4
system has been studied to improve the hydrogenstorage performances of LiBH4.

It showed the excellent cyclic property in 3:1 -BNLiBH4 sample with high capacity of hydrogen, at
400°C/10 MPa
One of the possible mechanisms is that the interaction
with LiBH4 and h-BN made h-BN broadened intercalating
space and non-crystallization structure. This special h-BN
could adsorb hydrogen with forming B-H and N-H bonds
according to the FT-IR results.

Experimental / Computational
LiBH4 (Sigma-Aldrich Ӌ95%) was vibratory ball milledwith 500 rpm for 1 hour. -BN (Alfa Aesar Ӌ99.5%) was
planetary ball milled with 600 rpm for different time. The
20 hours milled h-BN and pre-milled LiBH4 weremechanically milled for 1 hour in different mole ratio of
1:2, 1:1, 2:1 and 3:1, respectively.

Results and Discussion
The introduction of 20h-milled -BN led to a fasterdehydrogenation kinetics of LiBH4. The h-BN-LiBH4 withthe mole ratio 3:1 dehydrogenated over 3 wt.% in 1 hour
at 400 °C, which is much higher than 2 wt.% of milled
LiBH4. The TPD-MS profiles showed the decompositionof the higher content of -BN was big different from thepure LiBH4 with lower dehydrogenation temperature(~200 °C below the melt point of LiBH4 for 3:1 sample).

Fig. 1 Isothermal dehydrogenation curves at 400 ºC of (a)pre-milled LiBH4 and LiBH4-h-BN system with different
mole ratio (b) 2:1; (c) 1:1; (d) 1:2; (e) 1:3.
References[1] L. Schlapbach, A. Zuttel, Nature 414 (6861) (2001)[2] S. Orimo, J. Alloys Compd. 404-406 (2005)

PhD. candidate in School of Materials Science and Engineering, South China University ofTechnology. He focus research on the dehydrogenation of borohydride complex system and the
preparation of two-dimension material.

Jiuyi ZHU
Corresponding author: Min ZHU, Email: memzhu@scut.edu.cn, Tel: +86 20 87113923.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

HOW CATIONS MOVE IN BORON-HYDRIDE ELECTROLYTES: FIRSTPRINCIPLES MOLECULAR DYNAMICS
Tamio Ikeshoji,1,2 Atsushi Unemoto,2 Shigeyuki Takagi1, Motoaki Matsuo,1 Shin-ichi
Orimo1,2
1 Institute for Materials Research, Tohoku University, 2 Advanced Institute for Materials Research, Tohoku University
Abstract
First-principles molecular dynamics simulations could follow ion movement in electrolytes. We have simulated cation (Li,Na, Mg) movement in electrolytes of BH4 and B12H12 anions. Cations move in the electrolytes with keeping coordinationby H atoms of boron-hydrides.

Introduction
Since discovery of fast lithium ion conduction in
high-temperature phase of LiBH4 [1], these boronhydrides become a possible ionic conductor in batteries.
Solid-state lithium batteries have been constructed andshowed a good performance with high durability [2]. In
order to understand how cations are transferred in theelectrolytes and what roles hydrogen atoms play, firstprinciples molecular dynamics (FPMD) simulation has
been carried out. Large-size and long-time calculations
are necessary [3].

It is possible to understand the flexibility of the
H-coordination from the B-H angle distribution. In thecase of fast ionic conductors, it is widely distributed
because the cations move around. In the slow ionic
conductors, it is sharply distributed because the cations
are restricted at the energy minimum structure.

Computations
Two different FPMD codes, FEMETECK and
STATE, were used. The both are based on density
functional theory (DFT) for electronic structure
calculations with pseudo potentials and PBE functional
under the periodic boundary conditions. In some cases,
masses of atoms were tuned to have fast computations
with giving correct thermodynamic properties [3].

The calculations were performed using super computers at
Tohoku University and Kyushu University.

Results and Discussion
Cations in the electrolytes are surrounded byhydrogen atoms of boron hydrides. This feature wasconfirmed from radial distribution function of H to the
cations in all electrolytes calculated; LiBH4, Mg(BH4)2,
Li2B12H12, and Na2B12H12. In order to have fast cation
conductivity, H-coordination must be flexible for thecation movement. If H-coordination is sufficient at thetransition state of the ion transfer, the fast ion
conductance will be attained. H-coordination number
changes smoothly from high value to a little bit smallvalue at the transition state (Fig. 1) [4]. In the case ofslow ionic conductors, cations can not move to outside of
the H-coordinated space because it is difficult to havehigh coordination number at the transition state [3].

Tamio Ikeshoji

Fig. 1 Contour map of H-coordination number (H(Li)) of a Li
atom in bulk LiBH4. [4]References[1] M. Matsuo, Y. Nakamori, S. Orimo, H. Maekawa and H.
Takamura, Appl. Phys. Lett., 2007, 91, 224103.
[2] A. Unemoto, T. Ikeshoji, S. Yasaku, M. Matsuo, V.
Stavila, T. J. Udovic, and S. Orimo, Chem. Mater. 27,
2015, 5407-5416.
[3] T. Ikeshoji, E. Tsuchida, S. Takagi, M. Matsuo and S.
Orimo, RSC Adv., 2014, 4, 1366–1370.

[4] T. Ikeshoji, Y. Ando, M. Otani, E. Tsuchida, S. Takagi, M.
Matsuo and S. Orimo, Appl. Phys. Lett., 2013, 103,
133903.

1977

Doctor of Engineering, Tokyo Institute of Technology, Japan1978

Researcher, Government Industrial Research Institute Tohoku, AIST, MITI, Japan

2003 - 2010

Director, Research Institute for Computational Sciences, AIST, Japan

2010 - 2011

Professor, NICHe, Tohoku University, Japan2011-

Researcher in Tohoku University, AIST, and FC-Cubic

Corresponding author: Tamio Ikeshoji, ikeshoji@imr.tohoku.ac.jp, +81-22-215-2094

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

COMPLEX HYDRIDE ELECTRODES FOR HIGH-ENERGY DENSITY 
ALL-SOLID-STATE LITHIUM-SULFUR BATTERY
Atsushi Unemoto1, Motoaki Matsuo2, Tamio Ikeshoji1,2, Shin-ichi Orimo1,2
1
2

WPI–Advanced Institute for Materials Research (WPI–AIMR), Tohoku University, Sendai 980-8577, Japan.
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan.

Complex hydride is considered as a promising candidate electrolyte for high-energy density all-solid-state lithium-sulfur(Li-S) battery. We review here our research activities relevant to this battery using the complex hydride electrolytes.

Complex hydrides for high-energy density
Li-S battery
Lithium-sulfur (Li-S) battery, which promises an–1enhanced energy density (~2600 Wh kg ) compared tothe conventional lithium battery (~400 Wh kg–1) [1], isconsidered as one of the next generation energy
reservoirs. Complex hydride is a promising candidate
electrolyte for the Li–S battery owing to fast-ionic
conductivity, high thermal and electrochemical stabilities,
and high deformability [2–4]. We realised repeated
operation of a bulk-type all-solid-state Li-S battery using
a LiBH4 electrolyte at 393 K [3]. The operation
temperature could be decreased down to 373 K by using
a LiBH4–LiCl electrolyte [4].

temperature could be reduced down to 373 K by using
the LiBH4–LiCl electrolyte. These results demonstratethat the complex hydride electrolytes promise repeated
operation of the high-energy density bulk-type all-solidstate Li-S battery.
This research was funded by the Target Project 4 of
WPI–AIMR, E-IMR, JSPS KAKENHI (25220911), andALCA program from JST.

Demonstration of the bulk-type all-solidstate Li-S battery operation [3,4]To achieve repeated operation of the bulk-type all-solidstate Li-S battery, a high concentration of a robustinterface among the elemental sulfur, conductive additiveand electrolyte needs to be established in the electrodelayer. We succeeded in a mutual dispersion of elemental
sulfur and mixed conductive additives, comprised of
Ketjen Black (KB) and the activated carbon, Maxsorb®,
via a high-energy mechanical ball milling technique in the
S-C composite powder. Highly deformable nature of thecomplex hydride electrolytes allowed for introducing acharge-transfer interface between this S-C composite
powder and LiBH4 or LiBH4–LiCl merely by a coldpressing. As results of these microstructure optimizationof the composite electrode layer, we realized repeated
operation of the bulk-type all-solid-state Li-S battery.
When the LiBH4 electrolyte is used, high discharge
capacity was retained over the repeated battery cycles at
393 K, as shown in Fig. 1. The 45th discharge capacity
retained as high as 730 mAh g–1 (~1410 Wh kg–1) withnearly 100 % coulombic efficiency. The battery operation

Fig. 1 Discharge–charge profiles of the bulk-type allsolid-state Li–S battery operated at 393 K and 0.05 C [3].

References[1] Y.-X. Yin, S. Xin, Y.-G. Guo, L.-J. Wan, Angew. Chem.
Int. Ed. 52, 13186 (2013).
[2] M. Matsuo, S. Orimo, Adv. Energ. Mater. 1, 161(2011): A. Unemoto, M. Matsuo, S. Orimo, Adv. Funct.
Mater. 24, 2267 (2014).
[3] A. Unemoto, S. Yasaku, G. Nogami, Masaru Tazawa,
M. Taniguchi, M. Matsuo, T. Ikeshoji, S. Orimo, Appl.
Phys. Lett. 105, 083901 (2014).
[4] A. Unemoto, C. Chen, Z. Wang, M. Matsuo, T.
Ikeshoji, S. Orimo, Nanotechnology 26, 254001 (2015).

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 Cooperative Research Center for Energy Materials, Tohoku University. His
research interests are fundamentals and energy-related applications of hydrides. He was awarded“The Prize for Science and Technology (Research Category), The Commendation for Science andTechnology by the Minister, MEXT (2012)”.
Shin-ichi Orimo

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

Corresponding author: Shin-ichi Orimo, orimo@imr.tohoku.ac.jp, Tel.+81-22-215-2094

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

LOCAL ATOMIC ORDER IN THE Ni-BASED AMORPHOUS HYDROGEN PERMEATION MEMBRANES
1

1

2

3

4

5

5

2

S. SARKER , D. CHANDRA *, G. KING , T.J. UDOVIC , D. ISHEIM , M. DOLAN , D. VIANO , J.WERMER ,B. RUTA
1
UNIVERSITY OF NEVADA, RENO, NEVADA 89557, USA,
2
LOS ALAMOS NATIONAL LABORATORY, LOS ALAMOS, NM 87545
3
NIST CENTER FOR NEUTRON RESEARCH, MS 6102, GAITHERSBURG, MD 20899-6102
4
MAT. SCI.& ENGR., NORTHWESTERN UNIVERSITY, 2220 CAMPUS DR, EVANSTON, IL 60208
5CSIRO, DIVISION OF ENERGY TECHNOLOGY, KENMORE, QLD 4069, AUSTRALIA
6
ESRF, GRENOBLE, FRANCE

6

Abstract
Lattice dynamic and atom tomography studies of the NiNbZr alloys are being investigated. Atom probe tomography (APT) data
revealed Nb-rich and Zr-rich clusters embedded in a Ni-rich matrix. We used Fukuhara et al. reported icosahedral model to correlate our
APT found clusters. X-ray Photon Correlation spectroscopic (XPCS), neutron (elastic and inelastic) data, and atom probe tomography
data of these membranes are presented.
Introduction
Crystalline Pd/Pd-Ag membranes are widely used for hydrogen
separation from CO2 and other gases in power generation
applications. Inexpensive Ni-based alloys are being developed
to replace these noble metal alloy membranes. We are studying
amorphous ribbons of (Ni0.60Nb0.40)100-xZrx (x=0-30 at %)fabricated by melt-spinning method that exhibit relatively highopermeabilities of hydrogen between 200-400 C. Neutron HIPD
data (Los Alamos) showed Ni-Ni, Ni-Nb, or Ni-Zr interatomic
distances. Neutron FANS (NIST) data on these alloys yielded
possible positions of hydrogen. The compositions of the clusters
found deviated from the nominal overall composition of themembrane. We interpreted that our clusters are composed of
icosahedral structure proposed by Fukuhara et al.

Experimental / Computational
Atom Probe Tomography is used to obtain image of atomic
configuration in solids at Northwestern University. A nanoscaleneedle is made by using a Field Ion Beam (FIB) instrument. The
atom probe combines a time-of-flight (ToF) mass spectrometerfor elemental mapping coupled with position sensing system toobtain a 3D reconstruction of atoms probed. By applying a highvoltage (~10 kV) between the specimen and a counter electrode,a high electric field (~1010 V/m) is created on the apex of a
sharp (<100 nm radius) specimen held at cryogenic
temperatures. A local electrode atom probe LEAP® instrument isused in this study. X-ray photon correlation spectroscopy(XPCS) uses coherent x-ray scattering and can measure slow
2
6
dynamics typically 10
to 10 Hz [1]. The ESRF has a third
generation synchrotron radiation source at ID10B Troika-1beamline. The X-ray O= 1.55 Å with 8.1KeV photon energy
was selected by single bounce Si (111) monochromator having a-4-4
bandwidth of / ̱10 and an energy resolution E/E~10 .
Inelastic neutron scattering was used for measuring thevibrational spectra of materials. Filter-Analyzer Neutron
Spectrometer (FANS) at the NIST Center for Neutron Research(NCNR) is perfect for measuring the atomic vibrational dynamics
of hydrogen atom. Monochromatic neutrons of variable energy
are inelastically scattered from sample and detected at a fixed
final energy Ef after through a low-pass Bragg cutoff filter.
Inelastic neutron spectra are then recorded by scanning theincident energy and detecting all scattered neutrons with energy
Ef<Ecutoff.

