Unlocking the Energy Capabilities of Aprotic Lithium‐Oxygen Batteries by Anion‐Specific Adsorption Induced Interfacial Remodeling

Aprotic lithium‐oxygen (Li─O 2 ) batteries represent a disruptive energy storage and conversion technology yet face persistent challenges from the high overpotential and deleterious surface‐mediated Li 2 O 2 growth pathway. Herein, an electric double layer (EDL) remodeling strategy is proposed, enabled by anion‐specific adsorption to fundamentally address these limitations. Through coupling in situ spectroscopies with theoretical calculations on comparative Au | LiCl‐ and Au | LiClO 4 ‐DMSO model interfaces, it is demonstrated that the specific adsorption of Cl ‐ ions at the electrode surface generates an intensified interfacial electric field and thus substantially reduces the activation barrier for oxygen reduction reaction (ORR). Simultaneously, the surface‐negative‐charge environment electrostatically repels superoxide (O 2 ‐ ) intermediates, which not only redirect the ORR toward favorable solution‐mediated Li 2 O 2 nucleation but also mitigate O 2 ‐ ‐induced byproduct coverage (e.g., carbonate) on the electrode surface. Moreover, the Cl ‐ /Cl 3 ‐ redox mediator formed on charge effectively lowers Li 2 O 2 oxidation overpotential. Consequently, the optimized configuration endows LiCl‐based Li─O 2 batteries with significantly reduced discharge overpotential of 0.26 V, 1.66‐fold increased discharge capacity at 0.5 mA cm −2 , and 1.94‐fold extended cyclability at 500 mA g −1 compared to conventional LiClO 4 ‐based counterparts. This work establishes a paradigm of electrolyte engineering through rational EDL manipulation, providing fundamental insights into tailor‐designing better Li─O 2 batteries.