Sulfuration of Li‐Rich Mn‐Based Cathode Materials for Multianionic Redox and Stabilized Coordination Environment

Abstract Lithium‐rich transition metal oxides (LLOs) can deliver high specific capacity over 250 mAh g⁻¹, stemming from additional contribution of oxygen redox. However, the formation of O⁽²⁻ⁿ⁾⁻ (0 < n < 2) species and even oxygen gas during the deep oxidation stage leads to progressive structural transformation that cause voltage decay/hysteresis, sluggish kinetics, and poor thermostability, preventing real‐world application of LLOs. Therefore, the substantive key relies on enhancing the anionic redox stability in LLOs. Here, a sulfuration procedure of LLOs (S‐LLOs) is proposed, in which sulfur anions are incorporated into oxygen sites in the lattice structure and form polyanions on the surface. Proved by structural characterizations and density functional theory (DFT) calculations, sulfur anions in the interior lattice can reversibly participate in the redox process and enhance the integral coordination stability by mitigating undesired oxygen redox. Moreover, S polyanions at the surface form a protecting layer for interfacial stability. The electrochemical measurements indicate that S‐LLO demonstrates a high discharge capacity of 307.8 mAh g⁻¹, an outstanding capacity retention rate of 91.5% after 200 cycles, along with excellent voltage maintenance, rate capability, and thermostability. The sulfuration process of LLOs with multianionic redox mechanism highlights a promising strategy to design novel high‐energy‐density cathode materials with superior cycling performance.