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

Abstract 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@MoS ