Atomic d‐d Orbital Coupling Drives Interfacial Spin‐Related Electronic Redistribution for Accelerated Sulfur Redox Kinetics

ABSTRACT Heteronuclear Ni‐Co dual‐atom catalysts anchored on nitrogen‐doped carbon (NiCo DACs/NC) are constructed to clarify the relationship between intermetallic d‐d orbital coupling and bidirectional sulfur redox kinetics in lithium‐sulfur batteries. Combining spin‐resolved density functional theory, spin‐density mapping, and potential‐dependent magnetic measurements, we demonstrate that d‐oupling reconstructs the local 3d electronic structure, induces interfacial spin‐related electronic redistribution, and undergoes reversible dynamic evolution during sulfur reduction and Li 2 S oxidation. This regulation enhances polysulfide conversion, Li─S bond activation, and Li 2 S nucleation/deposition as well as oxidation/decomposition. Consequently, the NiCo DACs/NC‐based Li‐S battery delivers a discharge capacity of 1129.6 mAh g −1 at 1C and retains 864.6 mAh g −1 after 500 cycles (0.034% decay per cycle). Under a high sulfur loading of 9.12 mg cm −2 and lean electrolyte (3.5 µL mg −1 an areal capacity of 7.69 mAh cm −2 is achieved. A pouch cell delivers a component‐level energy density of 321.2 Wh kg −1 with 88.7% retention after 50 cycles. This work provides mechanistic insight into spin‐related electronic dynamics for designing high‐performance dual‐atom catalysts in Li‐S batteries.