Hydrogen Storage –high-capacity hydrides

Professor David Book School of Metallurgy & Materials University of Birmingham Birmingham, UK

d.book@bham.ac.uk www.hydrogen.bham.ac.uk

Hydrogen and Fuel Cell Supergen Hub Newcastle University 30th July 2014

Prof David Book; (Honorary staff: Prof. Rex Harris, Dr John Speight);

Dr Daniel Reed, Dr Shahrouz Nayebossadri, Dr Lydia Pickering, Sheng Guo,

Simon Cannon; 6 PhD & 4 Masters

Hydrogen Materials Group

www.hydrogen.bham.ac.uk

Dense-metal H2 separation membranes

• PEM Fuel Cells are poisioned by: CO > 10 ppm, and Sulphur at ~1 ppb. Pd alloy membranes can produce ultra-pure hydrogen.

à  Pd-Y-TM (TM = transition metal) alloy with high H2 permeability & ductile à  Developed thin-film Pd / porous stainless steel composites à  Pd-Cu-TM rolled alloy with improved H2S resistance à  Zr-based amorphous sputtered films

30 kg of LaNi5. à 5000 Ltrs of H2

MH store, in PEM-FC Portable Power

MH Compressor: 2-stage (AB5 and AB2 tanks) automated compressor

Time (min)

www.hydrogen.bham.ac.uk

Energy Demos – metal hydrides

New MH compressor à ESCHER project

33rd Int Vienna Motor Symp. 2012, N. Brinkman et al (GM Europe)

Weight of energy storage systems to take a car 500 km

33. Internationales Wiener Motorensymposium 2012

In the 1990s, power electronics and high power density electric motors made the performance of new electric vehicles competitive with ICE vehicles again. In the 2000s, a range of new vehicle, electronics, computer, and communications technologies enabled new propulsion and vehicle design and architecture concepts. In the future, the growth of renewable energy sources will drive an enhanced smart energy network encompassing electricity and hydrogen technology. However, further development of range-extender and fuel cell technology is necessary in parallel with improvement of batteries because the energy capacity of the battery and, therefore, the vehicle range remain limiting factors to pure battery-electric vehicles. When we take the different vehicle system efficiencies into account, driving a distance of 500 km requires 33 kg of diesel fuel (43 kg on a system basis, including the tank) compared to a lithium-ion battery at 540 kg for the cells (830 kg for the system). (See Figure 6.) Thus, for equal range, the mass of a lithium-ion battery is about 20 times that of a diesel fuel system. Refueling of a diesel tank also takes only two-to-three minutes, while today’s fast charging still requires 30 minutes to deliver 13 kWh using a 40-kW, high-power electric charger, although this reduces battery life. In addition, charging at 40 kW could have a significant impact on the grid. Hydrogen fuel cell storage systems have a mass of about 125 kg and can be refilled within three-to-five minutes, providing another EV option if quick refueling and longer driving range are required.

Figure 6 – Weight and volume of energy storage systems for a 500-km vehicle range.

Bild 6 – Gewicht und Volumen des Energiespeichersystems für eine Reichweite von 500 km.

Hydrogen Storage

Hyundai ix35 Fuel Cell

HYDROGEN STORAGE • Composite hydrogen tanks, plus solenoid valve, high pressure regulator & overflow control valve. • Range is 594 km

worldwide.hyundai.com

Ned T. Stetson, US DOE Annual Merit Review, 16 – 20 June 2014

Ned T. Stetson, US DOE Annual Merit Review, 16 – 20 June 2014

5.5

wt%

7.5

4.5 wt%

5.5

1.2

3.3

5.2

renewable energy resources should become commercially com-petitive and gradually replace fossil fuel reformation/gasification.Hydrogen, produced by electrolysis of water using electricitygenerated from renewable resources, has the potential to be theclean, sustainable and therefore climate-neutral energy carrier ofthe future, eventually eliminating greenhouse gas emissions fromthe energy sector.

