Tuning Bulk O2 and Nonbonding Oxygen State for Reversible Anionic Redox Chemistry in P2‐Layered Cathodes

摘要

Abstract Improving the reversibility of oxygen redox is quite significant for layered oxides cathodes in sodium‐ion batteries. Herein, we for the first time simultaneously tune bulk O2 and nonbonding oxygen state for reversible oxygen redox chemistry in P2‐Na0.67Mn0.5Fe0.5O2 through a synergy of Li2TiO3 coating and Li/Ti co‐doping. O2? is oxidized to molecular O2 and peroxide (O2)n? (n<2) during charging. Molecular O2 derived from transition metal (TM) migration is related to the superstructure ordering induced by Li doping. The synergy mechanism of Li2TiO3 coating and Li/Ti co‐doping on the two O‐redox modes is revealed. Firstly, Li2TiO3 coating restrains the surface O2 and inhibits O2 loss. Secondly, nonbonding Li?O?Na enhances the reversibility of O2?→(O2)n?. Thirdly, Ti doping strengthens the TM?O bond which fixes lattice oxygen. The cationic redox reversibility is also enhanced by Li/Ti co‐doping. The proposed insights into the oxygen redox reversibility are insightful for other oxide cathodes.