Progress and Prospect of Electrolyte Engineering Strategies for Wide‐Temperature Lithium–Sulfur Batteries

ABSTRACT Lithium–sulfur (Li–S) batteries have long been at the forefront of next‐generation high‐energy storage systems. Despite considerable research efforts focused on enhancing specific capacity and cycling stability, achieving reliable performance under extreme operating conditions remains an urgent yet underexplored challenge. Among the various components in Li–S batteries, the electrolyte exhibits the greatest sensitivity to temperature variations, and its thermal stability is decisive to the overall cell performance across a wide temperature range. This review systematically examines the reaction mechanisms of Li–S batteries and discusses the critical challenges faced by electrolytes under different temperatures. By summarizing recent advances in wide‐temperature electrolyte design, the pivotal role of electrolyte solvation structures in determining battery performance over extended temperature ranges are underscored. Accordingly, current strategies for wide‐temperature Li–S electrolytes are categorized and analyzed based on three representative solvation architectures, including weakly solvating electrolyte system (WSEs), highly solvating electrolyte system (HSEs), and moderately solvating electrolyte system (MSEs). New insights are also prospected to indicate the future research directions for wide‐temperature Li–S batteries through critically evaluating the intrinsic limitations associated with each type of solvation‐structured electrolytes. This review aims to provide constructive perspectives to guide the continued development of high‐performance electrolytes for wide‐temperature Li–S battery systems.