Results and Discussion

DhaneshChandraWe studied binary Ni60Nb40 and or Ni42Nb28Zr30. The Zr andNb rich clusters were detected in real space by APT.
Compositions of Nb and Zr rich clusters were obtained as
Ni38.64Nb17.9Zr43.45
and
that
of
Nb-richclusters
Ni31.78Nb46.5Zr21.7, as compared to the bulk nominal
composition of Ni42Nb28Zr30. Atom dynamic studies by XPCS
showed significant changes in the relaxation times as shown in
the Fig. 1 for Ni60Nb40 alloy. Addition of Zr to NiNb binary
making (Ni.60Nb.40)70 Zr30 alloy increases the permeability by
two orders of magnitude; the differences in the relaxation times
between the Zr and non-Zr alloys will be presented.
Neutron vibrational spectroscopy (NVS) to observe dynamics inamorphous materials, we found that the most prominent phononmodes of ZrH2 are around 138MeV, where vibrationalfrequencies of Zr tetrahedral site reside. The Ni60Nb40 (without
any Zr) content did not show significant neutron counts resulting
in a board (purple color) peak; also the H-loading is much lower
than the other samples, as expected. The NVS of Ni60Nb40
gave us an idea about other non-Zr4-type, weaker sites. We also
compared our phonon modes of ribbons at 120 MeV and 160
MeV which probably represent modes in Nb-hydride and othermixed phases. (B. Hauer, Udovic Physics Review, B,57 (1998)
18.

Fig.1. Two time correlation functions before andafter hydrogenation Normalized intensity autocorrelation functions at 373 K under vacuum (at1600 and 4600 s).

References[1] X-Ray Photon Correlation, Spectroscopy, Soft Matter
Characterization book by G. Grubel, A. Madsen, A. Robert M.
Matsuo, S. Orimo, Adv. Energy Mater. 1, 161 (2011Foundation Professor, Metallurgical and Materials Engineering, College of Engineering, LMR 468,
Mail Stop 388, University of Nevada, Reno (UNR), Reno, NV 89557-0140 Phone: Office: 775784-4960, Home: 775-747-7847, Fax: 775-784-4316. dchandra@unr.edu.
Research involves complex and classical hydrogen storage, computational CALPHAD type phase
diagram calculations, synthesis and characterization of amorphous membranes for hydrogen
separation, thermal energy storage in orientationally disordered plastic crystals, vapor pressure
measurements by using Knudsen effusion thermogravimetric method for alloys, hydrides, and othermaterials.

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

DEHYDROGENATION AND REGENERATION OF AMMONIA BORANE IN
IONIC LIQUIDS
Tessui Nakagawa1, Hiroki Uesato1, Sho Sashida1, Anthony K. Burrell2, Rico E. Del
Sesto2, Michael T. Janicke2, and Benjamin L. Davis2
1 University of the Ryukyus, 2 Los Alamos National Laboratory,
Dehydrogenation and regeneration properties of ammonia borane (AB; NH 3BH3) in Ionic liquid (IL) have been
investigated. 30:70 wt. ratio of AB-ILs desorbed >2 eq. H2 at 90 C with small impurity emission and forming solid
solution of PB and IL. Regeneration using hydrazine and liq. NH3 for 4 days at 40 C was succeeded with several
impurities probably due to catalytic effect of ILs, indicating selection of IL is important for regeneration of AB-IL mixtures.

Introduction
Ammonia borane (AB; NH3BH3) is a promising hydrogenstorage material in automotive applications. There arethree serious drawbacks for the on-board system, which
are slow dehydrogenation kinetics, impurity gas emission,and poor reversibility. In order to improve these
performances, we investigated the dehydrogenation andregeneration properties of mixtures of AB and Ionic
liquids (ILs) based upon 1-butyl-3-methylimidazolium
Chloride (BmimCl) likewise reported by Himmelberger, etal [1]. The weight ratio of AB:ILs at 3:7 was employed as
the tested materials due to near-saturated solution. *indicating ILs may act as a “negative” catalyst for the ABIL regeneration. The tendency of these by-products
seems to depend on the functional group. On the other
hand, Regeneration of half-dehydrogenated AB-BmimCl
was almost successful because less impurity, indicatingthat less interaction between spent fuel and ILs gives
clean regeneration. Above results confirm that ionic liquid
based ammonia borane have a potential for practical use
although improvement of mitigated issues, which aresmall impurities emission, slow kinetics at RT, andgeneration of by-products after regeneration, are stillrequired.

Experimental / Computational

Results and Discussion
TG-RGA-IR results showed that dehydrogenation of all
AB-ILs had completed by 150 °C with less impurities thanneat AB. Isothermal dehydrogenation of AB-ILs resulted
that ~2 eq. H2 desorbed from AB by 150 minutes at 90 °C(Fig. 1), while less than 0.08 eq. H2 desorbed with almost
no impurity species at RT. Solid and solution NMR results
showed the evidence of no reaction between AB and IL
but solid solution after dehydrogenation. Regeneration of
dehydrogenated AB-ILs resulted that the decoupled 11B     !  #$\However, there were several impurities in the profiles,

T. Nakagawa

AB-ILs Isothermal dehydrogenation@90 qC-1

2
Yield/mol H2 AB

Dehydrogenation properties of AB-ILs were evaluated byburettes system (isothermal at RT and 90 °C) and TGRGA-IR (heating up to 150 °C, 1 °C/min). Solid (MAS)and solution (1H, 11B, and 13C in d-MeCN) NMR profilesof AB-IL before/after dehydrogenation and after
regeneration were acquired. Regeneration of AB-ILs was
performed in liq. NH3 and N2H4 at 40 °C for 4 days.

1-1+BmimCl (2.0 eq. H2 AB )-1

+BmmimCl (2.0 eq. H2 AB )-1

0

+EmimCl (2.1 eq. H2 AB )0100
Time/min200

300

Fig. 1 dehydrogenation of AB-ILs at 90 °C
References[1] 1.
D.W. Himmelberger, L.R. Alden, M.E. Bluhm,
and L.G. Sneddon, Inorg. Chem. 48, 9883 (2009).

Tessui Nakagawa is currently an assistant professor in the Chemistry course, Faculty of Science,
University of the Ryukyus. Nakagawa received Ph.D from Hiroshima University in 2009 (Supervisor:
Prof. Yoshitsugu Kojima) and then worked at Hiroshima University (2009), Los Alamos National
Laboratory in the U.S. (2009-2012), and University of Tsukuba (2012). His research topics are (1)hydrogen storage alloys, (2) materials for ammonia capture, and (3) ammonia borane especiallymetal amidoboranes, ionic liquids, and regeneration. He has published a lot of reports such as
magnetic materials, hydrogen storage alloys, MH-amide systems, MH-borohydride systems, metal
amidoborane systems, ammonia borane (AB) –MOF, AB-ionic liquids (ILs), and regeneration of AB.
More information (website): http://chem.sci.u-ryukyu.ac.jp/?page_id=2791.

Corresponding author: Tessui Nakagawa, tessui@sci.u-ryukyu.ac.jp, +81-98-895-8535

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

Mg BASE TERNARY ALLOYS WITH IMPROVED HYDROGEN STORAGE
PROPERTIESMin Zhu, Yanshan Lu, Hui Wang, Liuzhang Ouyang, Jiangwen Liu
School of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong
Province, South China University of Technology, Guangzhou, 510641, China
Abstract:
Mg base ternary alloys Mg-In-Ni and Mg-Ag-Al with improved hydriding-dehydriding thermodynamic and kinetic
properties have been developed. The obtained alloys exhibit reversible hydrogen storage properties and altered reaction
pathway, in which the intermediated phases react with MgH2 in the dehydriding process, and contributes to theimprovement in the thermodynamics. Our work demonstrates the potential of exploring new Mg-based intermetallic
compounds for hydrogen storage applications.

Introduction
Mg is considered to be a promising metallic hydrogenstorage material with high capacity and abundantresource. However, the over-high operating temperature
due to unfavourable thermodynamics of magnesium
hydride (MgH2) hinders its practical applications. Herein
we investigate the reversible phase transformation of MgIn-Ni and Mg-Ag-Al ternary alloys during de/hydrogenation
cycles,andtheirde-/hydriding
thermodynamic and kinetic properties.

The phase transition of Mg-Ag-Al alloys in dehydriding
process was also revealed. It is found that he milled MgAg-Al alloy shows higher dehydriding pressure and fasterhydrogen sorption kinetics in comparison with those ofpure Mg.

Experimental
The Mg base ternary alloys were prepared by sintering
followed by mechanical milling. The phase structure, thethermodynamic and kinetic properties of alloys werecharacterized.

Results
Two new Mg-In-Ni ternary alloy phases Mg14In3Ni3 andMg2InNi with orthorhombic structure were discovered forthe first time. In the hydriding process, the Mg14In3Ni3
alloy decomposes into a mixture of MgH2 and Mg2InNi,
which is fully reversible in the dehydrogenation. For thedehydriding of MgH2 and Mg2InNi, a decrease of thereaction enthalpy (70.1 kJ mol-1 H2) is obtained compared-1H2), and thewith pure MgH2 (77.9 kJ mol
dehydrogenation activation energy is decreased to 78.5
kJ mol-1 from ~160 kJ mol-1 for pure MgH2. The alloy
Mg90In5Ni5 containing the Mg14In3Ni3 phase has
reversible hydrogen storage capacity of 3.3 wt%, and theminimum dehydrogenation temperature is reduced to 230
qC (See Fig. 1(a)).

཰0J+0J,Q1L0J,Q1L+ཱ0J+0J+
Fig. 1 The PCI curve showing the two-step
dehydriding stages of the alloy Mg90In5Ni5.

Min Zhu is a professor in South China University of Technology. His main research interest lies in
the fields of advanced energy storage materials, such as hydrogen storage materials, electrodematerials for super-capacity and lithium ion battery materials.

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

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

STRUCTURAL AND THERMODYNAMIC PROPERTIES OF  
HYDROGEN-RICH SOLID SOLUTIONS OF IRON *K. Aoki1, H. Saitoh2, and A. Machida2
1 Univ. of Tokyo, 2 Japan Atomic Energy Agency
Hydrogen-rich solid solutions of iron have been investigated at temperatures of 300-1000 K and hydrogen pressures of
4-6 GPa by neutron diffraction and synchrotron X-ray diffraction. Interstitial site occupancies of hydrogen atoms and ahydrogen-induced volume expansion were determined for an equilibrium state of fcc FeDx at 988 K and 6.3 GPa. Lattice
volumes of fcc and dhcp FeHx showed significant variation with temperature owing to hydrogen desorption on heatingand hydrogen absorption on cooling; they were converted into hydrogen compositions using the hydrogen-induced
volume expansion. From the hydrogen composition-temperature relations thus obtained, the enthalpies of solution ofhydrogen were derived for the hydrogen-rich solid solutions.

Introduction
Iron, a prototype of transition metals, has an enthalpy
of solution of hydrogen around 30 kJ/mol and small
solubilities under normal hydrogen pressures. The
chemical potential of hydrogen steeply increases oncompression and results in a drastic enhancement of thesolubility amounting to many orders of magnitude atgigapascal (GPa) range. Actually, a stoichiometrichydride FeH with a dhcp metal lattice is formed above 3.5
GPa. Besides the low-temperature dhcp FeH, a solid
solution state with an fcc metal lattice is present at hightemperatures above 550 K. The phase boundary
between the low temperature dhcp and high temperature
fcc phases is approximately determined by in situ X-ray
diffraction [1]. As expected from the positive enthalpy ofsolution, gradual desorption of hydrogen is expected forthe monohydride dhcp FeH on heating. The temperature
variation of hydrogen composition is essential forunderstanding the thermodynamic properties of hydrogenrich Fe-H system.

GPa, and that the fcc metal lattice expands in proportion
to deuterium composition [2]. From this linear relation, ahydrogen-induced expansion
of Fe atomic volume is3
derived to be 2.21-Å /D, which allows quantitative
estimation of hydrogen or deuterium composition fromlattice volumes measured by X-ray diffraction.
Synchrotron X-ray diffraction measurements haverevealed that the low-temperature dhcp FeHx survives up
to about 900 K far above the reported transition
temperature of 600 K and the high-temperature fcc FeHx
survives down to 300 K. The reflection peaks show shifts
to high angles on heating and to low angle on cooling
owing to hydrogen desorption and absorption,
respectively. The lattice volume vs temperature relations
are converted into the hydrogen composition vstemperature relations. We successfully derive theenthalpies of solution of hydrogen for the dhcp and fcc
solid solutions from Arrhenius plots of these x-T relations.

Experimental
Neutron diffraction measurements were made at theBL11, MLF, J-PARC. An iron rod was deuterized in adeuterium sealing capsule made of NaCl. Diffraction
profiles were accumulated every 2 min during the heatingprocess to 1000 K at an initial pressure of about 7 GPa.
One hour accumulated diffraction profile was taken at
988 K and 6.3 GPa for structural refinement of fcc FeDx.
Synchrotron X-ray diffraction measurements weremade at the BL14B1, Spring-8. Fe powder specimen washydrogenated in the same capsule as used for theneutrondiffraction
measurements.
Time-resolved
diffraction profiles were collected by 12-s accumulation
for dhcp and fcc solid solutions on heating or coolingprocess at a rate of 25 K/m.

Fig. 1 Phase diagram of Fe-H system. The inset shows
Time-resolved X-ray diffraction profiles collected onheating at an initial pressure of 5 GPa.

Results and Discussion

References

Neutron diffraction measurements on fcc FeDx haverevealed that deuterium atoms occupy octahedral sites
with an occupancy of 0.532 and tetrahedral sites with
0.056 in an equilibrium state achieved at 988 K and 6.3[1] Y. Fukai et al, J. Alloys Comp. 348, (2003)105–109.
[2] A. Machida et al. Nature Communications, 5(2014)
5063-(1)-(6).

Guest Researcher, Geochemical Research Center, The University of Tokyo, 2015~
Senior Researcher, Institute for Materials Research, Tohoku University, 2012~2015.
Director of Synchrotron Radiation Research Center, Japan Atomic Energy Agency, 2008~2010.
Director of Basic Research Division, National Institute of Materials and Chemical Research, 1999~2001.
Professor, Department of Chemistry, Tsukuba University, 1995~2000.
Graduated from the University of Tokyo, Doctor of Science, 1978.
Katsutoshi Aoki

Corresponding author: Katsutoshi Aoki, k-aoki@eqchem.s.u-tokyo.ac.jp, 81-3-5841-7625.

