Amphiphile‐Induced Dual‐Domain PDOL Electrolyte Enabling Decoupled Ion Transport and Interfacial Stability in Li‐S Batteries

Solid‐state lithium–sulfur (Li–S) batteries are widely regarded as promising storage systems owing to their intrinsic safety and high theoretical energy density. Nevertheless, their practical applications remain limited by coupled ion transport, interfacial instability, and polysulfide migration. Here, an amphiphile‐induced dual‐domain poly(1,3‐dioxolane) (PDOL) electrolyte is in situ polymerized to resolve this limitation. Microphase separation generates interconnected polar domains embedded within a nonpolar matrix. Li + transport is preferentially facilitated within polar domains, while polysulfide diffusion is spatially confined by nonpolar domains through decoupled ion/polysulfide transport pathways. At the lithium interface, phospholipid molecules form an adaptive interphase that regulates Li + flux, promotes inorganic‐rich solid electrolyte interphase (SEI) formation, and suppresses parasitic reactions. As a result, stable Li + plating/stripping is sustained for over 5500 h at 1 mA cm −2 , while Li–S full cells exhibit an initial capacity of 884.7 mAh g −1 with 74.6% retention after 400 cycles at 1 C. This work establishes a dual‐domain electrolyte design paradigm for decoupling bulk ion transport regulation and interfacial stabilization in Li–S batteries.