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Mixed anion complex hydrides for hydrogen storage

Chater, Philip A (2010)
Ph.D. thesis, University of Birmingham.

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The first examples of a new class of mixed anion complex hydride have been synthesised and characterised. The structures of three amide-borohydride complex hydrides of lithium and sodium, Li\(_4\)BH\(_4\)(NH\(_2\))\(_3\), Li\(_2\)BH\(_4\)NH\(_2\) and Na\(_2\)BH\(_4\)NH\(_2\), have been solved by powder diffraction methods and characterised by infrared and Raman spectroscopy. The thermal decomposition of these hydrogen rich materials was investigated and hydrogen was observed as the major gaseous product in all cases. Ammonia was observed as a minor product with the amount of ammonia release dependent on the sample composition and experimental set-up. Powder diffraction was used to identify the solid decomposition products and decomposition pathways are proposed. Two competing decomposition pathways, one forming metal hydride and boron nitride, the other forming metal nitridoborate, were identified for the lithium system and suggested for the sodium system. \(In\)-\(situ\) and \(ex\)-\(situ\) powder diffraction, differential scanning calorimetry and temperature programmed desorption were used to investigate the lithium amide-borohydride system in detail and a phase diagram was proposed. The reactions of metal hydrides with Li\(_4\)BH\(_4\)(NH\(_2\))\(_3\) were tested and were found to reduce the amount of ammonia released. A reversible hydrogen storage reaction was observed upon reaction with magnesium hydride, which was investigated with gravimetric methods and \(ex\)-\(situ\) powder diffraction to elucidate the reaction pathway.

Type of Work:Ph.D. thesis.
Supervisor(s):Anderson, P.A. (Paul Alexander) (1965-)
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Keywords:Hydrogen storage; Complex hydrides
Subjects:QD Chemistry
Institution:University of Birmingham
ID Code:733
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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