Anti‐Freezing Electrolytes in Aqueous Multivalent Metal‐Ion Batteries: Progress, Challenges, and Optimization Strategies

Abstract Aqueous rechargeable multivalent metal‐ion batteries (ARMMBs) have attracted considerable attention due to their high capacity, high energy density, and low cost. However, their performance is often limited by low temperature operation, which requires the development of anti‐freezing electrolytes. In this review, we summarize the anti‐freezing mechanisms and optimization strategies of anti‐freezing electrolytes for aqueous batteries (especially for Zn‐ion batteries). Besides, we investigate the possible interactions and side reactions between electrolytes and electrodes. We also analyze the problems between electrolytes and electrodes at low temperature, and propose possible solutions. The research progress in the field of low temperature energy storage for aqueous Mg‐ion, Ca‐ion, and Al‐ion batteries, and the challenges faced in their anti‐freezing electrolytes are investigated in detail. Last but not least, the outlook on the energy storage applications of ARMMBs is provided to guide the future research.