Synergistic pincer catalysis by closely adjacent single atoms and nanoclusters for superior lithium‐sulfur batteries

Abstract The practical application of lithium‐sulfur (Li‐S) batteries is seriously impeded by the notorious shuttle effect and sluggish reaction kinetics. Herein, we develop an advanced sulfur electrocatalyst that integrates single‐atom Co‐N 4 moieties with Co nanoclusters on N‐rich hollow carbon nanospheres (Co‐ACSA@NC). The proximity of single atoms and nanoclusters establishes a synergistic “pincer” interaction with polysulfides through dual modes of coordinate and chemical bonding. Moreover, electron donation from the Co nanocluster enhances the bonding between polysulfide and Co‐N 4 , further improving the immobilization and catalytic conversion of sulfur species. The hollow and porous carbon support not only exposes the abundant active sites efficiently, but also serves as a confined nanoreactor for well‐tamed sulfur reactions. As a result, the S/Co‐ACSA@NC cathode exhibits excellent cyclability over 500 cycles with minimal attenuation of 0.018% per cycle. A high areal capacity of 11.15 mAh cm −2 can be obtained even under high sulfur loading (13.1 mg cm −2 ) and lean electrolyte (E/S = 4.0 μL mg −1 ), while a 2.38‐Ah pouch cell is also demonstrated with a commendable energy density over 307.7 Wh kg −1 . This work offers a unique “pincer” catalysis strategy for boosting sulfur electrochemistry, paving the way to high‐performance and practically viable Li‐S batteries. image