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

NEUTRON STUDIES OF UNCONVENTIONAL HYDROGEN STORAGE
MATERIALS AND CATALYSTS
Martin Owen Jones1, Tom Autrey2, Bojana Ginovska2, Greg Schenter2, Josh Makepeace1, 4, Hazel
Hunter1, Tom Wood1, Timmy Ramirez Cuesta3, Bill David1, 4Affiliation 1 ISIS Neutron spallation facility, STFC, UK 2 PNNL, USA 3 SNS, Oakridge National Laboratory, USA, 4
Oxford University, UK
Neutron scattering techniques have been used to investigate a number of unconventional hydrogen storage media andcatalysts, in particular ammonia, which has a gravimetric hydrogen capacity 17.8wt% and frustrated Lewis acid bases(FLAB) catalysts which can heterolytically cleave H2 molecules at room temperature. He we will report on recent neutron
studies on solid state ammonia storage materials, ammonia cracking catalysts and solid state FLAB catalysts using boththe ISIS and SNS neutron spallation sources.

Introduction
Neutron scattering is a very powerful tool for the study ofhydrogen storage materials and hydrogenation catalysts
as the high neutron cross section of the hydrogen atom
makes it the strongest neutron scatterer [1]. Here we
report the use of neutron diffraction to investigate a new
catalyst for the decomposition of ammonia into nitrogenand hydrogen, a combined neutron diffraction, mass
spectroscopy and microwave dielectric study of solidstate ammonia storage materials and neutron
spectroscopy to investigate solid-state hydrogen splitting
catalysts.
Experimental / Computational

Neutron diffraction studies of ammonia cracking catalysts
were carried out on the Polaris diffractometer at the ISIS
neutron spallation facility on samples of nonstoichiometric imide catalysts ‘in-operando’ under flowing
ammonia (ND3) at 500oC [2]. Studies of solid-state
ammonia storage materials were also performed on the
Polaris diffractometer (Figure 1) in conjunction withsimultaneous mass spectroscopy and dielectriccharacterisation [3]. Inelastic neutron spectroscopy (INS)studies have been carried out on samples of 1-N-TMPCH2-2-[B(C6F5)2]C6H4 (QCAT) and its hydrogenatedproduct QCATH2 in conjunction with density functional
theory (DFT) modelling to investigate the mechanism ofhydrogen interaction and mass transport through solidstate FLAB catalysts.


Results and Discussion

Non-stoichiometric imide catalysts showed superior
catalytic activity when compared to ruthenium or nickel
based equivalents. Neutron diffraction demonstrated thatthe catalytically-active imide material was nonstoichiometric, closer in composition to the imide form
and that the stoichiometry was dependent on ammonia

flow. Microwave dielectric spectroscopy was used, in
conjunction with neutron diffraction and mass
spectroscopy, to determine the stoichiometry of solidstate ammonia storage materials. It was found thatmicrowave resonator techniques were an extremely
sensitive technique for determining ammonia content andcould also be used to follow phase transformation andthermal events on ammonia absorption. Inelastic neutron
spectroscopy with DFT modelling of QCAT and QCATH2
indicated there was no unambiguous physisorption
interaction below the temperature of reaction (H2heterolysis) and that the mass transport of hydrogenthrough the solid catalyst proceeded through adecrepitation mechanism.

Fig. 1 The Simultaneous Microwave Dielectric, Neutron
Diffraction and Mass Spectroscopy Apparatus.

References[1] G.E. Bacon, "Neutron Diffraction", Clarendon Press,
Oxford (1975).
[2] J. Hartley, A. Porch, M. O. Jones, Sensors &Actuators: B. Chemical 210 726-730 (2014).
[3] J. W. Makepeace, T. J. Wood, H. M. A. Hunter, M. O.
Jones and W. I. F. David Chemical Science 6(7) 38053815 (2015).

Martin Owen Jones is the Energy Materials Coordinator for the ISIS spallation neutron facility. He
has worked in many areas of energy materials including superconductors, transparent conducting
oxides and chemical energy storage. His most recent work has been in the use of ammonia as achemical energy vector.

Martin Owen
Jones
Corresponding author: Martin Owen Jones, martin-owen.jones@stfc.ac.uk, 00 44 1235567236

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

LONG-RANGE ORDERING OF DEUTERIUM ATOMS IN SUPERLATTICEALLOYS WITH PARTIAL Al/Si SUBSTITUTION
Sabrina Sartori and Matylda N. Guzik
Physics Department, Forskningsparken Gaustadalleen 21, University of Oslo, 0349 Oslo, Norway
Abstract
The structural aspects of Al/Si incorporation in La-Mg-Ni-based superlattice compounds are still missing. The main
identified challenge is related to the synthesis of a single or almost single phase sample. We present the successful
synthesis, deuteration and characterization of Al,Si-containing A2B7 and A5B19 phases.

Introduction
It is known that in some rare earth (RE) metal hydrides(e.g. LaNi5H6) disordered hydrogen atoms arrangements
can be observed. Recently, some evidences indicatedthat the RE–H/H–H distances may be much shorter thanit was thought and that additional, electronic factors play
an important role. It is also believed that they are
responsible for the preferred configurations of H atoms
around the transition metal, as found in the RET3Hx
system [1] (T = Transition metal). This suggests thatsome types of local order of hydrogen atoms, if verified inother systems, could support the idea that preferredhydrogen atoms configuration around the metal atoms
has influence on the properties and the storage capacityof the systems.

of secondary phases present in the starting alloys. The
detailed analysis of D-atoms distribution will be presented.
We believe these results will give important insight into
the nature of D–D separations in these compounds, andconsequently deuterium atom configurations andrepulsive D–D interactions.

Experimental
A series of (La,Mg)2(Ni,Al(Si))7 have been obtained bothwith metallurgical methods and by ball milling. The
samples were investigated by powder neutron diffraction(PND) during the in-situ deuteration performed at the
Canadian Neutron Beam Center, Chalk River, Canada.

Results and Discussion
Results suggest successful formation of deuterides(either with A2B7- or A5B19-type structure) in the studied
samples (see Figure 1). The obtained data confirm acomplete alloy ^ deuteride conversion in all samples.
The newly formed D-containing phases crystallize withthe same symmetry as the parent intermetallic alloys(P63/mmc). It also seems that the deuteration process
induces a partial/complete amorphisation/decomposition

Sabrina SartoriFig.1 Powder neutron diffraction data for (La,Mg)5(Ni,Al)19
and its deuteride(s), collected after exposure to 7 bar of
D2 gas for 20 hours and 1.5 months.

References[1] Y.E. Filinchuk, K. Yvon, Journal of Alloys andCompounds 404, 89 (2005).

Acknowledgments
The authors would like to gratefully acknowledge theskilful assistance from the beam scientist Julien Lang andprof. Jacques Huot.

Sabrina Sartori investigates materials for hydrogen storage since 2003. She has bee a postdoc at
the University of Padova (Italy) and a researcher at the Institute for Energy Technology (IFE,
Norway). Since 2013 she is a professor at the Physics Department of the University of Oslo,
Norway, where she established and leads a solid state laboratory. She is also coordinator of theEnergy and Environment group at the University Graduate Center UNIK, Norway. In 2012-2013 she
was awarded the Feinberg Foundation Visiting Faculty Program fellowship at the Weizmann Instituteof Science, Israel. She organized the 1st Gordon Research Seminar on H-M Systems at Stonehill
College, USA, in 2011. She is an expert member of the IEA Hydrogen Implementing Agreement
Task 32, and board member of the Norwegian Hydrogen Forum. She is also a member at the boardof directors of the Materials Research Society (MRS).

Corresponding author: Sabrina Sartori, Email: sabrina.sartori@fys.uio.no, Tel. +47 22859120

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

DEGRADATION UPON HYDROGENATION AND LOCAL STRUCTURE
K. Sakaki1*, H. Kim1, E. H. Majzoub2, A. Machida3, T. Watanuki3, K. Ikeda4, T. Otomo4, Y. Nakamura1
1 National Institute of Advanced Industrial Science and Technology, 2 University of Missouri, St. Louis, 3 Japan

Atomic Energy Agency, 4 Institute of Materials Structure Science, KEK
Abstract Relationship between degradation of V10Ti35Cr55 during cyclic hydrogenation and change in their local structure

was investigated using pair distribution function (PDF) obtained by synchrotron X-ray and neutron total scattering. In
addition, the combinational analyses of neutron PDF and first principle calculations with a special quasi-random
structure model were performed. Strong correlations were observed among the changes in hydrogen storage capacity,the -dependent peak broadening (dislocation density) and hysteresis factor for hydrogenation against cycles suggestingthat the degradation came from the accumulation of dislocations. The combinational analyses indicates that hydrogenatoms did not occupy the center of the tetrahedral site but shifted toward Cr atoms.

,QWURGXFWLRQ
Hydrogen storage is the key technology to utilizehydrogen society. Hydrogen storage materials have someadvantages, especially for stationary applications. The
issue to overcome is cyclic durability. Therefore,
relationship between cyclic durability and change inlocal structure was investigated using PDF obtained bysynchrotron X-ray and neutron total scattering. Here, wewill discuss about the degradation mechanism upon
cyclic hydrogenation from the view points of the
reduction of hydrogen storage capacity and change inlocal structure.

([SHULPHQWDO&RPSXWDWLRQDOSURFHGXUHVV10Ti35Cr55 was prepared by an arc melting with anannealing at 1673 K for 1 day and then was quenched
into iced-water. Pressure-Composition isotherms were
measured at room temperature at the designated cycles.
X-ray and neutron total scattering experiments werecarried out at BL22-XU of SPring-8 and NOVA of JPARC. The fine powders after the designated cycles
were loaded into a kapton capillary (1.0033 mm) for Xray and into a vanadium can (6 mm) for neutron.
First-principles calculations were performed using
VASP and the special quasi-random structure (SQS)
model with binary A8B8 with FCC structure to evaluate
the local atomic arrangements of di-hydride,.

5HVXOWVDQG'LVFXVVLRQand then the reduction rate became moderate. Rietveld
refinements of the diffraction patterns showed that thelattice strain was introduced with cycles without
reduction of the crystallite size. The -dependent peakbroadening in PDF patterns was developed with cycles,
suggesting that the dislocations were introduced in
V10Ti35Cr55 upon hydrogenation. Change in hydrogenstorage capacity and -dependent broadening had strong
correlations. Therefore, it is concluded that theaccumulation of the dislocations during cyclichydrogenation led the degradation of the hydrogenstorage capacity.
In neutron PDF of V10Ti35Cr55 deuterides, the average
structure model (CaF2 structure) could not reproduce thefirst and the second PDF peaks below 2.5 Å while
neutron diffraction patterns clearly showed CaF2
structure. The first principle calculations with a SQS
model showed that the hydrogen atoms likely to sit near
Cr atoms not at the center of tetrahedral site.
The detailed results will be explained in thepresentation.
This was supported by Photon and Quantum Basic
Research Coordinated Development Program. X-ray andneutron experiments were performed with the approvalof Nanotechnology Platform project in SPring-8 (A-13AE-0038, 2013B-E21, 2013B3783) and Neutron
Scattering Program Advisory Committee, KEK (No.
2009S06).

Hydrogen storage capacity and plateau pressure inhydrogenation dramatically decreased in the early cycles



Short CV
2004.4.~ present: National Institute of Advanced Industrial Science and Technology

Kouji SAKAKI
Corresponding author: Kouji Sakaki, kouji.sakaki@aist.go.jp, +81-29-861-3244.

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

INTERPHASE BOUNDARY AND SIZE CONFINEMENT EFFECT ON REVERSIBLE
HYDROGEN SORPTION REACTION AND ION TRANSPORT OF METAL
BOROHYDRIDES/NANOSCAFFOLD COMPOSITESYong Seok Choi1,2, Hyun-Sook Lee1,3, Son-Jong Hwang4, Young-Su Lee1, Young Whan Cho1, Kyu Hwan Oh2,
1. High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
2. Department of materials science and engineering, Seoul National University, Seoul 151-742, Republic of Korea
3. Department of Materials Science and Engineering, Yonsei University, Seoul 120-749 , Republic of Korea
4. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States
Abstract
When the characteristic size of the crystalline materials decreases down to a few nanometers, their intrinsic thermodynamic and kinetic
properties can change dramatically and they may behave quite differently from their bulk-phase counterparts. There are many ways to makesuch a nanostructured material but only few of them can produce thermodynamically stable structure so that they can sustain their initial structureduring and after the specific reaction at the given thermodynamic conditions. Here, we present a good example how this concept of the stablenanostructured composite can improve the reversible hydrogen sorption and ion transport properties of LiBH4 and LiBH4-Ca(BH4)2 by introducing
heterogeneous boundaries with high surface area mesoporous oxides and nanoparticles.

Generation of fluidic LiBH4 molecules, -LiBH4, was demonstrated
by NMR spectroscopy of LiBH4 bulk powder mixed with silica scaffold
surface materials under minor heat treatment. In the presence of the
fumed silica or mesoporous MCM-41 and SBA-15, LiBH4 showsincreased translational mobility at relatively low temperature (ca.
95 °C) and becomes liquid-like by evidence from 1H–11B -couplingin 1H and 11B MAS NMR or substantial line narrowing of 7Li static
NMR. This high diffusional mobility of LiBH4 at the molecular levelhas never been seen for bulk LiBH4, and the property is attributed tothe interfacial interaction with the mesoporous scaffold surfaces.
While -LiBH4 facilitates the confinement of LiBH4 itself into various
scaffold materials, LiBH4 migrates along the SBA-15 surface to reachother metal borohydride particles, Ca(BH4)2 in this case, andpromotes the formation of similarly fluidic LiBH4–Ca(BH4)2 composite(LC solid solution) for coconfinement into mesopores.  variabletemperature (VT) NMR spectroscopy detects the co-infiltration
process of eutectic LiBH4–Ca(BH4)2 composite (LC) into mesoporesof SBA-15. The infiltration rates measured for LiBH4 bulk powder or
LC composite showed dependence on pore sizes (MCM-41 vs SBA15) and heat treatment conditions (static vs MAS).
It has been known[1] that the eutectic composite of LiBH4Ca(BH4)2 shows low melting temperature, which have the potential topossess high Li ion mobility at low temperature. Furthermore,
previous NMR study[2] reveals that infiltration of materials into
mesoporous scaffolds could enhance the diffusional motion of theions. The eutectic composition of LiBH4-Ca(BH4)2 was ball milled,
and melt-infiltrated into mesoporous silica scaffolds (SBA-15) byannealing under hydrogen
atmosphere. The evidence for the infiltration of the LC composite into
mesoporous scaffolds was provided by X-ray diffraction analysis. In
addition, ionic conductivity of LC composite was evaluated byelectrochemical impedance
function of temperature.

spectroscopy

measurement

asaFig. 1 * Schematic illustration and in-situ NMR data
3
describing nanoconfinement mechanism.
References[1] J. Y. Lee, D. Ravnsbæk, Y.-S. Lee, Y. Kim, Y. Cerenius, J.-H.
Shim, T. R. Jensen, N. H. Hur, and Y. W. Cho,    
C.,113, 15080 (2009)[2] H.-S. Lee, S.-J. Hwang, H.-K. Kim, Y.-S. Lee, J. Park, J.-S. Yu,
Y.W. Cho,  @ %3(20) 2922 (2012)[3] H.-S. Lee, S.-J. Hwang, M. To, Y.-S. Lee, and Y. W. Cho,  
.,
119(17),9025(2015)

Short CVDr 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 Scienceand Technology. Since 2007, he has been one of the expert members of IEA-HIA Task 22 and 32 and member of ISO
TC197/WG25 for the revision of ISO 16111. Materials design and production of new composite materials for solid
electrolytes and active anode of lithium ion secondary batteries is one of the recent research topics of his group in KIST.

