Unlocking Cooperative Interfacial Orbital Coupling via Phosphorus‐Induced Bond Reconstruction in MoSe 2 /MXene for Accelerated Sulfur Redox Kinetics

The commercial progress of Li‐S batteries is seriously hindered by the slow sulfur redox kinetics and pronounced polysulfide shuttle. Herein, we propose a doping‐induced local‐strain strategy to reconstruct the bonding environment of MoSe 2 in MoSe 2 /crumpled MXene (CM), generating undercoordinated Mo sites and Se vacancies while weakening the intrinsic Mo‐Se d–p bonding interactions. Combined spectroscopic analyses and density functional theory calculations reveal that P‐induced lattice distortion shifts the Mo‐ d and Se‐ p band centers upward, and enhances Mo‐S d‐p and Li‐Se s‐p orbital interactions at the P‐MoSe 2 /LiPS interface. These cooperative interfacial interactions facilitate polysulfide conversion and lower energy barriers associated with Li 2 S nucleation and decomposition, enabling highly reversible sulfur redox chemistry. Consequently, the optimal P‐MoSe 2 /CM catalyst enables Li‐S cells with an exceptional capacity of 537 mAh g − 1 at 4C and cycling stability at 1C for 500 cycles. Furthermore, even with a low E/S ratio of 7.4 µL mg −1 and a high sulfur loading of 7.2 mg cm −2 , P‐MoSe 2 /CM full cell maintains an excellent retention of 60.6% after 400 cycles at 0.1C. This work paves the way for the rational design of anion‐doped transition‐metal dichalcogenide catalysts via simultaneous orbital hybridization to achieve rapid and reversible sulfur redox conversion in Li‐S batteries.