Electrolyte-Free Cathode Design for High-Sulfur-Loading All-Solid-State Li-S Batteries

All-solid-state lithium-sulfur batteries (ASSLSBs) with polymer electrolytes have high theoretical energy density and improved safety, providing appealing potential for next-generation energy storage. However, limiting the dissolution of long-chain polysulfides (LiPSs) in polymer electrolyte and achieving high S loading in cathodes remains a challenge. To tackle this issue, we demonstrate a 3D electrode composed of a mixture of styrene butadiene rubber and lithium carboxyl methyl cellulose as the binder, equipped with a high concentration of all-solid-state polyethylene oxide (PEO) -based electrolyte filled with LLZTO (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 ) and LiPSs (named LiPS/LLZTO-CL/S). The synergistic design exhibits outstanding structural stability, preventing the dissolution of long-chain LiPSs, enhancing the kinetics of short-chain LiPSs, alleviating volume expansion, and offering pathways for ion/electron transport. The battery possesses attractive cycling stability and can maintain high capacity retention (1106 mAh g −1 even after 500 cycles) at 0.2 C. Its structural and electrochemical advantages enable stable cycling at a high sulfur loading of 7.0 mg cm −2 and 0.5 C without electrolyte in the cathode. This work proposes a novel strategy for the structural design of high-loading polymer ASSLSBs.