Young Whan Cho

Corresponding author: Young Whan Cho, oze@kist.re.kr, +82-2-958-5465

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

MULTI-FUNCTIONAL ENERGY STORAGE MATERIALSTorben R. Jensen
Center for Materials Crystallography, 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. Here we report an
overview of our recent results within new hydrogen containing materials: ( ) synthesis of novel metal borohydrides andstudies of their properties for hydrogen storage or as ion conductors, ( ) tailoring materials properties by formation of
eutectic melting systems, and ( )  powder X-ray diffraction studies of hydrogen release and uptake reactions. We
conclude that the chemistry 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 andgeographically, 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]. New
synthesis techniques have recently produced series ofammine metal borohydrides, (BH4)·NH3,  = Mg, Ca,
Sr, Mn, Y, La, Ce, Gd and Dy, >30 new compounds e.g.
the first long series, Y(BH4)3·NH3,  = 1, 2, 4, 5, 6 and 7[6-8]. We present new mechanisms for gas release,which depends on the ammonia release temperature andthe stability 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 (/) ratio.

Torben R. Jensen

The structures of all new compounds are solved frompowder X-ray diffraction, spectroscopy and optimized by
DFT calculations. We demonstrate that structuraldynamics in the solid state, i.e. entropy effects, are of
extreme importance for detailed material property
analysis. We present a ‘paddle wheel’ mechanism, which
may be responsible for fast ionic conductivity [9]. We
conclude that the chemistry of hydrides is very divers,
towards rational design of multi-functional materials,
including new ion-conductors for batteries, hydrogenstorage materials, and possibly materials with new typesof optical properties.

References[1] Ley, et al,     17(3), 122 (2014)[2] Jepsen, et al,    , 17(3), 129 (2014)[3] Schouwink, et al, (  , 5, 5706 (2014)[4] Ley, et al,    . 24, 1654 (2012).
[5] Ley, et al, .  116, 21267 (2012)[6] Jepsen, et al,  8  8, 3472 (2015)[7] Jepsen, et al,  . 54, 7402 (2015)[8] Jepsen, et al,  8 8, 1452 (2015).
[9] Skripov, et al.,   117, 14965 (2013)

Torben received a Ph.D. degree in materials chemistry and did postdoctoral research at Risø
National Laboratory and DESY, Hasylab, Hamburg. He became Assistant Professor (2000) andResearch Associate Professor (2002) at the Interdisciplinary Nanoscience Center (iNANO) and
Department of Chemistry, Aarhus University. He was awarded a 8  research stipend (2002) by
the Danish research council, a     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. His research interests 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 about 200 research papers.

Corresponding author: Torben R. Jensen, trj@chem.au.dk, +45 87155939 (mobile: +45 2272 1486).

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

LITHIUM-SULFUR ALL-SOLID-STATE BATTERIES
Didier Blanchard1, Supti Das1, Peter NGene2, Petra de Jongh2,Tejs Vegge1
1 Department of Energy Conversion and Storage, Technical University of Denmark, Denmark, 2 Inorganic Chemistry and
Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands.
Abstract
We propose to develop all-solid-state lithium-sulfur batteries, of higher robustness, prolonged lifetime and higher energy
and power densities than current state-of-the art Li-ion batteries. Those batteries are build around nano-confined LiBH4
used as solid-state lithium electrolyte.

Introduction

Li-S All-solis-state batteries.

The development of better batteries for cost effective
electricity storage is paramount for large market
penetration of electrical vehicle and integration ofrenewable, but intermittent, energy sources into the grid
system. For today’s best technology, i.e. state-of- the-art
lithium-ion battery, limited improvement in capacity andcost are expected because of the use of liquid or gel
electrolytes which limits the choice of electrode materials
and exposes to safety concerns. Finding a solid-stateelectrolyte, to replace the liquid ones, with adequate
properties is a challenging task but we recently found that
if a lithium-ion containing light metal hydride (LiBH4) is
confined in a nano-porous scaffold, the lithium
conductivity is multiplied by 1000![1]. This solid-stateelectrolyte is stable against lithium metal and sulfur. It
opens the possibility to build safe and cost effective allsolid-state lithium-sulfur batteries of energy contents
more than three times the best current technologies(Fig.1).

As a proof of principle, we have built Li-S cells andconducted primary tests at room temperature. The
obtained capacities, retained over more than 30
charge/discharge cycles, are lower by one order ofmagnitude to the expected values. However, in thevoltamogram, the compelling absence of characteristic+
discharge plateaus from 2Li +S+2e-lLixSy+…lLi2S
reaction (at 2V and 2.4 V vs Li/Li+) indicates faster kinetic
in comparison with previously reported Li-S cells[3]Nanoconfined LiBH4
We found that the interface layer existing between thenanoporous scaffold and the borohydride is responsible
for the Li+ high conductivity. An appropriate treatment of
the scaffold surface would increase the bulk conductivity.
The solid electrolyte is purely Li+ conducting, there is noelectronic conductivity and the transference number for
Li+ is very close to 1, there is no cationic conductivity.
The solid electrolyte stability against lithium metal isproved via galvanostatic lithium platting-stripping cycles
using symmetric lithium electrode cells. Its thermal andelectrochemical stability has been proved for an
extended range of temperatures (up to 140oC) andvoltages (up to 6 V) which makes it compatible with mosthigh voltage cathodes.

D. Blanchard

Fig. 1 Illustration of developments towards
higher energy density lithium-ion batteries.
Based on a figure in [2]References[1] D. Blanchard; et al. Adv. Func. Mat. 25 (2015).
[2] N. S. Choi;et al. Angew. Chemie - Int. Ed.51 ( 2012)[3] S.-E. Cheon; et al. J. Electrochem. Soc.150 (2003)

D. Blanchard is, since 2013, Senior Researcher at the Technical University of Denmark, Departmentof Energy Conversion and Storage (Group leader Tejs Vegge). He joined the group in 2008, as
postdoctoral researcher and then scientist. His research focuses on materials for energy storage:solid-electrolytes, metal hydride batteries, ammonia storage and hydrogen storage in complex
hydrides. He developed this later field of research while being postdoctoral researcher in Bjorn
Hauback’s group at the institute for Energy Technology, Norway. D. Blanchard received his Ph.D.
from the Université Joseph Fourier, Grenoble (France), after a university curriculum in applied
physics, geophysics and atmospheric chemistry.

Corresponding author: Didier Blanchard, dibl@dtu.dk, +45 46775899.

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

DEVELOPMENTCONDUCTIONOF

Sendai, JAPAN 2016

COMPLEXHYDRIDES

FOR

FAST

IONIC

M. Matsuo1, A. Unemoto2, T.J. Udovic3, V. Skripov4, T. Ikeshoji1,2, B. Paik2, S. Orimo1,2
1 Institute for Materials Research, Tohoku University, 2 Advanced Institute for Materials Research, Tohoku University,
3 NIST Center for Neutron Research, National Institute of Standards and Technology, 4 Institute of Metal Physics, Ural
Branch of the Russian Academy of Sciences
Abstract
Complex hydrides have been attracting much attention not only as hydrogen storage materials but also as solid-state fastionic conductors. A review of our recent progress in the development of lithium and sodium fast-ionic conductors of Bbased and N-based complex hydrides is presented.

Introduction
Complex hydrides have been attracting muchattention as solid-state fast ionic conductors since wereported the fast lithium ionic conduction in LiBH4 [1]. The
development of fast ionic conductors is importantbecause of their potential applications as solid
electrolytes in rechargeable batteries [2]. We haveworked on the development of lithium ionic conductors aswell as sodium ionic conductors of complex hydrides.

NaBH4–NaNH2 system
Na2(BH4)(NH2) can be obtained by combining
NaBH4 and NaNH2 in a 1:1 molar ratio. Na2(BH4)(NH2)6
exhibits the sodium fast ionic conductivity of 1×10 S/cm
at room temperature because of the specificantiperovskite-type structure with vacancies on thesodium site although both NaBH4 and NaNH2 have very
10S/cm [3].
low ionic conductivities of below 10
Na2(BH4)(NH2) shows twice as high ionic conductivity by
RbCl addition possibly due to the partial replacement of[BH4] or [NH2] with Cl.

Hydro-C-Borates Na2B H

Na2B12H12, composed of the [B12H12]2 closoborate anions, exhibits superionic conductivity on theorder of 0.1 S/cm above its order-disorder phasetransition at about 530 K [4]. The rapid reorientationalmotions of the anions, evidenced by the NMR and QENS
measurements, play an important role in the formation of
the cation-vacancy-rich structures in the hightemperature disordered phase. In addition, threedimensional conduction pathways are formed in the

crystal lattices. Na2B10H10 is also a superionic conductor
displaying ionic conductivity of 0.01 S/cm over 380 K
triggered by the rapid reorientational motions of the2
[B10H10] anions [5]. Very recently, NaCB11H12, whichcontains the [BnHn]2-analogous, monovalent, icosahedral[CB11H12] anions, was found to exhibit superionic
conductivity surpassing 0.1 S/cm above 380 K [6].

References[1] M. Matsuo, Y. Nakamori, S. Orimo, H. Maekawa, H.
Takamura, Appl. Phys. Lett., 91, 224103 (2007).
[2] A. Unemoto, M. Matsuo, S. Orimo, Adv. Funct. Mater.,
24, 2267 (2014).
[3] M. Matsuo, S. Kuromoto, T. Sato, H. Oguchi, H.
Takamura, S. Orimo, Appl.Phys. Lett., 100, 203904(2012).
[4] T.J. Udovic, M. Matsuo, A. Unemoto, N. Verdal, V.
Stavila, A.V. Skripov, J.J. Rush, H. Takamura, S. Orimo,
Chem. Commun., 50, 3750 (2014).
[5] T.J. Udovic, M. Matsuo, W.S. Tang, H. Wu, V. Stavila,
A.V. Soloninin, R.V. Skoryunov, O.A. Babanova, A.V.
Skripov, J.J. Rush, A. Unemoto, H. Takamura, S. Orimo,
Adv. Mater., 26, 7622 (2014).
[6] W.S. Tang, A. Unemoto, W. Zhou, V. Stavila, M.
Matsuo, H. Wu, S. Orimo, T.J. Udovic, Energy Environ.
Sci., in press.

2007

Ph.D. degree in materials science Tohoku University, Japan

2008 - 2009

Postdoctoral Fellow, Institute for Materials Research, Tohoku University, Japan

2010 - 2011

Assistant Professor, Institute for Materials Research, Tohoku University, Japan

2012 -

Lecturer, Institute for Materials Research, Tohoku University, Japan

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

GRAPHENE<::
BASED Li- AND Na-ION
<!!
BATTERIESD. Pontiroli1, G. Magnani1, M. Gaboardi1, C. Milanese2, J. C. Pramudita3, N. Sharma3 andM. Riccò1
1

Department of Physics and Heart Sciences, University of Parma, 43124 Parma, Italy, 2 Pavia Hydrogen Lab,
Department of Chemistry, University of Pavia, 27100 Pavia, Italy, 3 Dalton Building, University of New South Wales,
Kensington, 2052, Sydney, Australia.
Abstract: We report our recent results on the ability of graphene-based materials and selected derivatives to behave as
high-performing anode in lithium- and sodium-ion batteries. The main results found are that, differently from graphite,
graphene-based materials are able to support Na-ion insertion in large extent, and that metal (Ni, Pt and Ir) nanoparticles
decoration of graphene can further improve the electrochemical performances in both Li- and Na-ion batteries.

Introduction
6000

Nowadays, rechargeable Li-ion batteries (LIBs) represent
the state-of-the-art for the power supply in technologicaldevices [1]. However, the wide-scale implementation ofthis technology, for example in the automotive field,
could raise issues, i.e. concerning the limited lithium
mineral reserves. The investigation of alternatives tolithium is hence highly desirable, although it requires theidentification of new materials suitable as components for
new batteries, possibly displaying similar or even better
performances with respect to the current systems. Here
we show that anodes based on graphene derivatives are+able not only to support the insertion of Li , but also of+
Na ions, with high capacity and stability upon cycling,allowing the development of novel Na-ion batteries [3].

100
5500
5000

Capacity (mAh/g)

80

discharge
charge60
Coulombic efficiency

1000
800

40

600
400

20

200
0

0
0

10

20

30

40

50

Cycle Number

Fig. 1: Cyclic performances of Ir-TEGO
electrode in Na-ion batteries

Experimental
Macroscopic amount of graphene, in form of thermal
exfoliated graphite oxide (TEGO), was obtained bythreating graphite oxide (GO) in a tube furnace at 1423 K
under dynamic vacuum [4]. Hydrogen treated TEGO (HTEGO) was obtained by exposing TEGO to H2 flux at1073 K. Metal (M = Ni, Pt, Ir) decorated TEGO (M-TEGO)
was prepared by impregnation of TEGO with M(acac)2 (M= Ni, Ir) or M = Pt carbonyl clusters Ptx(CO)y in THF. The
thermal decomposition of the organic molecules allowed
the decoration of graphene planes with M nanoparticles(typically <20 nm diameter).

