Dual‐Interface‐Dominant Cathode Architectures Enabling Fast Sulfur Redox and Stable Interfaces in All‐Solid‐State Li‐S Batteries

ABSTRACT All‐solid‐state lithium‐sulfur batteries (ASSLSBs) offer exceptional promise for next‐generation energy storage due to their high energy density and intrinsic safety. However, their practical application is hindered by sluggish sulfur redox kinetics and severe interfacial degradation. Here, we report a sulfur|carbon and sulfur|solid electrolytes (SEs) interfaces‐dominant cathode structure that concurrently enhances sulfur redox kinetics and interfacial stability. Conventional sulfur cathodes rely on randomly mixed sulfur|carbon, sulfur|SEs, and carbon|SEs three‐phase boundaries, which hinder efficient sulfur redox. This work presents an interfacial architecture that is realized through carbon host nanostructure engineering, where tailored surface area and porosity favor the spontaneous formation of sulfur|carbon and sulfur|SEs dual interfaces, thereby establishing complementary Li + and e − pathways and reinforcing electrochemical performance. At the same time, this strategy alleviates the formation of carbon|SEs interfaces, thereby blocking the initiators of electrolyte decomposition. As a result, ASSLSBs employing the dual‐interface‐dominant architecture achieve a high initial capacity of 1111 mAh g −1 at 0.2 C with a sulfur loading of 5 mg cm −2 , and exhibit long‐term cycling stability, retaining 1234 mAh g −1 (93.3%) over 100 cycles at a 0.1 C rate. This work highlights the critical role of rational carbon host engineering in constructing well‐defined interfaces for high‐performance ASSLSBs.