Vacancy-mediated hydrogen desorption in NaAlH4 -: art. no. 165101

First-principles calculations based on density functional theory are carried out to understand the mechanisms responsible for hydrogen desorption from Ti-doped sodium-alanate (NaAlH4). While the energy needed to remove a hydrogen atom from NaAlH4 with Ti substituted either at the Na site or at Al site is found to be significantly lower than that from the pristine NaAlH4, the presence of Na vacancies is shown to play an even larger role: It is not only an order of magnitude smaller than that from Ti-doped sodium-alanate, but the removal of hydrogen associated with a Na vacancy is exothermic with respect to formation of H-2 molecule. Furthermore, we show that the unusual stabilization of the magic AlH3 cluster in the vacancy containing sodium-alanate is responsible for this diminished value of the hydrogen-removal energy. It is suggested that this role of vacancies can be exploited in the design and synthesis of complex light-metal hydrides suitable for hydrogen storage.