The cation configuration of transition-metal (TM) layered oxides used as cathode materials for batteries, which significantly affects their intrinsic performance, is extremely important for understanding their electrochemical behavior and remained unclear until now. Herein, the local cation configuration of a series of Mn-based Li-rich layered oxides (Mn-LLOs) was revealed thoroughly by statistical methods, and the influence of the cation configuration on the cationic/anionic redox was also elucidated. Using neutron and synchrotron X-ray pair distribution function combined with Monte Carlo simulation, the existence of Li₂MnO₃ rather than Li₂MnO₃-like crystal domain in all Mn-LLOs is revealed strongly, showing each Li atom in the TM layer is surrounded by six Mn atoms with no Ni atom to form a LiMn₆ unit, and the reversibility of oxygen redox is closely related with those local structure environments. This work provides insights for the cation configuration investigation of oxide materials and also sheds light on the understanding of the local structure-activity relationship.

用作电池正极材料的过渡金属 (TM) 层状氧化物的阳离子构型会显着影响其固有性能，这对于理解其电化学行为极为重要，但迄今为止仍不清楚。在此，通过统计方法彻底揭示了一系列Mn基富锂层状氧化物（Mn-LLOs）的局部阳离子构型，并阐明了阳离子构型对阳离子/阴离子氧化还原的影响。利用中子和同步加速器X射线对分布函数结合蒙特卡罗模拟，存在Li ₂ MnO ₃而不是Li ₂ MnO ₃所有 Mn-LLO 中的类晶畴都被强烈揭示，显示 TM 层中的每个 Li 原子被六个没有 Ni 原子的 Mn 原子包围形成一个 LiMn ₆单元，氧氧化还原的可逆性与那些局部密切相关结构环境。这项工作为氧化物材料的阳离子构型研究提供了见解，也为理解局部构效关系提供了启示。