Water-in-Salt Electrolytes: Advances and Chemistry for Sustainable Aqueous Monovalent-Metal-Ion Batteries

Electrolytes play a vital role in the performance and safety of electrochemical energy storage devices, such as lithium-ion batteries (LIBs). While traditional LIBs rely on organic electrolytes, these flammable solutions pose safety risks and require expensive, moisture-sensitive manufacturing processes. Aqueous electrolytes offer a safer, more cost-effective alternative, but their narrow electrochemical window, corrosivity to electrodes, and enabling of dendritic growth on metal anodes limit their practical applications. Water-in-salt electrolytes (WiSEs) have emerged as a promising solution to these challenges. By significantly reducing water activity and forming a stable solid–electrolyte interphase (SEI), WiSEs can expand the electrochemical stability window, inhibit material dissolution, and suppress dendritic growth. This unique SEI formation mechanism, which is similar to that observed in organic electrolytes, contributes to the improved performance and stability of WiSE-based batteries. Additionally, the altered solvation structure of WiSEs minimizes the presence of free water molecules, further stabilizing the SEI and reducing water activity. This review comprehensively examines the composition, mechanisms, and characterization of WiSEs and their application in monovalent-metal-ion batteries.