High‐efficiency Lithium Metal Stabilization and Polysulfide Suppression in Li‐S Battery Enabled by Weakly Solvating Solvent

Lithium‐sulfur batteries (LSBs) are considered a highly promising next‐generation energy storage technology due to their exceptional energy density and cost‐effectiveness. However, the practical use of current LSBs is hindered primarily by issues related to the “shuttle effect” of lithium polysulfide (LiPS) intermediates and the growth of lithium dendrites. In strongly solvating electrolytes, the solvent‐derived solid electrolyte interphase (SEI) lacks mechanical strength due to organic components, leading to ineffective lithium dendrite suppression and severe LiPS dissolution and shuttling. In contrast, the weakly solvating electrolyte (WSE) can create an anion‐derived SEI layer which can enhance compatibility with lithium metal anode, and restricting LiPS solubility. Herein, a WSE consisting of 0.4 м LiTFSI in the mixture of 1,4‐dioxane (DX):dimethoxymethane (DMM) is designed to overcome the issues associated with LSB. Surface analyses confirmed the formation of a beneficial SEI layer rich in LiF, enabling homogeneous lithium deposition with an average Coulombic efficiency CE exceeding 99% over 100 cycles. Implementing the low‐concentration WSE in Li||SPAN cells yielded an impressive initial specific capacity of 671 mAh g−1. This research highlights the advantages of WSE and offers the pathway for cost‐effective electrolyte development, enabling the realization of high‐performance LSBs. The proposed weakly solvating electrolyte suppresses lithium dendrite formation via LiF‐rich SEI layers on the anode and reduces lithium polysulfide on the cathode, improving lithium‐sulfur battery performance.