Advances in Sulfur Cathodes for High‐Energy All‐Solid‐State Lithium Batteries With Sulfide Solid Electrolytes

All‐solid‐state lithium–sulfur batteries (ASSLSBs) have emerged as a promising candidate for next‐generation energy storage systems owing to the synthetic advantages of the high energy density, low cost and abundant resources of sulfur, and the high safety merit of solid‐state electrolyte (SSE). Among the various SSEs, sulfide electrolytes occupy an important position due to their high room‐temperature ionic conductivity and superior mechanical deformability. Nevertheless, the performance of ASSLSBs with sulfide SSEs is limited by challenges associated with the sulfur cathode, such as the electronic insulating properties of sulfur, the large volume changes during charge/discharge, and the low redox dynamics of polysulfides, which are responsible for poor rate capability and unstable interfacial contact. This review systematically summarizes recent advances in sulfur cathodes for ASSLSBs: cathode design and cathode–electrolyte interfacial engineering, including component optimization, doping, catalyst incorporation, interfacial instability, and mechanical contact issues at the cathode–electrolyte interface. The effects of sulfide electrolyte types, synthesis strategies, and air/moisture hydrolysis are also discussed. Furthermore, further development of ASSLSBs is also prospected. The review may be useful for the development of ASSLSBs and other sulfur‐based solid‐state batteries such as Na/K/Zn/Mg/Ca et al.