Raman studies on potential hydrogen storage materials The Hydrogen & Fuel Cell Researcher Conference University of Birmingham 17 th December 2013 www.hydrogen.bham.ac.uk Daniel Reed, David Book School of Metallurgy and Materials University of Birmingham, UK [email protected]
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Raman studies on potential hydrogen storage materials
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Raman studies on potential hydrogen storage materials
The Hydrogen & Fuel Cell Researcher Conference University of Birmingham
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