Delocalized Electrons of p‐Block Selenium Single Atoms Achieve Synergistic Regulation of Conversion Kinetics and Lithium Deposition for Lithium–Sulfur Batteries

ABSTRACT The practical applications of lithium–sulfur (Li─S) batteries are impeded by sluggish conversion kinetics of lithium polysulfides (LiPSs) and uncontrolled Li dendrite growth. While introducing single‐atom catalysts (SACs) stands out as a promising strategy to overcome these issues, the p‐block SACs exhibit great potential. However, the relationship between their synergistic regulation and atomic structure remains unclear. Here, by leveraging the p‐electron delocalization induced by the p‐π conjugated effect, p‐block Se SACs were proposed to synergistically regulate the lithium/sulfur electrochemistry. The experimental and theoretical results demonstrate that the unique Se‐C 2 coordination structure of Se SACs leads to activated p‐electrons, which not only facilitates LiPSs conversion by p‐p hybridization but also generates a uniform current distribution to guide Li plating and stripping behavior. Consequently, the Li─S batteries assembled with Se SACs demonstrate a low capacity decay rate of 0.056% per cycle over 1000 cycles at 1 C and achieve a high areal capacity of 5.58 mAh cm −2 under a high sulfur loading of 6.41 mg cm −2 and a low electrolyte/sulfur ratio of 8.3 µL mg −1 . This work elucidates the synergistic regulation of Se SACs from atomic orbital level and enlightens the application of p‐block SACs in Li─S batteries.