Electrolyte Design via Temperature-Responsive Solvation Structures for All-Climate Batteries

Abstract Extreme-temperature operation remains one of the greatest challenges for batteries, as low temperatures impede ionic transport and high temperatures accelerate side reactions. Understanding how temperature reshapes coordination equilibria is, therefore, essential for designing electrolytes with temperature-responsive solvation structures. This perspective examines the mechanistic basis of temperature-responsive solvation, starting with how temperature modulates cation-centered interactions, followed by the complementary roles of anion-centered interactions and broader intermolecular forces such as solvent–solvent and anion–anion correlations. Together, these interactions generate multiscale solvation reorganization that determines ion-pairing equilibria, mesoscale clustering, and interfacial chemistry. Building on these insights, molecular design strategies like using tailored solvents, engineered anions, and functional additives are outlined. Furthermore, the reciprocal relationship is analyzed where solvation structures reshape the solid-electrolyte interphase (SEI) and cathode-electrolyte interphase (CEI), which, in turn, modifies solvation structures. Emerging variable-temperature and operando techniques for visualizing reversible solvation switching and interphase evolution are summarized. By connecting molecular interactions to temperature-responsive solvation behavior, this work establishes guiding principles for electrolytes that enable all-climate batteries.