Ultrahigh‐Capacity Rocksalt Cathodes Enabled by Cycling‐Activated Structural Changes

Abstract Mn‐redox‐based oxides and oxyfluorides are considered the most promising earth‐abundant high‐energy cathode materials for next‐generation lithium‐ion batteries. While high capacities are obtained in high‐Mn content cathodes such as Li‐ and Mn‐rich layered and spinel‐type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn‐rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. It is shown that upon cycling of a cation‐disordered rocksalt (DRX) cathode (Li_1.1Mn_0.8Ti_0.1O_1.9F_0.1, an ultrahigh capacity of ≈320 mAh g⁻¹ (energy density of ≈900 Wh kg⁻¹) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn⁴⁺ and Li⁺ vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn⁴⁺ reduction, along with Li⁺ insertion transform the structure to a partially ordered DRX phase with a β′‐LiFeO₂‐type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high‐Mn DRXbut also provide guidance for the future development of Mn‐based, high‐energy density oxide, and oxyfluoride cathode materials.