Tuning Anionic Redox Activity and Reversibility for a High‐Capacity Li‐Rich Mn‐Based Oxide Cathode via an Integrated Strategy

Abstract When fabricating Li‐rich layered oxide cathode materials, anionic redox chemistry plays a critical role in achieving a large specific capacity. Unfortunately, the release of lattice oxygen at the surface impedes the reversibility of the anionic redox reaction, which induces a large irreversible capacity loss, inferior thermal stability, and voltage decay. Therefore, methods for improving the anionic redox constitute a major challenge for the application of high‐energy‐density Li‐rich Mn‐based cathode materials. Herein, to enhance the oxygen redox activity and reversibility in Co‐free Li‐rich Mn‐based Li1.2Mn0.6Ni0.2O2 cathode materials by using an integrated strategy of Li2SnO3 coating‐induced Sn doping and spinel phase formation during synchronous lithiation is proposed. As an Li+ conductor, a Li2SnO3 nanocoating layer protects the lattice oxygen from exposure at the surface, thereby avoiding irreversible oxidation. The synergy of the formed spinel phase and Sn dopant not only improves the anionic redox activity, reversibility, and Li+ migration rate but also decreases Li/Ni mixing. The 1% Li2SnO3‐coated Li1.2Mn0.6Ni0.2O2 delivers a capacity of more than 300 mAh g−1 with 92% Coulombic efficiency. Moreover, improved thermal stability and voltage retention are also observed. This synergic strategy may provide insights for understanding and designing new high‐performance materials with enhanced reversible anionic redox and stabilized surface lattice oxygen.