Prospective sustainable technologies that may supply hydro-gen in the future include photosplitting water using directsunlight and thermal splitting of water through high-temperaturethermochemical cycles. Current nuclear technology generateselectricity that can be used to produce hydrogen by electrolysisof water, enabling the nuclear energy industry to supply fuel tothe transportation sector. Advanced nuclear reactors are alsobeing developed that will enable high-temperature water electro-lysis (with less electrical energy needed) or thermochemicalcycles, which will use heat and a chemical process to dissociatewater. Fusion power, if successfully developed, could be theultimate source of a clean, abundant and carbon-free resource forhydrogen production.

Components of a national hydrogen delivery and distributionnetwork (including hydrogen pipelines) will need to be developedto provide a reliable supply of low-cost hydrogen to end users. Ifhydrogen is produced from hydrocarbons, the hydrogen networkwill need to be coupled to the infrastructure that will be neededfor carbon capture and storage. The use of hydrogen-fuelledvehicles will depend on successful development of an affordableand widespread refuelling infrastructure. Basic components of ahydrogen delivery and dispensing infrastructure need to bedeveloped, initially to supply local refuelling stations.

For hydrogen to become a viable energy carrier, advancedhydrogen storage technologies will be required. For hydrogen fuelcell transportation use—widely regarded as the first major inroadinto the hydrogen economy—neither cryogenic nor high-pressurehydrogen storage options can meet the mid-term targets (USDepartment of Energy, 2004). More compact, low-weight, low-cost, safe and efficient storage systems operating at near roomtemperatures and low pressures will need to be developed forautomotive as well as for stationary applications. Solid-statehydrogen storage using hydrides of light chemical elements looksto be the most promising method of achieving a high weightpercent and a high volumetric density of stored hydrogen (Fig. 4).At present, no known material meets these critical requirements.

Fuel cells have the potential to replace a very large proportion ofcurrent energy systems, from mobile phone batteries throughvehicle applications to centralised or decentralised stationary powergeneration. Fuel cells offer a very attractive technology evolutionpath in that they can deliver significant efficiency gains on today’scommercially available hydrocarbon fuels while also offering highefficiency in the future when hydrogen becomes widely available.The key scientific and technical challenges facing fuel cells are costreduction and increased durability of materials and components.

5. Conclusions

The development of hydrogen production, hydrogen storageand fuel cell technologies is set to play a central role in addressinggrowing concerns over carbon emissions and climate change aswell as future availability and security of energy supply. A studycommissioned by the Department of Trade and Industry (E4techet al., 2004) found that hydrogen energy offers the prospect ofmeeting key UK policy goals for a sustainable energy future.

Any assessment of the feasibility of a sustainable hydrogenenergy economy will involve an appraisal of the many steps thatwill have to be taken on the road to that future—not only steps insciences and technology, but also social and economic considera-tions. The ‘systems approach’ of looking at the future of hydrogenenergy, as outlined in the hydrogen strategic framework for theUK (E4tech et al., 2004), also concludes that there is no singleroute to a hydrogen economy; instead, many factors/variables areinvolved in determining its direction. It may therefore not only berather difficult, but indeed limiting, to attempt to establish onesingle path to the hydrogen economy at this juncture.

Together, hydrogen and fuel cells have the capability ofproducing a green revolution in transportation by removing CO2

emissions completely. Across the full range of energy use, thesetechnologies provide a major opportunity to shift our carbon-based global energy economy ultimately to a clean, renewable andsustainable economy based on hydrogen. The challenges aresubstantial and require scientific breakthroughs and significanttechnological developments coupled with continued social andpolitical commitment. The UK, however, has world-leadingscientific expertise and facilities, as well the renewable resourcesto accelerate the transition to a hydrogen era.

References

Appleby, A.J., Foulkes, F.R., 1993. Fuel Cell Handbook. Van Nostrand Reinhold, NewYork.

Crabtree, G.W., Dresselhaus, M.S., Buchanan, M.V., 2004. The hydrogen economy.Physics Today 57 (12), 39–44.

Department of Trade and Industry, 2003. Energy White Paper: our energyfuture—creating a low carbon economy. /http://www.berr.gov.uk/energy/whitepaper/2003/page21223.htmlS (accessed 15 May 2008).

Dutton, A.G., 2002. Hydrogen energy technology. Tyndall Working Paper TWP 17,Tyndall Centre for Climate Change, /http://www.tyndall.ac.uk/publications/working_papers/wp17.pdfS (accessed 15 May 2008).

