Dynamic Charge Redistribution Induced by Atomic Escape for Enhanced Polysulfide Regulation and Sulfur Redox Kinetics.

Sub-nanocatalysts still face the challenge of spatially inconsistent catalytic centers in suppressing lithium polysulfide (LiPS) shuttling and accelerating redox kinetics. To address this, we developed a carbon-confined thermal evolution strategy that converts vanadium clusters (V Cs) into high-density isolated single atoms (V SAs). This work is the first to demonstrate a top-down charge redistribution through atomic escape that dynamically eliminates low-charge-density regions, constructing highly efficient and uniform catalytic centers. Density functional theory (DFT) calculations reveal that the resulting high-charge-density V SAs exhibit superior LiPS adsorption (-0.82 eV toward Li2S6) and reduced Li2S nucleation barriers (-0.54 eV), drastically outperforming V Cs (-2.80 eV; 5.66 eV). Furthermore, in-situ characterization analysis directly validates the enhanced polysulfide anchoring capability and accelerated reaction kinetics. When incorporated into battery separators, the V SAs enable a high initial capacity (1527 mAh g-1) and ultralong stability (0.047% decay/cycle over 1000 cycles). Notably, under practical conditions, the system maintains 96% capacity retention after 100 cycles (5.2 mg cm-2 sulfur loading) and the high output capacity of 1071.9 mAh g-1 (pouch-cell configuration), demonstrating exceptional commercialization potential. This work establishes an atomic-level structure-charge density relationship and provides a universal design principle for advanced catalytic materials in energy storage.