Design of electrolyte for boosted aqueous battery performance: A critical review and perspective

Aqueous alkali and multivalent metal-ion batteries are practically advantageous for large-scale energy storage because of intrinsic safety and environmental friendliness. Drawbacks, however, include low energy density and short life because of limited electrochemical stability windows (ESWs) of aqueous electrolytes and rapid degradation of electrode materials with high water activity. Despite significant research, including water-in-salt and electrolyte additive(s), directed to the electrolyte to extend ESWs and to boost electrode stability, the practical application remains limited because of the present high cost and generally unsatisfactory performance. Although alkali and multivalent metal ions can have different coordinating structures with solvents and anions, electrolyte design strategies share fundamental mechanisms in either extending ESWs or achieving a passivation layer on the electrode material(s). Future development of aqueous batteries, therefore, is dependent on a systematic understanding and analysis of electrolyte research. Here, we report for the first time a systematic review of the design and engineering of emerging water-based electrolytes for boosted aqueous rechargeable batteries (ARBs) performance. We present a comparative summary of electrochemical stability windows and electrode/electrolyte interphases for five (5) electrolyte types; appraise strategies and the resulting impact of electrolyte properties on electrode interfacial stability; analyze in situ generated electrode/electrolyte interphases; classify advantages and drawbacks of selected strategies; and provide a perspective on future developments in aqueous alkali and multivalent metal-ion batteries, together with methods for the study of both electrolyte and derived interphase(s). We conclude that (1) the design of electrolytes of high concentration and hybrid and eutectic solvents are practically promising for high energy density ARBs; (2) there is a need to improve design for longer cycling life of ARBs; (3) research addresses boosting ESW of the electrolyte; and (4) it increased the understanding of the electrode/electrolyte interface stability via new electrode/electrolyte interphase structures. This review will be of benefit in the practical design of electrolyte(s) for aqueous batteries for high performance and, therefore, of interest to researchers and manufacturers. © 2023 Crown.