Complex‐Concentrated Anion Doping Enables Ultra‐Stable Lattice Oxygen and Structural Integrity in Lithium‐Rich Layered Oxide Cathodes

ABSTRACT Lithium‐ and manganese‐rich layered oxides (LMR) stand out as next‐generation lithium‐ion cathode chemistries, which harness both transition‐metal and lattice‐oxygen redox processes to deliver exceptional capacity and energy density. However, their full potential is hindered by intrinsic oxygen instability and structural degradation, resulting in pronounced voltage fade and capacity decay. Here, we present a complex‐concentrated anion‐doping paradigm in which multiple anions, F, Br, and S, are incorporated into the oxygen sublattice to enhance oxygen‐redox and structural stability. X‐ray absorption spectroscopy and aberration‐corrected scanning transmission electron microscopy confirm ultra‐stable local oxygen coordination environments during long‐term cycling, with detrimental phase transformations and oxygen‐loss‐induced cavitation dramatically inhibited. Notably, we show that the characteristic LiTM 6 transition metal (TM) honeycomb ordering is preserved even after electrochemical cycling. Concurrently, this strategy yields an unprecedented volume change of only 0.63% upon charging to 4.8 V vs. Li + /Li, achieving the first zero‐strain LMR cathode. The resulting LMR cathode delivers ultralow voltage fade (1 mV per cycle during the first 100 cycles and becomes negligible in subsequent cycles) and outstanding energy retention (93% after 200 cycles) in a pouch cell configuration. Our complex‐concentrated anion‐doping concept establishes a broadly applicable strategy for resolving chemo‐mechanical failure mechanisms in ceramic intercalation electrodes for next‐generation energy storage.