Reorganizing Helmholtz Adsorption Plane Enables Sodium Layered‐Oxide Cathode beyond High Oxidation Limits

Abstract Sodium layered‐oxides (Na_xTMO₂) sustain severe interfacial stability issues when subjected to battery applications. Particularly at high potential, the oxidation limits including transition metal dissolution and solid electrolyte interphase reformation are intertwined upon the cathode, resulting in poor cycle ability. Herein, by rearranging the complex and structure of the Helmholtz absorption plane adjacent to Na_xTMO₂ cathodes, the mechanism of constructing stable cathode/electrolyte interphase (CEI) to push up oxidation limits is clarified. The strong absorbent fluorinated anions replace the solvents into the inner Helmholtz plane, thereby reorganizing the Helmholtz absorption structure and spontaneously inducing anion‐dominated interphase to envelop more active sites for layered oxides. More importantly, such multi‐component CEI proves effective for the long‐term durability of a series of manganese‐based oxide cathodes, which achieves a 1500‐cycles lifetime against high oxidation voltage limit beyond 4.3 V. This work unravels the key role of breaking high‐oxidation limits in attaining higher energy density of layered‐oxide systems.