Indium Doping Stabilizes Lattice Oxygen in Li‐Rich Layered Cathodes via Electronic Structure Regulation

ABSTRACT Lithium‐rich manganese‐based layered oxides (LRM) are widely regarded as next‐generation cathode candidates owing to their excellent energy density. However, the practical deployment is severely hindered by irreversible capacity loss stemming from lattice oxygen instability. Herein, an electronic structure modulation via indium doping is proposed to suppress oxygen loss by mitigating the intrinsic kinetic and thermodynamic barriers. Distinct from traditional high‐valence dopants that impede the transport pathway, the large‐radius In 3+ acts as a robust structural pillar to physically expand the channels for Li + diffusion. Electronically, the strong hybridization between In 5s/5p and O 2p orbitals dramatically narrows the band gap, boosting intrinsic electronic conductivity by several orders of magnitude. Thermodynamically, the strengthened In─O covalency elevates the oxygen vacancy formation energy, effectively suppressing initial irreversible oxygen loss and persistent interfacial reactions. As a result, the optimized cathode delivers a remarkable reversible capacity of 300.3 mAh g − 1 and exceptional cycling performance. This work demonstrates an effective strategy for developing high‐performance cathodes for anion‐redox‐based batteries.