Enabling High‐Performance Layered Li‐Rich Oxide Cathodes by Regulating the Formation of Integrated Cation‐Disordered Domains

Abstract Layered Li‐rich oxide cathode materials are capable of offering high energy density due to their cumulative cationic and anionic redox mechanism during (de)lithiation process. However, the structural instability of the layered Li‐rich oxide cathode materials, especially in the deeply delitiated state, results in severe capacity and voltage degradation. Considering the minimal isotropic structural evolution of disordered rock salt oxide cathode during cycling, cation‐disordered nano‐domains have been controllably introduced into layered Li‐rich oxides by co‐doping of d 0 ‐TM and alkali ions. Combining electrochemical and synchrotron‐based advanced characterizations, the incorporation of the phase‐compatible cation‐disordered domains can not only hinder the oxygen framework collapse along the c axis of layered Li‐rich cathode under high operation voltage but also promote the Mn and anionic activities as well as Li + (de)intercalation kinetics, leading to remarkable improvement in rate capability and mitigation of capacity and voltage decay. With this unique layered/rocksalt intergrown structure, the intergrown cathode yields an ultrahigh capacity of 288.4 mAh g −1 at 0.1 C, and outstanding capacity retention of ≈90.0% with obviously suppressed voltage decay after 100 cycles at 0.5, 1, and 2 C rate. This work provides a new direction toward advanced cathode materials for next‐generation Li‐ion batteries.