Results and Discussion
Concerning Li-ion cells, TEGO shows high 1st discharge
capacity of 3070 mAh/g, which drops to 677 mAh/g at the
2nd discharge at 100 mA/g and stabilizes to 276 mAh/g at
the 50th cycle. H-TEGO shows improved performances,ndfeaturing initial discharge capacity of 6032 mAh/g and 2
discharge capacity of 1351 mAh/g. Then capacity
stabilizes at 488 mAh/g after 50 cycles.

Unlike graphite, which is not able to intercalate significant
amount of Na, TEGO and TEGO derivatives showinteresting performances also in Na-ion cells. The best
results were obtained with M-TEGO, with high discharge
capacities of 455 mAh/g after 20 cycles, 498 and 300
mAh/g after 50 cycles for Ni-, Ir- and Pt-TEGO
respectively (Fig. 1). Although further investigations are
required to better understand this mechanism, it seems
that M nanoparticles play a role in this process, possibly
acting as nucleation centres for the alkali insertion.

References[1] J. M. Tarascon, M. Armand,. Nature 414, 359 (2001)[2] G. Kucinskis, G. Bajars et al., J. Power Sources 240,
66 (2013)[3] J. C. Pramudita, D. Pontiroli et al., ChemElectroChem.
2, 600 (2015)[4] M. Gaboardi, D. Pontiroli et al., J. Mat. Chem. A, 2,
1039 (2014)

Daniele Pontiroli has worked at the Carbon Nanostructures Laboratory CNL,
http://www.fis.unipr.it/nanocarbon), headed by Prof. Mauro Riccò, at the Physics Department of the
University of Parma since 2003, first as a PhD student and later as a Post doc. His research activity
deals with the synthesis, the structural characterization, the study of the dynamical and transport
properties of functionalized carbon nanostructures, such as fullerene and graphenes, forapplications in the field of energy-storage.
Daniele Pontiroli

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

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10th Int. Symposium "Hydrogen & Energy"

NOVEL
HYDROGENDEVELOPMENT

Sendai, JAPAN 2016

STORAGEMATERIALSANDSYSTEMS

M. Dornheim, K. Taube, C. Pistidda, J.M. Bellosta von Colbe, O. Metz, C. Horstmann, G.
Capurso, A. Chaudhary, J. Jepsen, S. Boerries, F. Karimi, N. Bergemann, H. Cao, L. Thi
Thu, A. Santoru, G. Gizer, Y. Zhang
Department of Nanotechnology, Helmholtz-Zentrum Geesthacht, 21502 Geesthacht, Germany
In this presentation results concerning reaction mechanism, sorption behaviour, cycling stability of light weight hydrides
and Reactive Hydride Composites in lab-size and tank-size are presented.
The progress in tailoring reaction enthalpies and the optimisation of kinetics will be described.

Introduction
Light weight metal or complex hydrides offer the potential
for a safe and energy efficient hydrogen storagealternative for stationary as well as mobile applications.
Highest energy efficiencies, however, are achievable only
if both working temperature and the reaction enthalpy of
the respective hydrogen sorption process can be attuned
to the accompanying hydrogen consuming process insuch a way that the required heat for hydrogen release of
the hydride can be provided by the corresponding waste
heat. Since the tailoring of reaction enthalpies is an
important research task. One way to do this is to combine
different hydrides which react during decomposition in an
exothermal way with each other and thereby reduce thetotal value of reaction enthalpy while maintaining the
average of the hydrogen capacities of the single hydrides.

techniques as Sieverts, DSC, in-situ XRD, in-situ neutron
radiography, IR etc.

Results and Discussion
Different hydrogen storage material systems and theirkinetic/thermodynamic propterties are presented.
Results are shown both from lab-scale as well as
prototype tank scale measurements.
The possibility to produce such materials in reasonableamounts and qualities for hydrogen storage tanks is
discussed as well as advantages and disadvantages ofthese materials for hydrogen storage applications.

Experimental / Computational
Properties of different Reactive Hydride Composite
systems were characterised in detail using different

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,email: Martin.Dornheim@HZG.de, Tel. +494152872604

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

7KHUHOHYDQFHRIVWUXFWXUHDQGSURSHUWLHVRQ7LGRSHG0J1L7L9&U0QDOOR\DQG1D$O+GXULQJK\GURJHQDEVRUSWLRQGHVRUSWLRQF\FOHVXin Ju*, Chubin Wan, Yuting Wang, Runlan Wang, Xianhe Meng
Department of Physics, University of Science and Technology Beijing, Beijing, China, 100083, P. R. China
Abstract
The relevance of structure and properties of the Mg1.9NiTi0.1, TiVCrMn alloy and NaAlH4 samples doped with 5wt%Ti
additives, at various cycles are investigated using synchrotron X-ray diffraction (XRD) and X-ray absorption fine structure(XAFS) spectroscopy. To identify the micro-structural evolution after different cycles, we increased the absorptiondesorption number compared with the previous studies. The higher reversible hydrogen capacity of sodium alanate andMg2Ni alloy catalysed with Ti as dopant was obtained. After 20 and more cycles, the decrease in the cycling capacity of
Mg1.9NiTi0.1 alloy may be attributed to the increasing MgNi2 content. Also after 10 cycles, the Ti additives improve thecycling capacity of NaAlH4 samples with structural transformations.


Cyclic stability is one of the major criteria for
applicability of metal/metal hydride systems for reversiblehydrogen storage. The research on the cyclic stability of
Ti-doped Mg2Ni has been seldom investigated, especiallythe relevance of structure and properties. Otherwise,
different mechanisms have been proposed to explain theenhancement of the hydriding and dehydriding propertiesof NaAlH4 by dopants. Here we reported the mechanismof dopant enhancement effect and their cyclic behaviour.

.0
The preparation of samples was shown in ref. [1-5].
XRD spectra were measured at the station 4B9A of the
BSRF (Beijing, China), the EXAFS spectra were
measured at Station BL14W1 of the SSRF and at station
1W1B of the BSRF, respectively. IFEFFIT software wereused for analysing EXAFS data.


For example, Fig.1 shows that Mg1.9NiTi0.1alloy
showed the highest hydrogen capacity at 7th cycle,
whereas its hydrogen storage capacity slightly degradedafter 20 cycles. Fig.2 present the EXAFS spectra of
Mg1.9NiTi0.1alloy. All samples were characterized withrespect to the microstructure transformations during
repeated cycles by synchrotron radiation. The metastable
Ti doped Mg2Ni phases were formed and substantiallyenhanced the absorption/desorption kinetics.

Fig.1 Hydrogen cycling absorption and Desorption
behaviors of Mg1.9NiTi0.1 alloy.
Fig.2 EXAFS data for Mg1.9NiTi0.1alloy at different cycles,"
[1] Y.T. Wang,et al. Int. J Hydrogen Energy, 39: 1485814867 (2014)[2] Y.T. Wang, et al. Int. J Hydrogen Energy, 39: 1382413831 (2014)[3] C.B. Wan, et al. Int. J Hydrogen Energy, 37: 990-994(2012)[4] C. Fan, et al, Int. J Hydrogen Energy, 35: 8044-8048(2010)[5] C.B. Wan, et al, Int. J Hydrogen Energy. 34: 89448950 (2009)

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.
Prof. Xin Ju*Corresponding author:;LQ-XMX[#XVWEedu.cn, +86 10 62333921..

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

DEHYDROGENATION REACTIONS: TRANSIENT SPECIES AND PHASES
Elsa Callini1, Andreas Züttel1
1 EPFL, Laboratory of Materials for Renewable Energy, rue de l’Industrie 17, 1951 Sion, Switzerland.
Abstract
Several dehydrogenation reactions of metal borohydrides e.g. Ti(BH4)3 are investigated in view of the thermodynamics
and formed intermediate products. Evidences are collected by combined experimental methods and the reactions
modeling substantiates the data and unravels general trends. Finally the possibility of stabilizing these intermediates isenvisaged.

Introduction
The intermediates and/or products formed during thehydrogen desorption reactions are thermodynamicallyunstable. Their characterization and measurement as afunction of time and temperature is a key challenge tounderstand the reaction mechanisms and the upscaling.
[1].

Experimental / Computational
The new metal borohydride compounds weresynthesized by metathesis reactions and reactive milling
and analysed by optical spectroscopy.

Results and Discussion
We found that the metathesis product, Ti(BH4)3,
decomposes into diborane, hydrogen and TiH2. Therefore
it is an intermediate phase in the dehydrogenation
reaction of TiCl3 added LiBH4. Ti(BH4)3 is stable at room
temperature for few hours and therefore its detection ispossible. Several intermediate species have beentheoretically predicted but never experimentally shown,for instance V(BH4)3. The spontaneous release of gas
species from the products of the reaction of LiBH4 withchlorides will be analyzed and modeled. A
comprehensive bulk, surface and gas phase analysis of
the reactions products and eventually formedintermediate species will be presented. Finally the route
towards the control of spontaneous dehydrogenation
reactions and the stabilization of the intermediate species
will be presented [2].

Fig. 1 Stabilization of Ti(BH4)3.
References[1] E. Callini, A. Borgschulte, A.J. Ramirez-Cuesta, A.
Züttel, The Role of Ti in Alanates and Borohydrides:
Catalysis and Metathesis, Journal of Physical
Chemistry C, 118(1), 77 (2014).
[2] E. Callini, P. Á. Szilágyi, M. Paskevicius, N. P. Stadie,
J. Réhault, C. Buckley, A. Borgschulte and A. Züttel,
Stabilisation of gas species via incorporation in
porous medium, accepted in Chemical Science.

Elsa Callini was born in 1982 in Varese, Italy. In 2011 she graduated in Physics at the University of
Bologna, Italy. During the graduate school, she did part of her research activities at the Danish
Technical University in Denmark, at the Aarhus University in Denmark and at the California Instituteof Technology in USA. She worked till 2015 as PostDoc in the Complex Hydrides Group in the
Laboratory Hydrogen & Energy at Empa, Switzerland and she is now Scientist in the Laboratory of
Metrials for Renewable Energy at EPFL, Switzerland. Her main interests relate to the storage ofhydrogen in solid media and to materials characterization via optical spectroscopy.
Elsa Callini
Corresponding author: Elsa Callini, elsa.callini@epfl.ch, 0041 021 69 58212

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

TOWARDS NANOPOROUS HYBRID HYDRIDES
Fabrice Morelle1, Damir Safin1, Voraksmy Ban1, Nikolay Tumanov1, Yaroslav Filinchuk1*
1 Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium
Abstract
We report on synthesis and structure of a few new series of compounds, aiming to design porous frameworks where theclassical N-based bridging ligands would provide the porosity and the hydridic borohydride ligand would provide the{functionality of the framework owing to the hydridic nature of H exposed into the pores. Porous hybrid hydrides canshow unusual gas adsorption selectivity due to the specific guest-host interactions and high reactivity within the pores.

Introduction
Since the discovery of zeolites in 1756, microporous
materials have received an always increasing attention.
Among the various known MOFs, a family based on theimidazolate unit (Im ) and divalent metals shows typicalzeolite topologies due to the structure-directing effect of
the imidazolate ligand. In the other field of solid statechemistry, borohydrides M(BH4)n were intensively
investigated for their high hydrogen content. Porous
zeolite-like frameworks were synthesized with Mg2+ and2+
Mn [1, 2], where the BH4 unit has a structure-directing
effect, bridging via its edges. Combining hydridic andclassical ligands in the same structure could result instable hydridic compounds, with the tunable properties of
ZIFs. Here we report on the strategy of obtaining porous
hydridic MOFs and on the results obtained so far.*Results and Discussion
Firstly, we obtained a series of alkali metal imidazolate
precursors, MIm. While the alkali metal cations found in
the CSD show preferred coordination to the nitrogen
atom in the plane of Im, the alkali metal sites in MIm
series are distributed over a larger range of angles
around Im. The coordinative oversaturation of Im in the
MIm series ensures a coordination of the BH4- anion tometal atoms in the hybrid imidazolates-borohydrides.
Indeed, in the first hybrid hydride, Li2ImBH4, theborohydride group is linearly bridging two metal atoms.
Its fast rotation manifested by neutron powder diffraction(Fig. 1) is decoupled from the Li-ion dynamics, unlike inmetal borohydrides, where the two processes are linked
by the paddle-wheel mechanism. The strong Li-Im
coordination is responsible for this partitioning, and thelimiting ionic formula [Li2Im]+[BH4]- reflects the structuralchemistry and the properties of this compound.
Unfortunately, the structure of Li2ImBH4 is not porous.

11
Fig. 1 Structure of Li2Im BD4 solved by a combination of
SR-XPD and NPD, anisotropic temperature factors forthe D-atoms reveal the rotational disorder.
Secondly, the Im linker was functionalized by benz- andmethyl- substituents, which are known to favour porosity
in ZIFs. The resulting MbIm and MmIm were combinedwith MBH4, yielding hybrid hydrides, which are not porous.

Thirdly, we explored the role of neutral bridging N-based
ligands, obtaining a series of complexes with LiBH4,
where the borohydride group also plays a role of thebridging ligand. The highly ionic nature of the Li+ cation
limits the directionality of the BH4 coordination, and thus
leads to structures without porosity.
Fourthly, we focused on Mg-based ZIFs and obtained
MgIm2 in a form of the porous crystalline and amorphous
phases.

References[1] Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D.
Chernyshov, H. Hagemann, Angew. Chem. Int. Ed. 50,
11162 (2011).
[2] B. Richter, D. Ravnsbæk, N. Tumanov, Y. Filinchuk, T.
R. Jensen, Dalton Trans. 44, 3988 (2015).

