The Li4Ti5Oi2 defect spinel is a promising anode material for lithium ion batteries because it transforms to/from Li7Ti5Oi2 with a negligible volume change during charging/discharging. Ab initio calculation is a powerful approach for modern materials design and mechanistic studies. However, the atomistic models of the stoichiometric Li4Ti5Oj2 and Li7Ti5Oj2 defect spinel have not been optimized due to the requirements of large unit cells and numerous atomistic arrangements of Li and Ti ions at the 16d sites of the defect spinel. In this study, ab initio calculations were systematically performed and the most energetically favorable full supercell models were constructed for both Li4Ti5O12 and Li7Ti5O12 defect spinel. The equilibrium lattice parameter of Li4Ti5O12 was 8.4257 A, while a slight lattice shrinkage of 0.77% and an average intercalation voltage of 1.41 V during charging/discharging were obtained. Moreover, the Li4Ti5O12 phase shows insulating property with a wide bandgap of around 2.3 eV, while the Li7Ti5O12 phase exhibits metallic property. All the calculated structural and electrochemical properties agree closely with the experimental findings in literature. Further theoretical studies on the Li4Ti5O12 defect spinel or other defect spinel in general can be realized according to the full supercell models proposed in this study.
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