Stabilizing the Localized O 2 n− for Enhanced Cycling Stability in Li‐Rich Cathodes

Li‐rich layered oxides are regarded as the most promising next‐generation cathodes. However, the commercial application of Li‐rich cathodes is significantly hindered by the irreversible release of oxygen and severe voltage and capacity decay. Herein, a synergistic modification strategy is proposed that effectively achieves the simultaneous construction of oxygen vacancies, spinel phase structures, and a TiF 4 coating. This synergistic interface reconstruction not only synergistically stabilizes the localized O 2 n− and reduces the interfacial side reaction, but also constructs a 3D channel for Li + ion diffusion to enhance rate performance. The modified cathode demonstrates an outstanding discharge capacity of 269.3 mAh g −1 at 0.1 C, with nearly unchanged capacity after 300 cycles at 1 C. Moreover, the capacity retention remains as high as 96% after 200 cycles at both 2 C and 5 C. This work offers valuable new insights into enhancing the comprehensive electrochemical performance of Li‐rich layered oxides.