In Situ Induced Lattice‐Matched Interfacial Oxygen‐Passivation‐Layer Endowing Li‐Rich and Mn‐Based Cathodes with Ultralong Life

Abstract The high capacity of Li‐rich and Mn‐based (LRM) cathode materials is originally due to the unique hybrid anion‐ and cation redox, which also induces detrimental oxygen escape. Furthermore, the counter diffusion of released oxygen (into electrolyte) and induced oxygen vacancies (into the interior bulk phase) that occurs at the interface will cause uncontrolled phase collapse and other issues. Therefore, due to its higher working voltage (>4.7 V) than the activation voltage of lattice oxygen in LRM (≈4.5 V), the anion‐redox‐free and structurally consistent cobalt‐free LiNi_0.5Mn_1.5O₄ (LNMO) is selected to in situ construct a robust, crystal‐dense and lattice‐matched oxygen‐passivation‐layer (OPL) on the surface of LRM particles by the electrochemical delithiation to protect the core layered components. As expected, the modified sample displays continuously decreasing interfacial impedance and high specific capacity of 135.5 mAh g^‐1 with a very small voltage decay of 0.67 mV per cycle after 1000 cycles at 2 C rate. Moreover, the stress accumulation during cycling is mitigated effectively. This semicoherent OPL strengthens the surface stability and interrupts the counter diffusion of oxygen and oxygen vacancies in LRM cathode materials, which would provide guidance for designing high‐energy‐density layered cathode materials.