Li₂MnO₃ endows Li-rich layered oxides with a superior energy density; however, its electron transfer mechanism is still unclear. Here, the electronic and thermodynamic behavior of Li_xMnO₃ (x = 0.5–2) is determined using first-principles computations. The cationic redox, anionic redox, and local electron exchange in Mn-O polyhedron are revealed. An obvious electron donation inclination of manganese is demonstrated when the Li⁺ content is low. Through ab initio molecular dynamics, high valence Mn⁶⁺ and Mn⁷⁺ are generated in the form of MnO₄ tetrahedrons with structural transformation toward a disordered structure, controlled by the Li⁺ content and dynamic energy barrier. Furthermore, a local redox reaction between Mn⁶⁺ or Mn⁷⁺ and their surrounding oxygen atoms is elucidated. Consequently, a comprehensive understanding regarding the electron transfer in Li_xMnO₃ is provided. Our results bring insight regarding the electron transfer mechanism in Li-rich layered oxide cathode materials and encourage further reconsideration and investigation into its redox mechanism.

Li ₂ MnO ₃使富含锂的层状氧化物具有更高的能量密度；然而，其电子转移机理仍不清楚。在这里，Li _x MnO ₃（x = 0.5-2）的电子和热力学行为是使用第一原理计算确定的。揭示了Mn-O多面体中的阳离子氧化还原，阴离子氧化还原和局部电子交换。当Li ⁺含量低时，表明锰的明显的给电子倾向。通过从头算分子动力学，以MnO ₄的形式生成高价态的Mn ⁶⁺和Mn ⁷⁺由Li ⁺含量和动态能垒控制的结构向无序结构转变的四面体。此外，阐明了Mn ⁶⁺或Mn ⁷⁺与它们周围的氧原子之间的局部氧化还原反应。因此，提供了关于Li _x MnO _3中电子转移的全面理解。我们的结果带来了关于富锂层状氧化物阴极材料中电子转移机理的见识，并鼓励人们进一步重新考虑和研究其氧化还原机理。