Electronic structure and properties of lithium-rich complex oxides

Abstract

Lithium-rich complex transition-metal oxides Li${}_2$MoO${}_3$, Li${}_2$RuO${}_3$, Li${}_3$RuO${}_4$, Li${}_3$NbO${}_4$, Li${}_5$FeO${}_4$, Li${}_5$MnO${}_4$ and their derivatives are of interest for high-capacity battery electrodes. Here, we report a first-principles density-functional theory study of the atomic and electronic structure of these materials using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional which treats all orbitals in the materials on equal footing. Dimerization of the transition-metal ions is found to occur in layered Li${}_2$MoO${}_3$, in both fully lithiated and partially delithiated compounds. The Ru--Ru dimerization does not occur in fully lithiated Li${}_2$RuO${}_3$, in contrast to what is commonly believed; Ru--Ru dimers are, however, found to occur in the presence of lithium vacancies caused by lithium loss during synthesis and/or lithium removal during use. We also analyze the electronic structure of the complex oxides and discuss the delithiation mechanism in these battery electrode materials.

7 pages, 6 figures, 1 table

References in corpus (6)

• Covalent bonds against magnetism in transition metal compounds
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• Effect of disorder on the dimer transition of the honeycomb-lattice compound Li${}_2$RuO${}_3$

Cited by in corpus (1)

• Effect of Ti-doping on the dimer transition in Lithium Ruthenate