Raman studies on potential hydrogen storage materials
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1 Raman studies on potential hydrogen storage materials The Hydrogen & Fuel Cell Researcher Conference University of Birmingham 17 th December 2013 Daniel Reed, David Book School of Metallurgy and Materials University of Birmingham, UK
2 Raman studies on potential hydrogen storage materials Advantages of vibrational spectroscopy Use of vibrational spectroscopy in determining bonding in complex hydrides ABH 4 + MCl 2 Observing bonding not within the crystal lattice Kubas interations
3 Hydrogen Storage Technology Portfolio Chemical or complex hydrides Chemical or complex hydrides Involve Covalent bonding
4 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
5 Vibrational Spectroscopy
6 What is Raman Spectroscopy
7 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)
8 Complex hydrides Configuration of M-BH 4 bonding D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72
9 ABH 4 + MnCl 2 Mn(BH 4 ) 2 K 2 Mn(BH 4 ) 4 Na(BH 4 ) x Cl 1-x Reed et. al. to be published
10 Ammonia borane (NH 3 BH 3 ) D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp 62-72
11 NaAlH 4 Measured Calculated Reed et. al. to be published
12 THERMAL DECOMPOSITION
13 In-situ decomposition of LiBH 4 D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,
14 In-situ decomposition of LiBH 4 D. Reed, D. Book. Current Opinion in Solid State and Material Science, 2011, 15 (2), pp Reed, D; Book, D. MRS Symposium Proceedings 1216E, Fall 2009,
15 Reactive Hydride Composites J.J. Vajo et al. Journal of Alloys and Compounds (2007)
16 Effect of hydrogen back pressure (4LiBH 4 + YH 3 ) Dehydrogenation profiles of the 4LiBH 4 + YH 3 composite under (a) static vacuum and (b) hydrogen back pressure XRD patterns of the (a) as-milled and dehydrogenated samples of the 4LiBH4 + YH3 composite under (b) static vacuum and (c) hydrogen back pressure. J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59 63
17 Effect of hydrogen back pressure (4LiBH 4 + YH 3 ) Desorption under H 2 Desorption under Dynamic vacuum J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59 63
18 Effect of hydrogen back pressure (4LiBH 4 + YH 3 ) Desorption under H 2 YH YB 43 J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59 63
19 Effect of hydrogen back pressure (4LiBH 4 + YH 3 ) Desorption under Dynamic vacuum YB YH 34 J. Shim et. al. J. Phys. Chem. Lett. 2010, 1, 59 63
20 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: /cm402853k
21 Hoang et al. Chemistry of Materials, DOI: /cm402853k
22 H2 Hoang et al. Chemistry of Materials, DOI: /cm402853k
23 Kubas interaction Hoang et al. Chemistry of Materials, DOI: /cm402853k
24 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)
25 Acknowledgements Dr David Book Dr Ruixia Liu Ms Sheng Guo Dr David Antonelli Dr Tuan Hoang Dr YoungWhan Cho Dr Jae-Hyeok Shim UK Sustainable Hydrogen Energy Consortium ( , ) Hydrogen and Fuel Cell Research Hub ( ) Birmingham Science City - Hydrogen Energy ( ) Novel Complex Metal Hydrides for Efficient and Compact Storage of Renewable Energy as Hydrogen and Electricity (ECOSTORE) ( ) Korean Institute for Energy Research Measurement of Hydrogen Storage Materials (Mar 10 Apr 13)
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