Graphdiyne‐Based Heteronuclear Dual‐Atom Catalysts Enable High‐Energy‐Density Lithium–Sulfur Batteries

ABSTRACT The practical application of lithium–sulfur (Li–S) batteries are hindered by lithium (Li) polysulfides (LiPSs) shuttling, sluggish sulfur (S) redox kinetics, and Li dendrite growth. Here, we report heteronuclear Co‐Pt dual‐atom catalysts (DACs) anchored on graphdiyne (GDY) (Co‐Pt DAs/GDY) to boost S redox conversion kinetics and promote uniform Li deposition to enable high‐energy‐density Li–S batteries. The unique electronic coupling between sp ‐hybridized carbon of GDY and Co‐Pt dual atoms triggers a p ‐ d ‐ d orbital resonance. This resonance optimizes the interfacial electronic configuration to promote strong d ‐ p orbital hybridization with LiPSs, endowing dual‐atom sites with site‑isolated redox‑complementary catalytic behavior toward sequential S redox reactions. Meanwhile, adjacent Pt atoms tailor Co sites to a high‐spin state, further strengthening their adsorption and catalytic capabilities. Benefiting from these features, the redox kinetics and electrochemical performance of S cathodes are significantly enhanced, S@Co‐Pt DAs/GDY cathodes deliver a remarkable areal capacity of 21.3 mA h cm −2 and an excellent cycling stability under realistic conditions. Moreover, Co‐Pt DAs/GDY exhibits strong Li‐ion affinity and offers dual‐atom Li nucleation sites, enabling stable cycling of Li@Co‐Pt DAs/GDY anodes for more than 9200 h. Assembled Ah‐level Li–S pouch cells achieve a high‐energy‐density of 502 Wh kg −1 (based on the total cell mass).