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

Abstract 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 ( c ZLLTO NFs) with a core‐sheath structure, offering efficient ion‐electron dual carrier transport and excellent catalytic activity. Furthermore, the integrated component composed of the c ZLLTO@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.