Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications : Ab initio density functional calculations

Du, A.J., Smith, Sean, & Lu, G. (2006) Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications : Ab initio density functional calculations. Physical Review B (Condensed Matter and Materials Physics), 74(19), pp. 1934051-1934054.

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NaAlH4 and LiBH4 are potential candidate materials for mobile hydrogen storage applications, yet they have the drawback of being highly stable and desorbing hydrogen only at elevated temperatures. In this letter, ab initio density functional theory calculations reveal how the stabilities of the AlH4 and BH4 complex anions will be affected by reducing net anionic charge. Tetrahedral AlH4 and BH4 complexes are found to be distorted with the decrease of negative charge. One H-H distance becomes smaller and the charge density will overlap between them at a small anion charge. The activation energies to release of H2 from AlH4 and BH4 complexes are thus greatly decreased. We demonstrate that point defects such as neutral Na vacancies or substitution of a Na atom with Ti on the NaAlH4(001) surface can potentially cause strong distortion of neighboring AlH4 complexes and even induce spontaneous dehydrogenation. Our results help to rationalize the conjecture that the suppression of charge transfer to AlH4 and BH4 anion as a consequence of surface defects should be very effective for improving the recycling performance of H2 in NaAlH4 and LiBH4. The understanding gained here will aid in the rational design and development of hydrogen storage materials based on these two systems.

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41 citations in Web of Science®
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ID Code: 61160
Item Type: Journal Article
Refereed: Yes
Keywords: AIH4, BH4, complex anions, hydrogen storage
DOI: 10.1103/PhysRevB.74.193405
ISSN: 1550-235X
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2006 American Physical Society
Deposited On: 08 Jul 2013 04:06
Last Modified: 29 Jul 2013 23:35

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