Localized S‐Li2s Conversion with Accelerated Kinetics Mediated by Mixed Conductive Shell for High‐Performance Solid‐State Lithium‐Sulfur Battery

Abstract Solid‐state lithium‐sulfur batteries (SSLSBs) using polymer electrolytes are considered as one of the most promising energy storage systems due to their high specific energy, facile processability, and low cost. However, the sluggish solid‐state sulfur conversion kinetics limits their specific density and challenges the practical application. Here, to address this concern, a hollow carbon/Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 nanosphere (H‐C/LATP) structure is prepared, with high mixed electronic/ionic conductivity, as sulfur hosts for fabricating high‐performance polymer‐based solid‐state Li‐S battery. With the incorporation of the H‐C/LATP rigid shell, the localized sulfur conversion with accelerated kinetics is realized by introduced stable sulfur‐H‐C/LATP double‐phase interface and enhanced charge‐transfer behavior. In addition, H‐C/LATP shows excellent absorption ability toward lithium polysulfides, thus suppressing the shuttle effect in solid electrolytes. As a result, superior cycling stability and rate performance are achieved. The assembled SSLSB delivers a capacity of 1213.2 mAh g −1 in the first cycle and 948.3 mAh g −1 after 200 cycles at 0.1 C. Besides, high active material loading is also demonstrated in this configuration with stable capacity retention. This work provides a practical pathway for the sulfur cathode design in polymer‐based SSLSBs.