Tailoring Li‐Accelerated Motif Enables Lithium Stabilization and Polysulfide Conversion for Long‐Cycling Li–S Batteries

Abstract Lithium–sulfur (Li–S) batteries have long suffered from capacity degradation caused by polysulfide shuttle and lithium dendrite growth. Current research primarily focuses on developing catalysts to accelerate polysulfide conversion or designing solid electrolyte interphase (SEI) layers to suppress dendrite formation. However, simultaneous control of these dual challenges through a unified strategy remains unresolved. Herein, a novel catalyst design strategy endeavors to address these limitations. The catalyst‐coated separator integrates Li‐accelerated motifs into the Li anode, creating a localized microenvironment that enhances Li ⁺ migration kinetics to suppress dendrite growth at the anode side while boosting polysulfide conversion efficiency at the cathode side. In situ X‐ray diffraction, optical microscopy, and density functional theory (DFT) calculations reveal that the incorporation of Li‐accelerated motifs induces electron‐enriched interfacial states, enabling nearly barrier‐free Li ⁺ transport through accelerated ion migration. As a result, the battery achieves 82.8% capacity retention after 300 cycles at 1 C with an ultralow decay rate of 0.057% per cycle. Remarkably, Li||Li symmetric cells exhibit a record cycling stability exceeding 5000 h. This work presents an electron‐rich interface engineering strategy to simultaneously enhance polysulfide conversion kinetics and suppress dendrite proliferation, facilitating the development of practical high‐energy Li–S batteries.