Single‐Atom Vanadium Catalyst Boosting Reaction Kinetics of Polysulfides in Na–S Batteries

The practical application of the room-temperature sodium-sulfur (RT Na-S) batteries is hindered by the insulated sulfur, the severe shuttle effect of sodium polysulfides, and insufficient polysulfide conversion. Herein, on the basis of first principles calculations, single-atom vanadium anchored on a 3D nitrogen-doped hierarchical porous carbon matrix (denoted as 3D-PNCV) is designed and fabricated to enhance sulfur reactivity, and adsorption and catalytic conversion performance of sodium polysulfide. The 3D-PNCV host with abundant and active V sites, hierarchical porous structure, high electrical conductivity, and strong chemical adsorption/conversion ability of V-N bonding can immobilize the polysulfides and promote reversibly catalytic conversion of polysulfides toward Na₂ S. Therefore, as-fabricated RT Na-S batteries can achieve a high reversible capacity (445 mAh g⁻¹ over 800 cycles at 5 A g⁻¹ ) and excellent rate capability (224 mAh g⁻¹ at 10 A g⁻¹ ). The electrocatalysis mechanism of sodium polysulfides is further experimentally and theoretically revealed, which provides a new strategy to develop the highly stable RT Na-S batteries.