Integrated Sulfur Hosts with Ion‐Electron Dual Carrier Transport and Catalytic Activity for all‐Solid‐State Lithium–Sulfur Batteries

All-solid-state lithium-sulfur batteries (ASSLSBs) are considered promising next-generation battery technologies due to their high energy density and intrinsic safety. However, the poor electron and Li⁺ transport of sulfur-based cathodes, along with high interface resistance, result in insufficient sulfur utilization efficiency and subpar rate performance. Herein, a "one-stone-three-birds" design strategy of integrated sulfur hosts is proposed to enhance the solid-state redox reaction of sulfur species. By fabricating carbonized polyacrylonitrile-coated Zr-doped lithium lanthanum titanium oxide (ZLLTO) nanofibers (cZLLTO NFs) with a core-sheath structure, offering efficient ion-electron dual carrier transport and excellent catalytic activity. Furthermore, the integrated component composed of the cZLLTO@S cathode and the ZLLTO-based composite solid electrolyte is constructed by using the in situ polymerization, providing a stable electrolyte/electrode interphase. As a result, the assembled ASSLSB achieves a high initial discharge capacity (1016 mAh g^-1 at 0.1C), remarkable rate capability (686 mAh g^-1 at 4C), and excellent cycling performance (81.2% capacity retention after 500 cycles). These results offer valuable insights into the development of high-performance ASSLSBs.