Triggering Cationic/anionic Hybrid Redox Stabilizes High-temperature Li-rich Cathodes Materials via Three-in-one Strategy

Efficiently advancing lithium-ion batteries toward high energy density entails overcoming challenges in Li-rich layered oxides, including severe voltage and capacity fading, irreversible oxygen escape and compromised thermal robustness due to the uncontrollable oxygen anionic redox (OAR). Herein, a three-in-one modification strategy, aim at strengthening the reversibility of OAR and structural integrity of MnO6 octahedron, is rationally introduced on Li1.2Mn0.53Ni0.20Co0.07O2 cathode through a universal H3BO3-treatment. Through the introduction of oxygen vacancies and gradient B-doping, the energy level of unhybridized O 2p states is decreased to narrow the band energy gap with transition metal (TM) band, which triggers cationic/anionic hybrid redox at high voltage, thereby stabilizing the peroxo-like (O2)n- species and hindering irreversible oxygen escape, while the lithium borate nano-coating serves to mitigate side reactions, particularly during charging at elevated temperatures. As a result, the modulated cathode exhibits notable capacity retention of 96.3% after 500 cycles at 1 C with limited voltage fading rate (1.73 mV per cycle) and even stable cyclic performance at high temperature (60°C). This approach provides an effective and straightforward method to tackle the voltage decay and capacity fading of high-energy Li-rich layered cathode materials.