Zinc Chemistries of Hybrid Electrolytes in Zinc Metal Batteries: From Solvent Structure to Interfaces

Abstract Along with the booming research on zinc metal batteries (ZMBs) in recent years, operational issues originated from inferior interfacial reversibility have become inevitable. Presently, single‐component electrolytes represented by aqueous solution, “water‐in‐salt,” solid, eutectic, ionic liquids, hydrogel, or organic solvent system are hard to undertake independently the task of guiding the practical application of ZMBs due to their specific limitations. The hybrid electrolytes modulate microscopic interaction mode between Zn²⁺ and other ions/molecules, integrating vantage of respective electrolyte systems. They even demonstrate original Zn²⁺ mobility pattern or interfacial chemistries mechanism distinct from single‐component electrolytes, providing considerable opportunities for solving electromigration and interfacial problems in ZMBs. Therefore, it is urgent to comprehensively summarize the zinc chemistries principles, characteristics, and applications of various hybrid electrolytes employed in ZMBs. This review begins with elucidating the chemical bonding mode of Zn²⁺ and interfacial physicochemical theory, and then systematically elaborates the microscopic solvent structure, Zn²⁺ migration forms, physicochemical properties, and the zinc chemistries mechanisms at the anode/cathode interfaces in each type of hybrid electrolytes. Among of which, the scotoma and amelioration strategies for the current hybrid electrolytes are actively exposited, expecting to provide referenceable insights for further progress of future high‐quality ZMBs.