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An investigation into the synthesis and characterisation of metal borohydrides for hydrogen storage

Reed, Daniel Thomas (2010)
Ph.D. thesis, University of Birmingham.

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With relatively high gravimetric and volumetric hydrogen storage capacities, borohydride compounds are being investigated for their potential use as hydrogen storage media. A study has been made into the mechanical milling of metal chlorides with sodium borohydride to try to form homoleptic borohydrides. Mechanical milling of zinc chloride with sodium borohydride resulted in the formation of a covalent complex NaZn\(_2\)(BH\(_4\))\(_5\). Thermal decomposition occurred at 80°C with a mass change of 12 wt.%, associated with the evolution of hydrogen and diborane. A composite mixture with magnesium hydride a reaction between diborane and magnesium hydride was observed form magnesium borohydride. Mechanical milling of calcium chloride or magnesium chloride with sodium borohydride did not produce calcium borohydride and magnesium borohydride, but rather resulted in solid solutions where chlorine ions substitute for borohydride ions within the cubic sodium borohydride lattice. Thermal decomposition of milled calcium chloride and sodium borohydride occurs at a similar manner to that of Ca(BH\(_4\))\(_2\) (from Sigma-Aldrich). Milled magnesium chloride and sodium borohydride thermally decomposes via several unknown phases with a weight loss of 4.4 wt.% yielding Mg, MgB\(_2\), B, and [B\(_{12}\)H\(_{12}\)]\(^{2-}\). Lithium borohydride investigated using Raman spectroscopy. After heating lithium borohydride through its orthorhombic to hexagonal phase change (118°C) and melting point (280°C), shifts in Raman peak position and peak width were measured as a function of temperature. This work shows the in-situ decomposition of LiBH\(_4\) observing formation of lithium dodecaborane (Li\(_2\)B\(_{12}\)H\(_{12}\)) at 340°C and amorphous boron from liquid lithium borohydride.

Type of Work:Ph.D. thesis.
Supervisor(s):Book, David
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Metallurgy and Materials
Subjects:TJ Mechanical engineering and machinery
TP Chemical technology
TN Mining engineering. Metallurgy
Institution:University of Birmingham
ID Code:1008
This unpublished thesis/dissertation is copyright of the author and/or third parties.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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