Single Nickel Atom Catalysts Enable Fast Polysulfide Redox for Safe and Long‐Cycle Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have attracted great interest due to their low cost, high theoretical energy density, and environmental friendliness. However, the sluggish conversion of lithium polysulfides (LiPS) to S and Li2S during the charge/discharge process leads to unsatisfactory rate performance of lower to 0.1 C (1 C = 1675 mA g−1) especially for Li‐S pouch batteries, thus hindering their practical applications in high power batteries. Here, well‐defined and monodispersed Ni single‐atom catalysts (SACs) embedded in highly porous nitrogen‐doped graphitic carbons (NiSA‐N‐PGC) are designed and synthesized to form Ni–N4 catalytic sites at the atomic level. When serving as a bifunctional electrocatalyst, the Ni−N4 catalytic sites cannot only promote the interfacial conversion redox of LiPS by accelerating the transformation kinetics, but also suppress the undesirable shuttle effect by immobilizing LiPS. These findings are verified by both experimental results and DFT theoretical calculations. Furthermore, Li ions show low diffusion barrier on the surface of Ni−N4 sites, resulting in enhanced areal capacity of batteries. As a result, the Li–S battery delivers stable cycling life of more than 600 cycles with 0.069% capacity decay per cycle at a rate of 0.5 C. More importantly, the Li–S pouch cells with NiSA‐N‐PGC show an initial capacity of 1299 mAh g−1 at a rate of 0.2 C even with high sulfur loading of 6 mg cm−2. This work opens up an avenue for developing single‐atom catalysts to accelerate the kinetic conversion of LiPS for highly stable Li–S batteries. Ni single‐atom catalysts embedded in highly porous nitrogen‐doped graphitic carbon (NiSA‐N‐PGC) are synthesized by a facile and low‐cost strategy and are employed to modify the separators of Li–S batteries. The Ni−N4 catalytic sites in NiSA‐N‐PGC can not only accelerate the kinetic conversion of LiPS in charge‐discharge processes, but also suppress the undesirable shuttle effect by immobilizing the LiPS.