Raman studies on potential hydrogen storage materials

The Hydrogen & Fuel Cell Researcher Conference University of Birmingham

17th December 2013

www.hydrogen.bham.ac.uk

Daniel Reed, David Book

School of Metallurgy and Materials

University of Birmingham, UK D.Reed@bham.ac.uk

Raman studies on potential hydrogen storage materials

• Advantages of vibrational spectroscopy

• Use of vibrational spectroscopy in determining bonding in complex hydrides

– ABH4 + MCl2

• Observing bonding not within the crystal lattice

– Kubas interations

Hydrogen Storage Technology Portfolio

Chemical or complex hydrides

Involve Covalent bonding

Chemical or complex hydrides

What is Vibrational spectroscopy

• Non-destructive, non-invasive technique that provides information on the: – Composition

– Structure

– and interactions within the sample

• Looks at the interaction between light and matter – Measure the vibrational energy levels associated

with chemical bonds

Vibrational Spectroscopy

What is Raman Spectroscopy

Advantages of Raman

• Sensitive to crystalline and amorphous solids, liquids and gases

• Ability to follow a reaction across a change of state (e.g. solid to liquid)

• Works on a single excitation wavelength

• Use of different lasers can overcome fluorescence

Variable temperature (LN2 to 600 °C) Variable pressure (UHV to 100 bar)

Complex hydrides

Configuration of M-BH4 bonding

D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72

ABH4 + MnCl2

Mn(BH4)2

Na(BH4)xCl1-x

K2Mn(BH4)4

Reed et. al. to be published

Ammonia borane (NH3BH3)

D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72

NaAlH4

Measured

Calculated

Reed et. al. to be published

THERMAL DECOMPOSITION

In-situ decomposition of LiBH4

D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72 Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,

In-situ decomposition of LiBH4

D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72 Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,

Reactive Hydride Composites

J.J. Vajo et al. Journal of Alloys and Compounds 446–447 (2007) 409–414

Effect of hydrogen back pressure (4LiBH4 + YH3)

XRD patterns of the (a) as-milled and dehydrogenated samples of the 4LiBH4 + YH3 composite under (b) static vacuum and (c) hydrogen back pressure.

Dehydrogenation profiles of the 4LiBH4 + YH3 composite under (a) static vacuum and (b) hydrogen back pressure

J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59–63

Effect of hydrogen back pressure (4LiBH4 + YH3)

J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59–63

Desorption under H2

Desorption under Dynamic vacuum

Effect of hydrogen back pressure (4LiBH4 + YH3)

J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59–63

Desorption under H2

YH3 YB4

Effect of hydrogen back pressure (4LiBH4 + YH3)

J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59–63

YH3

Desorption under Dynamic vacuum

YB4 YH3

Kubas interactions

• Weak bonding energy (20-30 kJ/mol)

• Room temperature uptake

• Fast kinetics

• Makes use of hypervalent species

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

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

H2

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

Kubas interaction

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

Summary

• Sensitive to crystalline and amorphous solids, liquids and gases

• Combined with other techniques Raman can allow the determination of thermal decomposition mechanisms

• Combined with PDOS calculations allows simulated Raman spectra to aid interpretation

• Observed interactions between H2 and hypervalent metal centres (Kubas bonding)

UK Sustainable Hydrogen Energy Consortium (2003-07, 2007-11)

Birmingham Science City - Hydrogen Energy (2006-2016)

Hydrogen and Fuel Cell Research Hub (2012-17)

Novel Complex Metal Hydrides for Efficient and Compact Storage of

Renewable Energy as Hydrogen and Electricity (ECOSTORE) (2013-16)

Korean Institute for Energy Research

“Measurement of Hydrogen Storage Materials” (Mar 10 – Apr 13)

Acknowledgements

Dr David Book Dr Ruixia Liu Ms Sheng Guo

Dr David Antonelli Dr Tuan Hoang Dr YoungWhan Cho Dr Jae-Hyeok Shim