Deciphering Solvation Chemistry for Low‐Temperature Lithium‐Ion Battery Electrolytes: Mechanisms, Strategies, and Beyond

ABSTRACT Low‐temperature performance degradation limits lithium‐ion batteries (LIBs) in extreme climates and specialized applications. Electrolytes govern Li + transport and interfacial reactions, whereas their solvation chemistry controls ionic conductivity, desolvation kinetics, and interphase stability. This review analyzes low‐temperature electrolyte failure through three coupled limitations: hindered ion transport, increased desolvation barriers, and interfacial instability. We then examine how solvation‐structure design and interfacial regulation address these limitations. Recent advances are organized around solvent selection, multicomponent synergy, weakly solvating and high‐concentration electrolytes, and functional additives. Particular attention is given to polarity‐gradient engineering and fluorine‐coordinated electrolytes, which homogenize solvation environments and extend coordination chemistry beyond oxygen. We also assess emerging uses of machine learning and multiscale simulation in electrolyte discovery. Finally, we identify practical challenges and propose closer integration of modeling with experimental characterization to guide high‐performance low‐temperature electrolytes.