Designing Weakly Solvating Electrolytes for Low‐Temperature Lithium Batteries

ABSTRACT The reliable operation of lithium‐based batteries (LBBs) under subzero conditions remains a fundamental challenge due to sluggish ion transport, increased interfacial impedance, and unstable solid–electrolyte interphases (SEIs). Popular high‐ and localized high‐concentration electrolytes partially alleviate these issues but still suffer from excessive viscosity and strong Li ⁺ ‐solvent binding that hinder low‐temperature kinetics. Weakly solvating electrolytes (WSEs) offer a new paradigm by weakening Li ⁺ coordination, promoting anion‐dominated solvation, and accelerating desolvation and interfacial charge transfer. This review provides a comprehensive review of WSEs, focusing on working mechanisms, structural design strategies, and interfacial chemistries. We also address molecular‐level solvation insights with electrolyte engineering to discuss how WSEs promote uniform lithium deposition, inorganic‐rich SEIs, and stable cycling at subzero temperatures. Finally, the review highlights future research directions—from quantitative solvation–performance correlations and data‐driven electrolyte design to interfacial diagnostics and scalability. By integrating molecular‐level understanding with predictive modeling and engineering validation, WSEs offer a transformative route toward all‐climate rechargeable batteries capable of stable and efficient operation from arctic to desert environments.