Reversible anionic redox chemistry in layered Li_4/7[□_1/7Mn_6/7]O₂ enabled by stable Li–O-vacancy configuration

The combination of anionic and cationic activities within Li-rich materials breaks through the traditional capacity limitation and achieves high-energy-density batteries. However, the utilization of anionic oxygen redox reactions always leads to detrimental lattice oxygen release, which accelerates structural distortion and electrochemical performance deterioration. In contrast to the typical Li–O–Li configuration in Li-rich layered oxides, not only can oxygen redox behaviors be triggered within layered Li_4/7[□_1/7Mn_6/7]O₂ (□: Mn vacancy) with Li–O-vacancy configuration, but lattice oxygen loss can be effectively suppressed. Upon Li⁺ (de)intercalations, Mn vacancy within the TM layer also enables reversible structural evolution and Li migration processes, further boosting high output capacity and long-term cycling stability. Besides, not only can the irreversible/reversible anionic/cationic redox reactions be clearly unraveled, but their capacity distributions can be roughly quantified upon cycling. Overall, our findings demonstrate that the introduction of Mn vacancy provides a promising configuration to achieve high-capacity cathode candidates for next-generation Li-ion batteries.