Jiashuo Zhang, Tao Liu, Xusheng Dong, Zhongju Chen, Bin Tang, Fanxing Bu, Hong-Peng Li, Zhen Zhou, Dongliang Chao, Ruizheng Zhao
, they undergo crystallization at low temperatures and evaporation or heat-driven side reactions at high temperatures, which have raised performance and safety concerns. Addressing these challenges requires simultaneous thermodynamic and kinetic insights into electrolyte behavior under such conditions. Among various strategies, tuning intermolecular interactions to optimize the electrolyte coordination environment has been proven to be especially effective. However, comprehensive treatments that integrate both low- and high-temperature regulation and provide underlying electrochemical mechanisms remain scarce. This review (i) dissects the failure modes of AMBs under extreme temperature conditions, (ii) discusses advances related to molecular-interaction tuning for wide-temperature performance, and (iii) offers perspectives and design guidelines for future research and development.