Engineering d‐p Orbital Hybridization with P, S Co‐Coordination Asymmetric Configuration of Single Atoms Toward High‐Rate and Long‐Cycling Lithium–Sulfur Battery

Abstract Single‐atom catalysts (SACs) have been increasingly explored in lithium–sulfur (Li–S) batteries to address the issues of severe polysulfide shuttle effects and sluggish redox kinetics. However, the structure‐activity relationship between single‐atom coordination structures and the performance of Li–S batteries remain unclear. In this study, a P, S co‐coordination asymmetric configuration of single atoms is designed to enhance the catalytic activity of Co central atoms and promote d‐p orbital hybridization between Co and S atoms, thereby limiting polysulfides and accelerating the bidirectional redox process of sulfur. The well‐designed SACs enable Li–S batteries to demonstrate an ultralow capacity fading rate of 0.027% per cycle after 2000 cycles at a high rate of 5 C. Furthermore, they display excellent rate performance with a capacity of 619 mAh g −1 at an ultrahigh rate of 10 C due to the efficient catalysis of CoSA‐N 3 PS. Importantly, the assembled pouch cell still retains a high discharge capacity of 660 mAh g −1 after 100 cycles at 0.2 C and provides a high areal capacity of 4.4 mAh cm −2 even with a high sulfur loading of 6 mg cm −2 . This work demonstrates that regulating the coordination environment of SACs is of great significance for achieving state‐of‐the‐art Li–S batteries.