Constructing Resilient Cross‐Linked Network Toward Stable All‐Solid‐State Lithium‐Sulfur Batteries

Abstract Lithium‐sulfur batteries utilizing sulfide solid electrolytes hold considerable potential for achieving both high energy density and enhanced safety. However, the substantial volume changes experienced by sulfur during cycling result in mechanical stress accumulation, leading to mechanical degradation and thereby degrading overall electrochemical performance. In this study, a stress‐buffer strategy is proposed to address this challenge by engineering a mechanically resilient crosslinked structure for the composite sulfur cathode. This structure is accomplished through the integration of a highly flexible thermoplastic elastomer (ethylene vinyl acetate, EVA), which enables stress release during sulfur volume variations by the repeated stretching and shrinking of EVA, thereby maintaining stable ionic/electronic diffusion channels within the electrode. By virtue of the mechanically stable architecture, the stress evolution experienced by the entire sulfur electrode is substantially reduced, witnessing a remarkable decrease of ≈33.7%. Consequently, the S‐EVA composite cathode demonstrates exceptional electrochemical performance, especially cycling stability. Notably, the S‐EVA composite cathode, with a high loading of 7.5 mg cm −2 , exhibits stable cycling performance close to 3.0 mAh cm −2 within 50 cycles. This work not only offers novel insights into mitigating the mechanical stress within the electrode but also paves the way for developing durable high‐performance all‐solid‐state batteries.