Short CV. Yaroslav Filinchuk studied Chemistry at Lviv National University and received PhD in
Inorganic Chemistry in 2002. He joined the University of Geneva in 2000, where he begun to workon metal hydrides with Prof. Klaus Yvon. In 2006-2010 he worked at the Swiss-Norwegian
Beamlines at the European Synchrotron Radiation Facility. Since 2011 he is a professor of structuralchemistry at the Université catholique de Louvain (UCL, Belgium). He received ESRF young
scientist award in 2010 and published about 200 papers (h index 40). His research interests include
chemistry of hydrogen-rich solids, in particular for hydrogen storage, porous materials, and various
applications of crystallography in materials science.
Y. Filinchuk
Corresponding author: Yaroslav Filinchuk, yaroslav.filinchuk@uclouvain.be, Tel. +32-10-47-2813.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

MUON SPECTROSCOPY FOR THE STUDY OF HYDROGEN STORAGE
MATERIALS
Mauro Riccò1, Daniele Pontiroli1, Mattia Gaboardi1
1 Dipartimento di Fisica e Scienze della Terra, Università di Parma, Viale delle Scienze 7/a, 43124 Parma Italy.
Abstract: In a muon spectroscopy experiment, the spin evolution of polarized positive muons implanted in the sample
under investigation is studied. In most of the insulating materials, during their thermalization process, the muons trap anelectron and form muonium. Although 10 times lighter than atomic hydrogen, muonium behaves chemically in the same
way and can be considered an isotope of hydrogen. The study of the behavior of muonium in materials for hydrogenstorage shows how a single atom of hydrogen would react within the material and can show processes which cannot be
observed with any other technique. Two examples will be shown in which μSR has been used to study the storage
mechanism of alkali clusters intercalated fullerides: Li6C60 and Li12C60.

Introduction

Results and Discussion

When a positive muon (μ+) is implanted in insulating
materials it can capture an electron to form muonium(Mu), a light isotope of hydrogen. This process makes
muon spin relaxation (μSR) a powerful technique forunderstanding hydrogen interaction with matter, such as
in hydrogen-storage materials, where absorption is often
accomplished through H2 dissociation followed by H
chemisorption on suitable frameworks.
Sodium and Lithium intercalated fullerides were recently
demonstrated to be quite efficient hydrogen absorbers[1,2]. In these materials the alkali ions occupy both thetetrahedral and octahedral sites. The presence of alkali
clusters in the octahedral voids seems to mediate thehydrogen dissociation and facilitate its chemisorption bysignificantly lowering the hydrogenation temperature, withrespect to bare C60 (550° C). Very little is known howeveron the mechanisms driving the H2 absorption.

The zero field μSR experiments on Li6C60 show asizeable missing fraction attributed to the formation of amuon adduct radical of C60. This indicates that muonium
promptly reacts with the material and binds to the C60
molecule with a good efficiency. The temperaturedependence study shows that this reaction is much more
efficient at low temperatures [3]. This indicates that thecluster mediated dissociation of the H2 molecule is theprocess requiring the high temperature (290°C)
necessary for hydrogen absorption. A different scenario
is observed in Li12C60 where no missing fraction isobserved, but a slow precession of the muon spin isevident. The only source of such a small field can be thedipolar interaction with a Li nucleus, thus proving thestabilization of a Mu-Li bound (covalent) state,
representing the first step of LiH formation [4].
In summary, μSR performed on alkali cluster intercalated
fullerides proved to be an unique tool for understanding
the different steps of the complex hydrogenation process
in these systems, suggesting the employment of thistechniques also with other hydrogen-storage materials.

Experimental
Muon Spin Relaxation experiments were performed on
both Li6C60 and Li12C60, two exponents of this new classof hydrogen absorbing fullerides, with the EMU
spectrometer at the ISIS Muon Facility (Oxford, UK). Bothzero field experiment and repolarization experiments
were carried on.

References[1] P. Mauron, M. Riccò et al.     37(2012) 14307.
[2] J. A.Teprovich et al. ( @  12 (2012) 582.
[3] M. Aramini, M. Riccò et al.   67 (2014) 92.
[4] M. Gaboardi, M. Riccò et al.   90 (2015) 130.

Mauro Riccò is associate professor at the Physics Department of Parma University since 2004. He
is the founder and coordinator of the Carbon Nanostructures Laboratory (CNL,
http://www.fis.unipr.it/nanocarbon/), one of the pioneer laboratories for the research on fullerenes
and graphene. He is the author of a hundred publications on international journals on themes
regarding the application of carbon nanostructures as novel hydrogen absorbers, elements forbatteries and superconducting and magnetic materials.
Mauro Riccò
Corresponding author: Mauro Riccò, mauro.ricco@fis.unipr.it, Tel. +39 349 6609300.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

EXPLORATION OF HYDROGEN-RICH MATERIALS
Shigeyuki Takagi1, Yuki Iijima1, Toyoto Sato1, Hiroyuki Saitoh2, Kazutaka Ikeda3, Toshiya
Otomo3, Kazutoshi Miwa4, Tamio Ikeshoji1, Katsutoshi Aoki5, Shin-ichi Orimo1,6
1 Institute for Materials Research, Tohoku University, 2 Quantum Beam Science Center, Japan Atomic Energy Agency,
3 Institute of Materials Structure Science, High Energy Accelerator Research Organization, 4 Toyota Central R&D
Laboratories, Inc., 5 The University of Tokyo, 6 WPI-Advance Institute for Materials Research, Tohoku University
Abstract
Recent discovery of the highest Tc superconductivity in sulfur hydride system has led to a renewed interest in hydrogenrich materials. Here we present a novel strategy in obtaining the further hydrogen content in the complex transition-metal
hydrides.

Introduction
Despite many exploratory studies over the past several
decades, the presently known transition metals that form
homoleptic transition-metal hydride complexes are limited
to the Groups 7–12. This limitation has become a major
barrier to obtaining the further hydrogen content in thecomplex transition-metal hydrides, as illustrated in Fig. 1.
In this presentation, we present evidence for theformation of the first Group 6 hydride complex [CrH 7]5– in
Mg3CrH8 [1], and discuss the prospects for other hydridecomplexes with the ninefold H coordination of Groups 3–
6 elements.

Mg 3 CrH 8>&U+@#
0J!

+

+

Experimental / Computational
The possibilities for synthesis of novel complex transition-metal hydrides are examined using first-principles
DFT calculations, followed by experimental examinations.
The predicted materials are synthesized using a multianvil high-pressure apparatus, and characterized by neutron diffraction and IR spectroscopy.

Results and Discussion
Our theoretical calculations reveal that pentagonalbipyramidal H coordination allows the formation of bonds between H and Cr in [CrH7]5–. The results arestrongly supported by neutron diffraction and IR spectroscopic measurements. Given an increasing trend in H
coordination number with decreasing atomic number oftransition metals, our results suggest high potential forfurther H coordination, such as a ninefold coordination, ofthe unexplored elements of the Groups 3–6, as illustrated
in Fig. 1.
This work was supported by JSPS KAKENHI (grant
numbers 26820312, 26820313, 25220911, 25420725),

7UDQVLWLRQPHWDO
Hydride com plex w ith
ninefold H coordination

Fig. 1 Schematic drawing of a novel strategy in obtaining thefurther H content in the complex transition-metal hydrides.

the Photon and Quantum Basic Research Coordinated
Development Program by MEXT, and Collaborative
Research Center on Energy Materials in IMR (E-IMR),
Tohoku University. The calculations are partiallyperformed using SR16000 supercomputing resources at
the CCMS of IMR, Tohoku University. The neutron
scattering experiment was approved by the Neutron
Scattering Program Advisory Committee of IMSS, KEK(Proposal No. 2014S06).

References[1] S. Takagi, Y. Iijima, T. Sato, H. Saitoh, K. Ikeda, T.
Otomo, K. Miwa, T. Ikeshoji, K. Aoki, S. Orimo, Angew.
Chem. Int. Ed. 54, 5650 (2015).

2008

Ph. D, Meiji University, Japan

2008 – 2009

Postdoctral Fellow, Yokohama National University, Japan

2009 – 2011

Postdoctral Fellow, University of Tennessee, USA

2011 – 2011

Postdoctral Fellow, IMR, Tohoku University, Japan

2011 – present Assistant Professor, IMR, Tohoku University, Japan
Shigeyuki Takagi
Corresponding author: Shigeyuki Takagi, shigeyuki.takagi@imr.tohoku.ac.jp, +81-22-215-2094

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

NITROGEN
STORAGEBASED

Sendai, JAPAN 2016

COMPOSITE

MATERIALSFOR

HYDROGEN

Etsuo Akiba1,2,3, Hai-Wen Li1,2, Biswajit Paik1, Huaijun Lin1, Jianhui Wang4
1

International Research Center for Hydrogen Energy, Kyushu University, 2International Institute for Carbon-Neutral
Energy Research (WPI-I2CNER), Kyushu University, 3Department of Mechanical Engineering, Kyushu University, 4
Department of Chemical System Engineering, The University of Tokyo
A reversible hydrogen storage capacity of ~7wt% at ~150ιC without releasing ammonia can be achieved using amechanically activated three-component composite of Mg(NH2)2–4LiH–LiNH2. This is the first example for amide-based
composite with three components for hydrogen storage.

Introduction
During our investigation of hydrogen storage materials
for on board application, we have found an interestinghydrogen storage composite materials with threecomponent such as Mg(NH2)2–4LiH–LiNH2. This is thefirst example for amide-based composite with threecomponents [1]Fig. 1 shows the system and composite that we
synthesized. Especially, the composition D (Mg(NH2)2–
4LiH–LiNH2) in Fig. 1 shows hydrogen release of 7.7
mass% without ammonia release as shown in Fig. 2.

Experimental / Computational
The composite was prepared by mixing commerciallyavailable Mg(NH2)2 (HydroLabo), LiH (Alfa Aesar) and
LiNH2 (Aldrich) in a mole ratio1 : 4 : 1. The powders
were ball milled by planetary ball-milling machine (10stainless steel balls with ball-to-powder mass ratio 30 :1) for 20 h at 400 rpm under Ar. X-ray diffraction,
Raman spectrometer, TG-DTA-MS and pc isothermmachine were used for characterization.

Results and Discussion
We have picked upthreechemicalsamong
Mg(NH2)2,
LiNH2, LiH and MgH2
and made composites
with various ratios ofchemicals. Finally, it
was found the system
Mg(NH2)2–LiH–LiNH2
is the most promisingfor hydrogen storage
on board.
Fig. 1 Three component composite

Etsuo Akiba

Fig. 2 TG–DTA profiles of dynamic (after the 1st cycle)
and isothermal mass-loss (as-milled) for Mg(NH2)2–
4LiH–LiNH2 composite. (Inset): mass spectra of m/z = 2
and 17 corresponding to dynamic heating (5ιC min-1).

References[1] B. Paik, H-W Li, J. Wang, E. Akiba,  .,2015, 51, 10018.

Acknowledgement
This work is supported by NEDO under “Hydrogen
Utilization Technology Development’’ and the‘‘Feasibility Study on Advanced Hydrogen Storage
Materials for Automotive Applications (2012)’’.

Professor Etsuo Akiba is the Head of Hydrogen Storage Division and the principal researcher ofInternational Institute for Carbon-Neutral Energy Research (I2CNER), and professor of Faculty ofEngineering, Kyushu University from December 2010. He earned Ph. D degree from The Universityof Tokyo in 1979 in physical chemistry. He joined National Institute for Advanced Industrial Scienceand Technology (AIST) in 1979 and started the research on hydrogen storage materials. During his
over 35-year carrier, he developed various types of materials including Ti based BCC structured
alloys that was used for on board hydrogen storage in the first TOYOTA fuel cell vehicle in 1996. He
has determined the crystal structures of novel hydrides using neutron diffraction including LaNi5H3,
SrAl2H2 and BaAlH5.He received several awards including the Herbert C. Brown Award forInnovations in Hydrogen Research, Purdue University, USA in 2008 and The IPHE TechnicalAchievement Award in 2010.

Corresponding author: Etsuo Akiba, e.akiba@mech.kyushu-u.ac.jp, Phone +81-29-802-3231

㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

RESEARCH AND DEVELOPMENT OF ADVANCED HYDROGEN
STORAGE CORE CHARACTERIZATION TECHNIQUES AND MATERIALSTom Gennett, Jeff Long, Craig Brown, Mark Bowden, Abhi Karkamkar, Tom Autrey
National Renewable Energy Laboratory, Lawrence Berkeley National Laboratory, National Institute of Standards andTechnology, Pacific Northwest National Laboratory
Abstract.   $  '  *  + $ $ ;
 ' < >$ $    * @       
 *  [   '  * \  $                   '     ]    $        '       *   ^ ] ^    _     *   \` * $ $+ '  '   ;* 
 '  ' *           {# _>                |#}]~_*; '  $  '*     $ '   *           \      $    *   *    ^ *@* *'     ; $ |}}$
^;
 '  *       |#}  *$  *    $ \Introduction
In this presentation we will provide an overview of theCore Characterization Capabilities of the NREL, LBNL,NIST and PNNL collaboration and an in-depth descriptionof the characterization capabilities at PNNL. First
experiments focusing on decomposition pathways ofcomplex hydrides, equilibrium temperatures for liquid
carriers and low temperature NMR techniques tomeasure physi-sorption of H2 in MOFs will be described.
These experiments are designed with a goal of providing
experimental benchmarking for computational methods.

calorimetry to measure enthalpies of H2 uptake by liquidorganic hydrogen carriers (LOHC), e.g., the liquid CBNmaterials developed by Liu and co-workers. Reaction
calorimetry provides a critical compliment to PCT for themeasure of enthalpies and is particularly suited for thethermodynamic characterization of reversible LOHC.

