Designing Better Aqueous Electrolyte for Wide‐Temperature‐Adaptive Zn‐Based Batteries: From the Perspective of Water Structure Order

Abstract Aqueous zinc‐based batteries (AZBs) are promising alternatives to lithium‐ion batteries due to their safety, low cost, and environmental compatibility. However, their reliability under extreme conditions is limited by electrolyte instability and interfacial degradation. Most existing reviews focus on low‐temperature performance by discussing the disruption of hydrogen‐bond networks to suppress freezing and improve the low‐temperature performance. To discuss these issues from a deeper perspective, this review emphasizes a more fundamental mechanism—regulating the tetrahedral structural order of water, which is the underlying driver of water crystallization. Performance enhancement strategies are further summarized at elevated temperatures, with a particular focus on the role of high‐temperature regulation. Strategies such as entropy modulation, hybrid antifreeze hydrogels, and chaotropic anion engineering that regulate water's structural order and behavior are highlighted. Specifically, how various entropy strategies significantly improve ion transport and prevent water crystallization are emphasized. Additionally, interfacial stabilization strategies, such as in situ solid‐electrolyte interphase formation and self‐regulating solvation structures, are summarized to mitigate dendrites and cathode dissolution. Finally, emerging directions, including AI‐assisted electrolyte design, self‐healing materials, and smart thermal management, providing a roadmap for wide‐temperature AZBs, are discussed.