Does Water‐in‐Salt Electrolyte Subdue Issues of Zn Batteries?

Abstract Zn‐metal batteries (ZnBs) are safe and sustainable because of their operability in aqueous electrolytes, abundance of Zn, and recyclability. However, the thermodynamic instability of Zn metal in aqueous electrolytes is a major bottleneck for its commercialization. As such, Zn deposition (Zn 2+ → Zn(s)) is continuously accompanied by the hydrogen evolution reaction (HER) (2H + → H 2 ) and dendritic growth that further accentuate the HER. Consequently, the local pH around the Zn electrode increases and promotes the formation of inactive and/or poorly conductive Zn passivation species (Zn + 2H 2 O → Zn(OH) 2 + H 2 ) on the Zn. This aggravates the consumption of Zn and electrolyte and degrades the performance of ZnB. To propel HER beyond its thermodynamic potential (0 V vs standard hydrogen electrode (SHE) at pH 0), the concept of water‐in‐salt‐electrolyte (WISE) has been employed in ZnBs. Since the publication of the first article on WISE for ZnB in 2016, this research area has progressed continuously. Here, an overview and discussion on this promising research direction for accelerating the maturity of ZnBs is provided. The review briefly describes the current issues with conventional aqueous electrolyte in ZnBs, including a historic overview and basic understanding of WISE. Furthermore, the application scenarios of WISE in ZnBs are detailed, with the description of various key mechanisms (e.g., side reactions, Zn electrodeposition, anions or cations intercalation in metal oxide or graphite, and ion transport at low temperature).