E4tech, Element Energy, Eoin Lees Energy, 2004. A strategic framework for hydrogenenergy in the UK. Final report to the Department of Trade and Industry, /http://www.berr.gov.uk/files/file26737.pdfS (accessed 15 May 2008).

European Commission, 2003. Hydrogen energy and fuel cells: a vision of ourfuture. /http://www.europa.eu.int/comm/research/energy/pdf/hydrogen-re-port_en.pdfS (accessed 15 May 2008).

European Hydrogen and Fuel Cell Technology Platform, 2005. DeploymentStrategy. /https://www.hfpeurope.org/hfp/keydocsS (accessed 15 May 2008).

Harris, R., Book, D., Anderson, P.A., Edwards, P.P., 2004. Hydrogen storage: thegrand challenge. The Fuel Cell Review, June/July, pp. 17–23.

International Energy Agency, 2006. Hydrogen production and storage: R&Dpriorities and gaps. /http://www.iea.org/Textbase/papers/2006/hydro-gen.pdfS (accessed 15 May 2008).

King, D.A., 2004. Environment—climate change science: adapt, mitigate, or ignore?Science 303, 176–177.

Powell, J.C., Peters, M.D., Ruddell, A., Halliday, J., 2002. Fuel cells for a sustain-able future? Tyndall Working Paper TWP 50, Tyndall Centre for Climate

ARTICLE IN PRESS

Fig. 4. Gravimetric and volumetric densities of various hydrogen storage options(including the weight and volume of storage tanks). ‘DoE target’ represents the USDepartment of Energy target for hydrogen storage material.

P.P. Edwards et al. / Energy Policy 36 (2008) 4356–4362 4361

P.P. Edwards, V.L. Kuznetsov, W.I.F. David, N.P. Brandon, Energy Policy 36 (2008) 4356–4362

complex hydrides

porous

LaNi5 V-Mn metal hydrides

Hydrogen Storage

Magnesium

A. Zuettel, A. Borgschulte, Int. Symp. on H2 Energy, Richmond, USA, 12-15 Nov 2007

Andreas Züttel, University of Fribourg, 15.12.2002 12

COMPLEX HYDRIDES

Examples: NaAlH4 Mg(AlH4)2 LiBH4 Mg(BH4)2 Al(BH4)3

+ -

A. Züttel et al, J. of Power Sources 118, p.1, 2003

Zn-Na Borohydride

Lithium Borohydride

D. Reed, PhD thesis, Birmingham, 2010

Borohydrides

Filters

Beam  Steers

Sample

Pinhole

Gra3ng

CCD Focusing  Lenses

Raman spectroscopy is used to study vibrational, rotational, and other low-frequency modes in a material.

Dan Reed & David Book

Raman Spectroscopy

633nm  

488nm  

785nm  

Dan Reed & David Book

100 bar cell

High-pressure Raman spectroscopy system

Gas control

Samples cells: 1 bar – 77 to 900 K 1 bar – 300 to 1300 K

100 bar – 300 to 900 K 100 bar – 77 to 600 K

In-situ decomposition of LiBH4

Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,

In-situ decomposition of LiBH4

Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,

B12H12 B12H12 a-B

LiBH4 LiBH4

Li2B12H12

200

300

400

500

100

T °C

In situ Raman: LiBH4 (Stretch Region)

Recent applications of Raman spectroscopy to the study of hydrogen storage materials D. Reed and D. Book, Current Opinion in Solid State and Materials Science, 15, pp.62-71, 2011

Decomposition of LiBH4: Confocal Microscopy during in-situ Raman

Room  Temperature  Aldrich  LiBH4   150°C  β-­‐LiBH4  

350°C  Liquid-­‐LiBH4  450°C  Liquid-­‐LiBH4  

Hydrogen  Bubble  

Dan Reed, et al

LiBH4

•  Using Raman, able to observe formation of amorphous BxHy phases, as a function of conditions

•  Depending on stability of BxHy phase à either want to avoid, or try to utilise.

•  Problems: •  High temperatures required to desorb hydrogen •  difficult to reform LiBH4 (600 °C, 100 bar H2)

•  Can form part of Reactive Hydride Composite (i.e. mixed with other hydride and/ or borohydride)

Demonstration of Cycling of 12% wt H

900 atm H2 MgB2 �����o Mg(BH4)2 XRD, IR, MAS 11B NMR ����Û&� Rönnebro, Jensen, and Severa US patent application U.S. Patent 12/553,633. G. Severa, E. Rönnebro, C.M.Jensen; Chemical Commun. 2010, 46, 421.

Approach Reversible Dehydrogenation of Mg(BH4)2

Collaboration with Sandia and Pacific Northwest National Laboratories

Magnesium borohydride

Demonstration of Cycling of 12% wt H

900 atm H2 MgB2 �����o Mg(BH4)2 XRD, IR, MAS 11B NMR ����Û&� Rönnebro, Jensen, and Severa US patent application U.S. Patent 12/553,633. G. Severa, E. Rönnebro, C.M.Jensen; Chemical Commun. 2010, 46, 421.

Approach Reversible Dehydrogenation of Mg(BH4)2

Collaboration with Sandia and Pacific Northwest National Laboratories

Demonstration of cycling of 12 wt%

G. Severa, E. Rönnebro, C.M. Jensen, Chem. Comm, 46, p.421, 2010

Dehydrogenation .

First example of the reversible, solid state dehydrogenation of a ERURK\GULGH�DW�WHPSHUDWXUHV�EHORZ�����Û&� 11B NMR Re-hydrogention:

Hydrogen Cycling of Mg(BH4)2 Under Mild Conditions

M. Chong, A. Karkamkar, T. Autrey. S. Jalisatgi, S. Orimo, C.M. Jensen; Chem. Commun. 2011, 37, 1330.

Accomplishments (FY11)

M. Chong et al, Chem Comm 37, p.1330, 2011

Dehydrogenation .

First example of the reversible, solid state dehydrogenation of a ERURK\GULGH�DW�WHPSHUDWXUHV�EHORZ�����Û&� 11B NMR Re-hydrogention:

Hydrogen Cycling of Mg(BH4)2 Under Mild Conditions

M. Chong, A. Karkamkar, T. Autrey. S. Jalisatgi, S. Orimo, C.M. Jensen; Chem. Commun. 2011, 37, 1330.

Accomplishments (FY11)

First H2 cycling of a borohydride < 350 °C

Mg(BxHy)n MgB12H12 Mg(BH4)2

MgB2H6 or MgB5H9 or Mg(B5H8)2 or Mg(B3H8)2 …. etc ???

What  is  Mg(BxHy)n  ?    

reversible  

R.Newhouse et al., J. Phys. Chem. C., 2010; M.Chong et al., Chem. Commun., 2011; Y.Yan et al., Mater. Trans., 2011

Decomposition mechanism of α-Mg(BH4)2

G.Soloveichik et al.

Proposed mechanisms (Li et al, Energies, 2011)

As-received Mg(BH4)2 XRD

Raman spectrum (488 nm Laser)

[BH4]- stretching

[BH4]- bending

Mg(BH4)2 (06496HMV, May 2012) (Cu Kα)

Sheng Guo et al

←1.3wt%→ ← 0.9wt% → ← 4.1wt% → ← 5.0wt% → ← 0.9wt% →

Total 12.2 wt%

H2 B2H6

In situ XRD

(collected at every 25°C

. heating rate 2°C/m

in in flowing H

e) (1bar A

r 40m

l/min)

(4ba

r Ar 1

00m

l/min

)

Sheng Guo et al

In situ Raman spectra of Mg(BH4)2 (5°C/min in Ar)

[BH4]- stretching

[BH4]- bending

[B12H12]2-

[B12H12]2-

[BxHy]n-

Mg(BH4)2

Investigation of dehydrogenation processes in disordered γ-Mg(BH4)2 J Alloys and Compounds 580, pp. S296-S300, 2013 Sheng Guo, Hoi Yan Chan, Daniel Reed and David Book

v α/γ-Mg(BH4)2

Ø  β-Mg(BH4)2 decomposes via amorphous phases MgBxHy compounds to Mg.

Ø  Further studies needed to identify MgBxHy phases

Ø  One of the amorphous phases has been confirmed as MgB12H12 by in-situ Raman spectroscopy.

Ø  6.3 wt% (300 °C), 12.2 wt% (400 °C) H2 released

v  γ-Mg(BH4)2 after milling Ø  Amorphous-Mg(BH4)2 is formed after 100 bar H2 ball milling for 2 h Ø  Temperatures of desorption are reduced

Investigation of dehydrogenation processes in disordered γ-Mg(BH4)2 J Alloys and Compounds 580, pp. S296-S300, 2013 Sheng Guo, Hoi Yan Chan, Daniel Reed and David Book

à Will study full hydrogen cycling, in situ Raman

Reactive hydride composites

John Vajo et al, Int. Symp. on H2 Energy, Richmond, USA, 12-15 Nov 2007

Reactive Hydride Composites

� High gravimetric storagecapacity

� Favourable thermodynamicproperties

� Reversibility under moderateconditions in case ofborohydrides

� Further improvement of sorption kinetics

� Role of additives?

� Influence on microstructure?

� Enhancing H diffusion?

DOEsystemtarget 2007

Equilibrium Temperature of Reaction [rC]

Rev

ersi

ble

H2

capa

city

[wt.%

]

0 100 200 300 4000

2

4

6

8

10

12

14

FeTiH1.7LaNi5H6

(LiBH4)

(KBH4)

(NaBH4)

MgH2

Mg2NiH4

Mg2(Ni0.5,Cu0.5)H4

NaAlH4

technically interesting

region

-30 -40 -70Regions of Reaction Enthalpy [kJ/(mol H2)]

6LiH + 3Mg(NH2)2

MgH2+Ca(BH4)2

MgH2+2LiBH4

(Martin Dornheim, HZG)

Hydride 1 Hydride 2 New Compound H2 Gas

++

Martin Dornheim (hydrogen.hzg.de)

complex hydrides

porous

LaNi5 V-Mn metal hydrides

Hydrogen Storage

Magnesium

www.hydrogen.bham.ac.uk Melt-spinning

Mg sputtered films (800 nm)

H2 ab

sorp

tion

/ wt%

25 °C

Time (hours)

Mg nanomaterials

H2 desorption under vacuum, for different substrates

Melt-spun Mg-based material

MOF Cu-BTC 77 K

131 K

S. Tedds, A. Walton, D. Broome, D. Book, “Characterisation of Porous Hydrogen Storage Materials: Carbons, Zeolites, MOFs and PIMs”, Faraday Discussions 151, pp.75-94, 2011

Variable-temperature adsorption isotherms measured for a range of porous materials

H2 Storage: Porous Materials

D. P. Broom, D. Book , “Hydrogen Storage in Nanoporous Materials” In “Advances in hydrogen production, storage and distribution”. Ed. A. Basile & A. Iulianelli; Woodhead Publishing, July2014.

•  Weak bonding energy (20-30 kJ/mol)

•  Room temperature uptake

•  Fast kinetics •  Makes use of

hypervalent species

Adsorption of hydrogen by Hydrogenated Alkyl Titanium (III) Hydride

generally showed adsorption values at 77 K that were only 1.5times higher than at 298 K. The gravimetric and volumetricadsorption without saturation of H150-6h was 1.84 wt % at 85bar and 298 K, with a volumetric density of 23.4 kg of H2/m

3.This value is over 3 times that of compressed gas under thesame conditions. At 77 K, this sample adsorbs 2.80 wt %, and36 kg of H2/m

