Electrolyte Design Strategies for Aqueous Sodium‐Ion Batteries: Progress and Prospects

Abstract Sodium‐ion batteries (SIBs) have emerged as one of today's most attractive battery technologies due to the scarcity of lithium resources. Aqueous sodium‐ion batteries (ASIBs) have been extensively researched for their security, cost‐effectiveness, and eco‐friendly properties. However, aqueous electrolytes are extremely limited in practical applications because of the narrow electrochemical stability window (ESW) with extremely poor low‐temperature performance. The first part of this review is an in‐depth discussion of the reasons for the inferior performance of aqueous electrolytes. Next, research progress in extending the electrochemical stabilization window and improving low‐temperature performance using various methods such as “water‐in‐salt”, eutectic, and additive‐modified electrolytes is highlighted. Considering the shortcomings of existing solid electrolyte interphase (SEI) theory, recent research progress on the solvation behavior of electrolytes is summarized based on the solvation theory, which elucidates the correlation between the solvation structure and the electrochemical performance, and three methods to upgrade the electrochemical performance by modulating the solvation behavior are introduced in detail. Finally, common design ideas for high‐temperature resistant aqueous electrolytes that are hoped to help future aqueous batteries with wide temperature ranges are summarized.