Experimental
The NMR laboratory at PNNL contains a range ofspectrometers with frequencies ranging from 300 to 850
MHz, and includes a variety of Magic Angle Spinningsolid-state probes that reach 60 kHz spinning speed. This
allows for detailed investigation of the chemical
environment of a wide range of nuclei, including kinetic
studies at non-ambient temperatures. A high-pressure
sample-rotor system has recently been constructedwhich allows studies at gas pressures of 100 bar andtemperatures up to 150 °C.[1] Reaction calorimetry using
a Calvet C80 calorimeter fitted with commerciallymodified mixing cells that permit the introduction ofhydrogen at variable pressures was used to measure theenthalpies of hydrogen addition and release in cyclic
CBN materials.[2]Results and Discussion
PNNL has access to a wide range of characterization
tools, particularly in its User Facility at the Environmental
Molecular Sciences Laboratory (EMSL). There are twostrengths of EMSL particularly useful for hydrogenstorage research: the electron-microscopy facility and thehigh-field Nuclear Magnetic Resonance (NMR) laboratory.
We expect to ascertain both binding energies, andpossible binding sites and correlate those to theproperties evaluated in the Engineering Center of
Excellence. PNNL has established the use of reaction

Fig. 1 Variable pressure (1-100 bar) variable temperature(-100 to 100 °C) NMR vessel to measure equilibrium asfunction of temperature and pressure to provide
enthalpies and entropies of H2 release and uptake.[3]References[1] Bowers, G.M., D.W. Hoyt, S.D. Burton, B.O. Ferguson,
T. Varga, and R.J. Kirkpatrick. 2014. Journal of Physical
Chemistry C, 2014, 118, 3564.
[2] Luo, W; Campbell, P.; Zakharov, L.; Liu, S. J. Am.
Chem. Soc., 2011, 133, 19326.
[3] Curtis, C. J.; Miedaner, A.; Ellis, W. W.; DuBois, D. L.
J. Am. Chem. Soc. 2002, 124, 1918.

Tom Autrey is a Staff Scientist in the Fundamental and Computational Science Directorate at the
Pacific Northwest 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.
Corresponding author: Tom Autrey, tom.autrey@pnnl.gov, (509) 375-3792
Tom Autrey㸫㸫

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 "    0   )@) "   5..6 *    "( %"   @0 
 "   5.. 0 @   " : ; ) ) * 5..E$  2 
% 0 0    $ <<   ) =   )"( (    2  (  % L   2 $ , N % -@O.O@HHI5HO

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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/her scientific work of a life time.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2007

Prof. Dr. Ronald Griessen

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

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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

Louis Schlapbach started his scientific work in 1970, 38 years ago, with theinvestigation of the Hall effect, electrical transport and magnetic susceptibility of liquid
rear earth elements like Cerium. 30 years ago in 1970 he was coauthor with Busch andWaldirich on a paper about the hydrides of La-Ni compounds. LaNi5 was subsequently
investigated in view of the structure, surface segregations, hydrogen occupation ofinterstitial sites and as electrode material.LaNi5 is still the base material for most of theelectrochemical applications of metal hydrides today. The work on LaNi 5 wascomplemented by the research on FeTi. Louis Schlapbach realized the importance ofthe surface composition for the hydrogen sorption process and he was able to describe
the role of the surface-active species. Furthermore, he investigated the changes of thesurface composition of LaNi5 and FeTi in oxidizing atmospheres and he found theformation of metallic clusters as superparamagnetic particles acting as the active sites
in hydrogen dissociation and recombination. The investigation of the surface of metal
hydrides was further intensified by means of X-ray photoelectron spectroscopy. Louis
Schlapbach was the first scientist correctly describing the activation process of a metal
hydride and, furthermore, to model the chemical composition and states of theelements in a surface profile. He also succeeded to analyze the electronic structure ofraere earth elements and their hydrides by means of photoemission spectroscopy. In
1990 Louis Schlapbach edited the two books "Hydrogen in Intermetallic Compounds I& II" of the Springer Sereies. The books became a very important reference for all the
researchers active in the field of hydrides.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Dr. Gary Sandrock

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

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Prof. Dr. Jens Norskov

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

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rüdiger Bormann was born September, 14 1952 in Germany. He
received 1977 his diploma in physics (Metalphysics), from the
University Göttingen and 1979 his Dr. rer. nat. from the University
Göttingen. From 1981 to 1982 he was visiting scientist in theDept. of Applied Physics at Stanford University, U.S.A. From1982 to 1988 he was Assistant Professor (Hochschulassistent) at
the University Göttingen where he received the Habilitation
University Göttingen, venia legendi in 1988. From 1989 to 1997
he was Professor of Metalphysics (GKSS Research Centre,
Geesthacht and Hamburg University of Technology) and from1996 to 2009 he was director of the Institute for Materials
Research, GKSS Research Centre, Geesthacht and since 2009
he is Professor of Applied Materials Physics and President of theProf. Dr. Rüdiger Bormann University of Bayreuth. Rüdiger Bormann died on 13. January
2013 in an accident in Cologne, Germany.

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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

Prof. Dr. Ivor Rex Harris

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2010

Prof. Dr. Rainer Kirchheim

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

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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

Prof. Dr. Koji Hashimoto

Prof. emeritus Koji Hashimoto has published over 520 papers in scientific journals in
addition to review articles and book chapters. He has worked on corrosion-resistantalloys, electrolysis, especially he pioneered the electrolysis of seawater. He tailored thecatalysts for carbon dioxide methanation, in particular, he has built a prototype plant for
global CO2 recycling in 1995 on the roof top of the Institute for Materials Research,
Tohoku University. The plant consists of power generation by photovoltaic cells,
hydrogen production by seawater electrolysis and methane formation by the reaction ofcarbon dioxide with hydrogen, carbon dioxide recovery at an energy consuming district,and transportation of carbon dioxide. The plant uses tailored key materials with highperformance and durability, that is, cathodes for hydrogen production, anodes for only
oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for
rapid and selective production of methane by the reaction of carbon dioxide withhydrogen. The performance of the plant has substantiated that global CO 2 recycling
can supply abundant energy generated from solar energy on deserts in the form of
methane and can really prevent global warming induced by carbon dioxide emissions.
In 2003, he has built a pilot plant of global CO2 recycling at Tohoku Institute ofTechnology which is the minimum unit of industrial scale for seawater electrolysis andcarbon dioxide methanation.
He is in the Editorial Board of "Corrosion Science", a Member of NACE International,
the Electrochemical Society and the International Society of Electrochemistry. Memberof Japan Society of Corrosion Engineering, the Japan Institute of Metals, the Surface
Finishing Society of Japan, the Iron and Steel Institute of Japan, the Electrochemical
Society of Japan, the Society of Chemical Engineers, Japan, the Chemical Society ofJapan, and other scientific societies in Japan.
He received many awards among those also The Electrochemical Society Fellow
Award in 1997 in recognition of contribution to the advancement of science andtechnology, for leadership in electrochemical and solid state science and technology
and for active participation in the affairs of the Electrochemical Society, Inc.
We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogenand the use of hydrogen for the reduction of CO2 with the Science of Hydrogen &Energy prize 2011.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2012
Mogens Mogenson is research professor in the fuel cells andsolid state chemistry division, Risø National Laboratory for
Sustainable Energy, Technical University of Denmark (DTU).
He has spent 37 years in electrochemistry. He received his
MSc in 1973 and PhD in 1976 from the Department ofMetallurgy, DTU. After a postdoctoral period at the
Department of Chemistry A, DTU, and a short period in thebattery industry (Hellesens A/S), he was employed at Risø
National Laboratory in 1980. He was manager for numerous
projects and programs (mainly within R&D of practicalelectrochemical cells such as solid oxide fuel cells) and now
the Strategic Electrochemistry Research Center (SERC). He
has coauthored more than 250 scientific papers and reports,and has 16 patents/patent applications.
Prof. Dr. Mogens MOGENSON
Prof. Mogens Mogensen from the Risø National Laboratory for sustainable Energy made anenormous contribution in the development for electrochemical systems like SOFCs (High
Temperature Solid Oxide Fuel cells), SOEC (Solid Oxide Electrolyser Cells) as well as oxygen
separation membranes over the last 20 years. His topics in this field include the material
development for electrodes, electrolytes as well as interconnects, coatings and sealing’s.
Mogens is known for his broad knowledge and understanding of the total systems andespecially the deep knowledge of the thermodynamics and electrochemical behavior of thecells.
The driving force behind his research activities are the principle understanding of the aging
mechanisms in SOEC and SOFC systems, the electrochemical behavior, but also thedevelopment of new materials for better performance and competitive prices. In the field ofadvanced materials he was very active and successful in the development of catalytic metaloxides with fluorite and perovskite related structures. These compounds are extremely flexible
with respect to substitution of host cations and non-stoichiometry. By this purpose he has done“material engineering” by tailoring the basic materials properties for aspects like high electronic
and ionic conductivity, matching thermal expansion coefficient, stability in hydrogen and/or
oxygen atmosphere, etc. The development of novel materials was leading to the “world record”
in power density for electrochemical cells, accompanied by a low aging- and degradation rate(>1%/1000h) and an outstanding mechanical strength and flexibility. Mogensen was also very
active in cells and stack development with high electrical efficiency and fuel flexibility including
natural gas, biogas, diesel, LPG, methanol, DME and ethanol.
Recently his topic and interest are the synthetic fuels derived from water and CO2. This isinteresting as the produced syngas (H2 + CO) can react to form methane, which is a moresuitable energy carrier. In this process, the catalytic process is taking place inside the cell, so
the reaction heat can be utilized.
We award Prof. Mogens Mogenson for his outstanding work on the electrochemistry ofelectrolysers and fuel cells with the Science of Hydrogen & Energy prize 2012.

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th
10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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

Mr. Katsuhiko Hirose

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

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10 Int. Symposium "Hydrogen & Energy"

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

Prof. Dr. Hans Geerlings

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2014

Prof. Dr. Andreas Zu t t eI

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

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

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10 Int. Symposium "Hydrogen & Energy"

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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 EPR-spectroscopy
and solid state chemistry, with a minor in philosophy ofscience. His PhD in physical chemistry he received from theRadboud 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 thevrije universiteit amsterdam, with the main areas of research:HTc-superconductivity,
switchable
mirrors,hydrogenstorage, hydrogen sensing. He is co-founder 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', Scientificdirector Sustainable Energy Technologies-3TU, Chair of theexam 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 forapplications based on metal hydrides, such as hydrogen sensors, hydrogen storage, hydrogenmembranes and chemochromic windows. In addition, he investigate the mechanism of photoelectrochemical 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 thehydrogen 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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10 Int. Symposium "Hydrogen & Energy"

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SCIENCE OF HYDROGEN & ENERGY AWARD 2015
1993-1995 JSPS (Japanese Society for the Promotion of
Sciences) Research Fellow. 1995 Ph. D., Fac. Integrated
Arts and Sci., Hiroshima University, 1995 - 2002 Research
Associate, Hiroshima University. 1998 - 1999 Guest
Researcher, Max-Planck Institute for Metal Research, asAlexander von Humboldt Foundation and Japanese Ministryof Education Fellows. 2002 Associate Professor, Institute forMaterials Research (IMR), Tohoku University. 2009
Professor, Institute for Materials Research (IMR), Head of
Hydrogen Functional Materials Division, Tohoku University

Prof. Dr. Shin-Ichi Orimo

Shin-Ichi 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 andthe hydrogen sorption kinetics came from Orimo's group. Especially to mention the relationshipof the hydrogen desorption temperature and the cation electronegativity. Very early Orimo'sgroup also worked on the combination of complex hydrides and amides. Recently, the hightemperature phase of LiBH4 was stabilized by a partial substitution of the [BH4] with the iodinions leading to a very high ionic conductivity at ambient temperature.
We award Prof. Shin-Ichi Orimo for his outstanding work in the science of hydrides, thediscovery of new hydride systems and tunable properties of hydrides with the Science ofHydrogen & Energy prize 2015.

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10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2015
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 post-doctoral
fellowship at the University of Pennsylvania, Philadelphia,
USA. Recently, he edited the “Handbook of Hydrogen
Storage” and is operating agent of IEA-HIA Task 32“Hydrogen-based energy storage” since 2013. His current
research interests focus on nanoporous and nanoscalematerials for gas storage and separation.
Dr. Michael Hirscher

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., “Room-temperature hydrogen storage in nanotubes” Science 2000, 287,
(5453), 593-593.) which turned out to be a missinterpretation of the measurements. M. Hirscher
carefully investigated the surface site occupation of the carbon nanostructures and theinteraction energy. His present studies focus on novel nanoporous framework materials, e.g.,
metal-organic frameworks (MOFs), with high specific surface area and microporosity, which canbe applied for cryo-adsorption tanks.

Furthermore, these crystalline, nanoporous framework materials are investigated for their ability
to separate isotopes of light gases, e.g., hydrogen-deuterium mix--tures, by quantum sieving.
We award Dr. Michael Hirscher for his outstanding work in the science of the interaction ofhydrogen with porous nanostructures, the investigation and description of the quantity ofhydrogen as well as the adsorption energy of the Van-der-Waals interaction of hydrogen withvarious nanoporous materials with the Science of Hydrogen & Energy prize 2015.

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th
10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2015
Head of Physics Department, Institute for Energy
Technology (IFE), 2011- Scientific responsible Energy
Storage, IFE, 2009- Principal Scientist New Materials, IFE,
2007- Adjunct Professor of Physics, University of Oslo (UiO),
2000- Deputy Head of Physics Department, IFE, 20012011 Principal Research Scientist, Physics Department, IFE,
1993-2007. Postdoctoral Associate, NTH, 1988-1991; IFE,
1991-1993. Fellow, NTH and Research Council of Norway(RCN), 1983-1988. Dr. ing. (PhD) Norwegian Institute ofTechnology (NTH), Trondheim, Norway 1988. Siv. ing.
(Master degree) NTH, Trondheim, Norway 1981.
Prof. Dr. Bjørn Hauback
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 andmagnetic 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 heinvestigated the hydrogen desorption reaction of alanates and borohydrides in great detail bysynchrotron and neutron diffraction.
Bjørn Hauback was Operating Agent for IEA Hydrogen Implementation Agreement Task 22 "Fundamental and Applied Hydrogen Storage Materials Development" from 2006. Within thistask an enormous progress on the investigation and understanding of complex hydrides wasachieved.
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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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2016
Dr Young Whan Cho has been working on hydrogen storage materials since 2002 andis 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 Scienceand Engineering of University of Science and Technology. Since 2007, he has been oneof the expert members of IEA-HIA Task 22 and 32 and member of ISO TC197/WG25 forthe revision of ISO 16111. Materials design and production of new composite materials
for solid electrolytes and active anode of lithium ion rechargeable batteries is one of therecent research topics of his group in KIST.
Prof. Young Whan cho

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 thebasic sorption properties of calcium borohydride and its composites with other metal hydrides and borohydrides, notably
Ca(BH4)2-LiBH4 system. Many contributions for the understanding of the crystal structure of newly found intermediates
and mixed-ionic borohydrides through first principle calculations came from Cho’s group. His group has been working on
the nano-confinement 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 designand synthesize novel interface controlled superionic conductors with various complex hydrides for electrochemicalenergy storage applications.

