Electrolyte and Interphase Engineering of Aqueous Batteries Beyond “Water‐in‐Salt” Strategy

Abstract Aqueous batteries are promising alternatives to non‐aqueous lithium‐ion batteries due to their safety, environmental impact, and cost‐effectiveness. However, their energy density is limited by the narrow electrochemical stability window (ESW) of water. The “Water‐in‐salts” (WIS) strategy is an effective method to broaden the ESW by reducing the “free water” in the electrolyte, but the drawbacks (high cost, high viscosity, poor low‐temperature performance, etc.) also compromise these inherent superiorities. In this review, electrolyte and interphase engineering of aqueous batteries to overcome the drawbacks of the WIS strategy are summarized, including the developments of electrolytes, electrode–electrolyte interphases, and electrodes. First, the main challenges of aqueous batteries and the problems of the WIS strategy are comprehensively introduced. Second, the electrochemical functions of various electrolyte components (e.g., additives and solvents) are summarized and compared. Gel electrolytes are also investigated as a special form of electrolyte. Third, the formation and modification of the electrolyte‐induced interphase on the electrode are discussed. Specifically, the modification and contribution of electrode materials toward improving the WIS strategy are also introduced. Finally, the challenges of aqueous batteries and the prospects of electrolyte and interphase engineering beyond the WIS strategy are outlined for the practical applications of aqueous batteries.