Multiscale Structural Engineering of Sulfur/Carbon Cathodes Enables High Performance All‐Solid‐State LiS Batteries

Abstract Constructing all‐solid‐state lithium–sulfur batteries (ASSLSBs) cathodes with efficient charge transport and mechanical flexibility is challenging but critical for the practical applications of ASSLSBs. Herein, a multiscale structural engineering of sulfur/carbon composites is reported, where ultrasmall sulfur nanocrystals are homogeneously anchored on the two sides of graphene layers with strong SC bonds (denoted as S@EG) in chunky expanded graphite particles via vapor deposition method. After mixing with Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 (LSPSCL) solid electrolytes (SEs), the fabricated S@EG‐LSPSCL cathode with interconnected “Bacon and cheese sandwich” feature can simultaneously enhance electrochemical reactivity, charge transport, and chemomechanical stability due to the synergistic atomic, nanoscopic and microscopic structural engineering. The assembled InLi/LSPSCL/S@EG‐LSPSCL ASSLSBs demonstrate ultralong cycling stability over 2400 cycles with 100% capacity retention at 1 C, and a record‐high areal capacity of 14.0 mAh cm −2 at a record‐breaking sulfur loading of 8.9 mg cm −2 at room temperature as well as high capacities with capacity retentions of ≈100% after 600 cycles at 0 and 60 °C. Multiscale structural engineered sulfur/carbon cathode has great potential to enable high‐performance ASSLSBs for energy storage applications.