Lithium-rich complex transition-metal oxides Li2MoO3, Li2RuO3, Li3RuO4, Li3NbO4, Li5FeO4, Li5MnO4 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 Li2MoO3, in both fully lithiated and partially delithiated compounds. The Ru-Ru dimerization does not occur in fully lithiated Li2RuO3, in contrast to what is commonly believed; Ru-Ru dimers are, however, found to occur in the presence of neutral 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.

中文翻译：

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富锂复合氧化物的电子结构和性能。

富锂复合过渡金属氧化物Li2MoO3，Li2RuO3，Li3RuO4，Li3NbO4，Li5FeO4，Li5MnO4及其衍生物是高容量电池电极所关注的。在这里，我们报告使用Heyd-Scuseria-Ernzerhof（HSE）筛选的杂合官能团对这些材料的原子和电子结构进行第一原理密度泛函理论研究，该方法可以平等地处理材料中的所有轨道。发现在完全锂化和部分去锂化的化合物中，层状Li2MoO3中都会发生过渡金属离子的二聚化。与通常认为的相反，Ru-Ru二聚化在完全锂化的Li2RuO3中不会发生。然而，发现Ru-Ru二聚体在中性锂空位的存在下发生，该空位是由合成期间的锂损失和/或使用期间的锂去除引起的。