Understanding Lattice Oxygen Redox Behavior in Lithium‐Rich Manganese‐Based Layered Oxides for Lithium‐Ion and Lithium‐Metal Batteries from Reaction Mechanisms to Regulation Strategies

Abstract Lithium‐rich manganese‐based layered oxides (LMLOs) are considered to be one type of the most promising materials for next‐generation cathodes of lithium batteries due to their distinctive anionic redox processes contributing ultrahigh capacity and energy density. Unfortunately, their practical applications are still plagued by several challenges such as undesirable interfacial reactions and structural evolution, as well as voltage hysteresis/recession, in which irreversible anionic redox behavior bears the brunt as the primacy factor. Undoubtedly, a deep understanding of anionic redox reaction mechanisms and irreversible behavior of oxygen species is crucial in order to provide essential guidance for modification strategies for LMLOs. In this paper, the fundamental understanding of intricate anionic redox reaction mechanisms from thermodynamics models to kinetic anionic redox reaction pathways is comprehensively reviewed, and the existing challenges of LMLOs related with irreversible oxygen reaction behavior are analyzed. Furthermore, numerous representative modification strategies for overcoming these challenges, coupled with their underlying mechanisms for regulating anionic redox reversibility are summarized. In addition, the aspects of multi‐scale structural modifications, integration of interdisciplinary technologies, and application in quasi‐/all‐solid‐state battery systems are given some emphasis in terms of further improvement of LMLOs‐based cathode materials for advanced lithium batteries‐based energy storage systems.