Directional Catalysis of Sulfur at Highly Ordered Triple‐Phase Interfaces in All‐Solid‐State Lithium‐Sulfur Batteries

ABSTRACT Sluggish sulfur reaction kinetics present a critical barrier to the practical application of sulfide‐electrolyte (SE) based all‐solid‐state lithium‐sulfur batteries (ASSLSBs). Achieving high performance requires both lowering the intrinsic energy barrier for sulfur conversion and engineering efficient transport pathways. Herein, we address these challenges by designing atomically dispersed cobalt sites on carbon nanotubes to directionally catalyze sulfur conversion at the triple phase interface. Strong orbital hybridization between Co 3d and S 3p states strengthens chemical bonding, effectively accelerating both sulfur reduction and lithium sulfide oxidation. The interfaces tailored for directional catalysis maximize highly ordered C/S/SE triple‐phase interfaces and minimize SE/C interfaces, establishing hierarchical ionic/electronic transport networks while mitigating side reactions. Consequently, the engineered cathode delivers a high reversible capacity of 1108 mAh g − 1 at 0.5 C, retaining 97 % capacity over 500 cycles. The resulting batteries also demonstrate remarkable robustness under demanding conditions. This work offers a powerful catalysis‐driven strategy for high‐performance ASSLSBs.