We award Prof. Young Whan CHO for his outstanding work in the science of metal hydrides, the discovery of newreactive hydride composite systems and method to change the basic properties of complex hydrides with the Science ofHydrogen & Energy prize 2016.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2016

Prof. Craig Jensen

Dr. Craig Jensen is a full professor of Chemistry at the University of Hawaii and thefounder/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 ofhydrogen 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 co-authored 141 peer-reviewed
publications, 9 U.S. patents, and one book. Additionally, Prof. Jensen has presented over
160 invited seminars at universities, government labs, private companies, andconferences in 24 different countries. Since 1997, he has been a member of theInternational Energy Association’s hydrogen storage expert’s groups. During the period
1999-2003, he was commissioned as the only foreign “committeeman” on the WE-NET
project, a working group of top Japanese experts charged with the development ofadvanced hydrogen storage materials. He was a co-chairman of the 2006 International
Symposium on Metal-Hydrogen Systems and the 2007 Hydrogen-Metal Systems Gordon
Research Conference. In 2003, Dr. Jensen founded Hawaii Hydrogen Carriers, LLC andhas since served as the company president.

Prof. Jensen's early research activities focused on the synthesis and characterization of novel organo-transition 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 groupcompounds. In the late 1990’s, he began his studies of the reversible dehydrogenation of complex hydrides. His efforts inthis 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 thehydride with titanium halides. These efforts led to collaborations that resulted in the development of novel processes forthe reversible dehydrogenation of lithium aluminum hydride (with Prof. Sean McGrady) and the first structuralcharacterizations of gamma and beta alane (with Prof. Bjorn Hauback). He next extended his studies of complex
hydrides to boron-based 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 in2010. Their cycling of 11.2 wt% hydrogen through the reversible hydrogenation of MgB2 to Mg(BH4)2 stands as thehighest hydrogen storage capacity that has been experimentally demonstrated for any material that can be directlyhydrogenated. However, cycling of Mg(BH4)2 to MgB2 requires extreme reaction conditions. A recent collaboration with
Dr. Tom Autrey and Prof. Shin-ichi 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 thepractical utilization of metal hydrides. Since 2006, his company, Hawaii Hydrogen Carriers, LLC has focused on thedesign, 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 solid-state metal hydridehydrogen 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.㸫㸫

10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

SCIENCE OF HYDROGEN & ENERGY AWARD 2016
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 8  research stipend(2002) by the Danish Research Council, a     research stipend (2005) from theCarlsberg Foundation and a Doctor of Science degree (D.Sc. in 2014) from the Facultyof Science and Technology at Aarhus University. His research interests are focused onsynthesis, structural, physical and chemical properties of new inorganic materials andutilisation of synchrotron X-ray radiation for materials characterization. He has publishedmore than 200 research papers.

Prof. Torben R. Jensen

Torben R. JENSEN initiated his research career within inorganic materials science, and then moved to biophysics andback 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 X-ray
beams generated by synchrotrons for advanced materials characterisation. Jensen and his group have developed
knowhow, new sample environments and gas-control for in-situ powder diffraction investigations of solid-gas reactions.
This is now implemented at several synchrotron facilities and has led to a variety of collaborations world-wide. A
multitude of new advanced synthesis techniques have also been developed, e.g. new approaches for mechanochemistry,in particular investigation of the reaction mechanisms. Solvent-based methods have been used for preparation of new
precursors and several synthesis techniques have been combined to develop novel materials.
The first nano-porous metal hydrides, J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 solvent-based 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NH3,  = 1, 2, 4-7, of generalinterest, also within coordination chemistry. Detailed structural investigations of metal borohydrides and their ammonia
and anion-substituted derivatives reveal that dynamic (entropy) effects may lead to either a contraction or an expansionof the solid state. Jensen also proposed that dynamic or entropy effects are responsible for fast cationic conductivity andion substitution in the solid 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 structure-property relationships towards rational
design of novel, useful, and functional ‘energy materials’. During the past few years the Jensen research group has beenamong the most productive for synthesis of new materials. The group has published 130 peer-reviewed 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 structure-property relationships with the Science of Hydrogen & Energy prize 2016.

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10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

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, includinghydrogen storage materials, electrode materials for Ni-MH and lithium ion batteries.

Prof. Min Zhu
Min ZHU’s work is mainly focused on the syntheses, characterization and properties of hydrogen storage materials andanode materials of lithium ion battery. His fundamental researches help to understand the hydriding/dehydriding reaction
mechanisms related to the multi-phase structure, nanostructure and multi-valence catalysts in different Mg-based
nanocomposite systems. He has developed some novel synthesis processes to obtain Mg-based nanocomposite with
nanocatalysts in-situ 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, byforming Mg-based solid solution in Mg-In, Mg-In-Ni, Mg-In-Y systems. All these are his important contributions in Mgbased materials for reversible hydrogen storage. Meanwhile, Zhu’s group found the excellent hydrolysis performance ofnanocomposites in Mg-TM-RE 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 haspromoted 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 multi-phase andmulti-scale structure, and the obtained Mg, Sn-C, Si-C base materials composites have shown excellent kinetic andcycling performance.

We award Prof. Min ZHU for his outstanding works in the science of Mg-based hydrogen storage alloys as well as his
effort in developing materials synthesis methods for hydrogen storage and lithium ion battery with the Science ofHydrogen & Energy Prize 2016.

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th
10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2011
Ms. Alondra Torrres Trueba“Hydrogen Storage in Structure II
Clathrate Hydrates with Various
Promoters”
Department of Process & Energy,
Delft University of Technology,
Delft, Netherlands

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

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

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2012
Mr. Andreas Bliersbach“How to Watch Hydrogen Diffuse in
any Absorbing Material”
Department of Physics andAstronomy, Materials Physics
Division, Uppsala University,
Sweden.
Born 1986 in Cologne, Germany.
2011 Diploma in physics at the
RheinischeFriedrich-Wilhelms
University Bonn, Germany. 2008 –2009 studies and research, as
exchange student, at Uppsala
University, Sweden. 2010 – 2011
research on hydrogen diffusion innano sized materials by direct
imaging at Uppsala University,
Sweden. Since December 2011
PhD student at EMPA, 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 nano-sized materials motivate fascinating applications and scientific questions.
Even though diffusion is one of the most studied phenomena the complex combination ofquantum effects and dynamic interplay with the displacement of host atoms [1,4] is still only
partially understood. We present a method to quantify chemical diffusion of hydrogen in nanosized materials. The changes in the absorptance of a vanadium single crystal thin-film, inducedby hydrogen, are observed visually and in real-time as a function of position. Concentration
profiles and their evolution in time, during chemical diffusion, can be measured down to ahydrogen content corresponding to just a few effective monolayers, randomly distributed within
VHx.

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2013
Mr. Moreno De Respinis“Optimization of Anneal Procedure in Metal Oxides: Case
Study of Nanostructured Tungsten Processed via Low-Energy
Helium-Ions”
Delft University of Technology, Faculty of Applied Siences,
Department of Chemical Engineering, Materials for Energy
Conversion and Storage; Julianalaan 136, 2628 BL Delft, The
Netherlands
Moreno de Respinis received his bachelor degree in physics at
the University of Milan in 2008, and earned his master degree
in sustainable energy with study line hydrogen and fuel cells at
the Technical University of Denmark (DTU) in 2011. He
concluded his master with a fellowship at the Lawrence
Berkeley National Laboratory with Dr. Heinz M. Frei’s group, in
which he performed mechanistic studies of water photooxidation by visible-light driven Co3O4 catalyst. He is currently
a Ph.D. student at Delft University of Technology where he isresearching on photoanodes for solar water splitting.

“Optimization of Anneal Procedure in Metal Oxides: Case Study of Nanostructured
Tungsten Processed via Low-Energy Helium-Ions”
One challenge in developing highly efficient nanostructured photoelectrodes is to control theirmorphology, crystal phase and stoichiometry. We present a novel physical processing route thatuses high-flux of low-energy helium- ion to generate porous structures on tungsten targets.
Optimal anneal condition to form WO3 photoanode is determined via in-situ XRD. SEM images
show mesoporous crystalline structure, and feature sizes depend on substrate temperature andcan be tuned between 30 nm and 1 μm. Our research shows that a two-step anneal procedureis optimal to oxidize surface nanostructures into crystalline WO3, preserving the bulk as metallic
W for good electrical contact. As a result, IPCE of 20% is obtained, resulting in an AM1.522
photocurrent of 0.75 mA/cm at 1.23 VRHE (compared to 0.15 mA/cm after standard thermaloxidative anneal). The excellent control over feature size offers an exciting new processing
route to nanostructure materials for e.g. solar water splitting.

㸫㸫th
10 Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2014
Mr. Yixiao Fu"Study on the hydrogenexchange behavior in themetal hydride-LiBH4
composite"
School of Materials Scienceand 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 andEngineering in Department ofMaterials, South China
University of Technology(SCUT), Guangzhou, China.
He is currently a M.S
candidate at SCUT. Focusedon LiBH4-MgH2 system andMagnesium core-shellstructure.

"Study on the hydrogen exchange behavior in the metal hydride-LiBH4 composite"
Hydrogen-exchange effect discovered in hydride composite gives an angle to study the nonreaction interaction between components and to study detailed desorption mechanism.
Although obvious phenomena had been observed to prove the existence of this effect, the detailmechanism 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 bothhydrides are crucial for the exchange to happen. Desorption gas specie in LiBH4-VD2 systemdrastically changed after melting of LiBH4 and only then showed obvious H-D exchange
phenomena, in LiBH4-MgD2 system inhibition of desorption of MgD2 by 4MPa H2 nearlyannihilate B-D signal in FTIR indicating nearly no D atoms was found in LiBH4.

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2015
Dr. Shunsuke KATO
"In Situ X-Ray Photoelectron Spectroscopy
Studies on Hydrogen
Storage and Catalysis"
2005 Master of Engineeringfrom Tokai University, Japan.
2007 PhD student at theLaboratory for Hydrogen &Energy, Empa, Swiss Federal
Laboratories
for
Materials
Science and Technology, andat 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 ofRadio- and Environmental
Chemistry,Paul
Scherrer
Institute, Switzerland. Since
2014 Postdoc at Empa, Swiss
FederalLaboratories
for
Materials
ScienceandTechnology.

"In Situ X-Ray Photo-electron Spectroscopy Studies on Hydrogen Storage and Catalysis"
The aim is to develop X-ray photoelectron spectroscopy for in situ investigations relevant to awide range of research fields such as heterogeneous catalysis and energy storage. Near
ambient pressure X-ray photoelectron spectroscopy has become an emerging tool for
determining electronic structure and depth resolved chemical composition for interfacial
reactions. 㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST H2FC POSTER AWARD 2015
Mr. Nikolai BILISKOV"Synthesis andCharacterisation of New
Aminoboranes""
Laboratory of Solid State andComplex
Compounds
Chemistry, Ru|er Boškovi}
Institute, Bijenic ka c. 54, HR10000 Zagreb, Croatia

Born September 17, 1974 inPula, Croatia.1999 Masters
degree of inorganic chemistryatFacultyof
Sciences,
University of Zagreb; thesis at
Facultyof
ScienceinZagreb.2009 PhD degree inphysical chemistry at Ru|er
Boškovi} Institute, Zagreb
thesis"” 2012
Research
associate at the Laboratory ofSolid State and Complex
Compounds
Chemistry,
DivisionofMaterials
Chemistry, Ru|er Boškovi}
Institute, Zagreb 2014 Visiting
scientist at EMPA, Dept.
HydrogenandEnergy,Dübendorf, Switzerland"Synthesis and Characterisation of New Aminoboranes"
A series of single- and bimetallic amidoboranes and their complexes with ammonia borane wereprepared by ball milling from ammonia borane and corresponding metal hydrides. Products arecharacterised 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. 㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2016
Ms. Efi HADJIXENOPHONTOS"Hydrogen sorption Kinetics in Magnesium andTitanium 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 chemistryin Montpellier. After French, I added English to myscience skills through MESC, an international
master's offering a unique experience to explore
electrochemistry and materialsಳ science, whileworking at various European universities. During
my master's I was elected class president for my
teamwork skills ಳand ability to manage andcoordinate the multi-lingual/multi-cultural group. My
academic work stood out enough that a position for
my master's thesis project was created for me inMontreal, 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 tospend 10 additional months doing research on
nanocarbon materials and ionic liquids for solidstate electrochemical capacitors. Today, I am
combining my degrees, lab experience, andlanguages 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 bymechano-chemical 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 H-sorption 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 dissociationof H2 molecules and diffusion of H atoms in the material. Thin films were deposited in order toquantitatively determine diffusion coefficients and measure kinetic barriers at the interfaces. A
main focus here is the comparison of these properties between TiH2 and MgH2.

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016BEST POSTER AWARD 2016
Ms. Guanqiao LI"Dehydriding Properties of LiBH4
Combined with Mg2FeH6""
Institute for Materials Research,
Tohoku University, Sendai 980-8577,
Japan
WPI-Advanced Institute for Materials
Research, Tohoku University, Sendai
980-8577, Japan
2006, bachelor of science, Peking
University.
2011-2013, master course in the
Graduate School of Environmental
Studies, Tohoku University.
2013 until now, Ph. D student in the
Graduate School of Environmental
Studies,
TohokuUniversity.
Research on complex hydrides forhydrogen storage materials in Prof.
Shin-ichi 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 (TG-MS)
measurements, a unique one-event dehydrogenation proces of LiBH4 and Mg2FeH6 has beenrealized. This event has been conrmed to be simultaneous dehydrogenation by using Mg2FeD6
instead of Mg2FeH6 to combine with LiBH4 by which the hydrogen related species released fromthe two components could be distinguished. Also, H-D exchange between LiBH4 and Mg2FeDs
occurred during the mechanically milling and heating process has been found by this method.
The H-D exchange indicates active interaction between LiBH4 and Mg2FeD6 that is crucial to thedehydrogenation property of the composites.

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016

PARTICIPANTS

㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫

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Sendai, JAPAN 2016㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫10th Int. Symposium "Hydrogen & Energy"

Sendai, JAPAN 2016㸫㸫