Hydrogen storage – Perspectives from Norway Bjørn C. Hauback

Physics Department

Institute for Energy Technology, Norway

bjorn.hauback@ife.no www.ife.no

Institute for Energy Technology (IFE)

• Established in 1948 • 600 employees • 2 research reactors • Renewable energy • Petroleum • Nuclear technology

JEEP II reactor

Energy storage – an issue … • The sun is not

always shining • The wind is not

always blowing

• FC-cars with hydrogen need storage of H2

Hydrogen is one solution to the storage challenge – solid materials could be the long term solution

www.toyota.com/mirai

Solid storage materials

• H2 molecules adsorbed on surfaces

• Carbon-based materials • MOFs Need low temperatures

• H atoms absorbed in bulk

• Interstitial hydrides • Chemical hydrides • Complex hydrides

H atoms absorbed in metals and alloys

M(s) + x/2 H2 MHx(s) + energy

Schlapbach and Züttel (2001)

Hydride phase: • H atoms in the metal lattice • Chemical M-H bonds:

• Metallic • Ionic • Covalent

• Most metals form hydrides

Research hydrogen storage materials in Norway IFE 60 years’ experience in studies of metal hydrides.

Acta Cryst. (1955)

Nanostructured materials for solid-state hydrogen storage

IFE partner in most EU-projects (17) in this field since 2002:

National collaboration:

Collaboration with Japan since 2005:

H2FC

Neutrons to “see” hydrogen – IFE’s JEEP II reactor a

b

c

a

b

c

… as seen by X-rays

… as seen by neutrons

AlD3

Why hydrogen storage in metal hydrides • High volumetric hydrogen density • Pressures <<35-70 MPa • Safety

Different use → different needs → different materials

• Gravimetric hydrogen density • Thermodynamics (temperature for H-sorption) • Kinetics of hydrogen uptake and release

• Cost (materials, tank, processing)

Al-based hydrides: Alanates (e.g. NaAlH4, LiMg(AlH4)3) AlH3: 10.1 wt%

B-based hydrides Mg(BH4)2: 14.8 wt% Ca(BH4)2: 11.6 wt%

Mg-based hydrides:

MgH2: 7.6 wt% Transition-metal-based, e.g. Mg-Fe-Co-H

Nanomaterials for hydrogen storage

Mg-, Al- and B-based

bcc-alloys

Understanding of catalysts Destabilization by halide-substitution

Metal hydrides – IFE topics

Alanates

Li3AlD6 NaAlD4

JEEP-II

Mg(AlH4)2 Na2LiAlH6 LiAlD4 KAlD4 K2NaAlD6 LiMg(AlD4)3 LiMgAlD6 β-LiAlD4

• NaAlH4 reversible (5 wt%) at moderate conditions! • Ti as catalyst in NaAlH4, but not understood • AlH4 tetrahedra or AlH6 octahedra

Hauback (2008); Sato, Sørby, Ikeda, Sato, Hauback, Orimo (2009); Pitt, Hauback et al. (2012, 2013)

Ca(AlH4)2 CaAlD5

Borohydrides for hydrogen storage • Complex hydrides with BH4 anions • Highest storage capacities:

• LiBH4: 18.4 wt%, 120 kg H2/m3 • Mg(BH4)2: 14.8 wt%, 80 kg H2/m3 • Ca(BH4)2: 11.5 wt%, 108 kg H2/m3

Frommen, Hauback et al (2010)

LiYb(BH4)4

Olsen, Frommen, Sørby, Hauback (t2013)

• Only partly reversible • Complex hydrogenation/

dehydrogenation processes

Y(BH4)3

• New compounds? • Modify thermodynamics/kinetics

• Anion/cation substitution? • Effect of additives/catalysts? • Nanoconfinement?

New compounds: Rare-earth (RE) borohydrides • More stable than transition metal borohydrides

• Hydrogen storage up to about 6.5 wt%

LiRE(BH4)3Cl RE=La, Ce, Pr, Nd, Sm, Gd

α-RE(BH4)3 RE=Sm, Gd, Tb, Dy, Er, Tm, Yb

β-RE(BH4)3 RE=Sm, Er, Yb

LiRE(BH4)3Cl RE=Yb, Lu

Yb(BH4)2-xClx

Frommen, Sørby, Fjellvåg, Ravindran, Vajeeston, Fjellvåg, Hauback (2011) Olsen, Frommen, Sørby, Hauback (2013) Olsen, Frommen, Sørby, Jensen, Hauback (2014)

Electrolyte in Li-ion batteries?

bcc alloy hydrides Ti-V-based bcc hydrides + Excellent kinetics + Excellent thermodynamics * Decent H capacity: 2-3 wt% - Vanadium very expensive

Ferrovandium (much cheaper) to replace V. Reduced H-capacity, why?

1 2 3 4 5 6 7 8 9 100

20

40

parti

al g

(r) (a

rb. u

nits

)

r (Å)

Fe-D Fe-Va Ti-Va V-Va

Pair distribution function (PDF) Neutron scattering

Fe Vacancy

Fe V Ti

H

iTHEUS – Fundamental investigations on Improved Materials and Storage Concepts for a Hydrogen based Integrated Total Energy Utilisation System (2013-15)

• AIST (Japan) – Dr. A. Nakano • Tohoku Univ. (Japan) – Prof. S.-I. Orimo • IFE, Norway – Prof. B.C. Hauback • HZG (Germany), EMPA (Switzerland),

Aarhus Univ. (Denmark)

Present Collaboration with Japan

Running FP7 EU-project with both Tohoku University and IFE as partners.

Summary

• Excellent ongoing collaboration between Japan and Norway on hydrogen storage materials

• Solid materials/metal hydrides: (still) an alternative for hydrogens storage

• Several other applications of metal hydrides:

• MH-batteries, MH in Li-ion batteries, heat storage, smart windows, H-sensors

• Basic research important. Collaboration needed to solve the scientific challenges and to understand/develop novel materials/systems

Thank you very much for your attention

bjorn.hauback@ife.no