In Situ Construction of NiFe LDH@MoS ₂ Heterostructure with Built‐in Electric Field Coupling Mo Vacancies Promotes Rapid Reaction Kinetics for Chloride Ion Batteries

Layered double hydroxides (LDH) are promising cathode materials for chloride-ion batteries (CIBs), offering tunable interlayer structure and high theoretical capacity. However, their practical viability is constrained by poor conductivity and sluggish redox kinetics. Herein, NiFe LDH@MoS₂ heterostructure is developed via sequential ion-exchange followed by in situ hydrothermal treatment. The existence of MoS₂ introduces molybdenum vacancies that act as interfacial anchoring sites while modulating the electronic structure of NiFe LDH through charge redistribution, significantly enhancing bulk conductivity. The heterointerface further exploits Fe─O─H─Cl coordination and S-Cl dipole interactions, synergistically accelerating charge transfer. The NiFe LDH@MoS₂ cathode demonstrates 133 and 119.6 mAh g^-1 after 800 and 500 cycles at 300 and 500 mA g^-1, respectively, with negligible capacity decay (0.070% and 0.063% per cycle). Mechanistic studies confirm that Cl-storage involves reversible Cl^- shuttling within the LDHs gallery, accompanied by redox reactions of double-metallic centers in LDH host layers, while MoS₂ simultaneously functions as an electron-highway network and a structural buffer that homogenizes interfacial electric fields, thereby steering coordinated charge compensation across heterointerfaces. This work unveils the importance of heterointerface engineering in regulating both ion/electron dynamics for LDH-based energy storage systems, offering a universal design principle for high-performance halogen-ion batteries (HIBs).