Transition‐Metal Vacancy Manufacturing and Sodium‐Site Doping Enable a High‐Performance Layered Oxide Cathode through Cationic and Anionic Redox Chemistry

Triggering the anionic redox chemistry in layered oxide cathodes has emerged as a paradigmatic approach to efficaciously boost the energy density of sodium‐ion batteries. However, their practical applications are still plagued by irreversible lattice oxygen release and deleterious structure distortion. Herein, a novel P2‐Na0.76Ca0.05[Ni0.23□0.08Mn0.69]O2 cathode material featuring joint cationic and anionic redox activities, where native vacancies are produced in the transition‐metal (TM) layers and Ca ions are riveted in the Na layers, is developed. Random vacancies in the TM sites induce the emergence of nonbonding O 2p orbitals to activate anionic redox, which is confirmed by systematic electrochemical measurements, ex situ X‐ray photoelectron spectroscopy, in situ X‐ray diffraction, and density functional theory computations. Benefiting from the pinned Ca ions in the Na sites, a robust layered structure with the suppressed P2‐O2 phase transition and enhanced anionic redox reversibility upon charge/discharge is achieved. Therefore, the electrode displays exceptional rate capability (153.9 mA h g−1 at 0.1 C with 74.6 mA h g−1 at 20 C) and improved cycling life (87.1% capacity retention at 0.1 C after 50 cycles). This study provides new opportunities for designing high‐energy‐density and high‐stability layered sodium oxide cathodes by tuning local chemical environments. A novel P2‐Na0.76Ca0.05[Ni0.23□0.08Mn0.69]O2 cathode featuring joint cationic and anionic redox chemistry is evaluated in sodium‐ion batteries. Random vacancies in the transition‐metal sites effectively activate the anionic redox, and Ca ions riveted in the Na sites serve as “pillars” to stabilize the layered structure and enhance the anionic redox reversibility upon charge/discharge, thus rendering fabulous rate capability and respectable cyclic stability.