3. This volumetric performance is greater thanthat of MOF-177 (32 kg/m3).31 Hysteresis was observed on allsamples in the H series at 77 K (but not at 298 K), and vacuumwas required to drive out the ∼35% adsorption capacityremaining at the end of the adsorption−desorption cycles. It isbelieved that the strong interaction of H2 with Ti(III) sorptioncenters is one of the main causes of hysteresis at low pressures.This bonding interaction was even visible by Raman spectros-copy at a low hydrogen pressure of 1 bar (see RamanSpectroscopy Studies below). Generally, hydrogenation at 150°C for 2−6 h at 80 bar hydrogen pressure followed by a 2 hevacuation at 150 °C provided materials with the bestadsorption performance. By comparison of the gravimetricadsorptions at 298 and 77 K, the retentions of excessadsorption capacities could be calculated, and they rangedfrom 39 to 88% (Table T3). This is much higher than those ofMOF-5 and carbon AX-21, which retain 5.5% and 13.2%,respectively, and comparable to the levels of Cr hydrazides, inwhich the Kubas interaction was shown to be responsible foradsorption.32 Void space was removed from the H150-6hsample by compression at 500 psi, and the compressedmaterials exhibited 1.34 wt % or 2.63 wt % at 298 or 77 K and85 bar, respectively, demonstrating that compression does notlead to enhanced performance as it does for the hydrazides,possibly because of loss of surface area or collapse of thestructure (Figure S10). Calculations on the basis of gravimetricadsorption and the titanium content in each sample resulted inaverage numbers of hydrogen molecules per titanium atom(Table T4) ranging from 1.16 to 1.39 H2/Ti at 77 K and 0.64−0.76 H2/Ti at 298 K and 85 bar.Excess storage isotherms up to 140 bar for H160-6h recorded

on a PCT Pro instrument (Figure 2) show 3.49 wt % at 298 K,rising in a linear fashion without yet reaching saturation at thispressure. This corresponds to a volumetric density of 44.3 kg/m3, 3.88 times higher than compressed hydrogen storage underthe same conditions (11.4 kg/m3 according to the ideal gaslaw). The lack of saturation at this pressure suggests aperformance plateau above 150 bar. On the basis of 57.83% Tiin the materials, we can calculate an average number of H2 perTi center of 1.44 H2/Ti under these conditions. From the

difference in the molar masses of pure-phase TiH3 and H150-6h, a value of 5.8 wt % without saturation can be extrapolated at298 K and 140 bar for the pure hydrocarbon-free material. Acycle of 10 adsorption and desorption cycles is shown in Figure3, demonstrating full reversibility under these conditions.

Figure 1. Hydrogen adsorption−desorption excess storage isothermsof H-series materials. Samples at 77 K were run immediately aftersamples at 298 K; ca. 150 mg of each material was used.

Figure 2. Adsorption up to 140 bar of 150 mg of H150-6h on a PCTPro instrument calibrated against 100 mg of AX-21 (0.8 wt % at 100bar) to ensure accuracy (Figure S2c).

Figure 3. (a) Cycle of 10 adsorption and desorption isotherms up to85 bar for H150-6h on the PCI instrument. Approximately 150 mg ofmaterial was used. Errors are estimated at ±0.06 wt %. (b) Cycle of 10adsorption and desorption isotherms up to 140 bar for H150-6h onthe PCT instrument. Errors are estimated at ±0.28 wt %.

Chemistry of Materials Article

dx.doi.org/10.1021/cm402853k | Chem. Mater. 2013, 25, 4765−47714768

Hoang et al. Chemistry of Materials, DOI: 10.1021/cm402853k

Kubas interaction?

• Triangular M(H2) unit of a dihydrogen complex is expected to exhibit 6 vibrational modes: H-H stretch, symmetric and asymmetric M-H2 modes, 2 deformation modes, & torsional mode.

Hoang et al. Chemistry of Materials, DOI: 10.1021/cm402853k

?

D.M. Heinekey, W.J. Oldham, Chemical Reviews 93, No. 3010, 1993

Kubas interaction? 100 bar H2 at room temperature

Observation of TiH5 and TiH7 in Bulk-Phase TiH3 Gels for Kubas-Type Hydrogen Storage T.K.A. Hoang, L. Morris, D. Reed, D. Book, M.L. Trudeau, D.M. Antonelli Chemistry of Materials, 2013, 25 (23), pp 4765–4771

Summary q  Developed an in situ Raman spectroscopy system

for H2 storage materials (-196 to 600 °C in 100 bar H2; -196 to 800 °C in 1 bar H2 or CH4)

q  Borohydride-based compounds produced by ball-milling (& from partners): amorphous intermediate phases observed q  New reversible reaction pathways? q  Identify reversible Mg(BH4)2-based materials

q  Room temperature H2 absorption in Ti-based complex (Univ S. Wales)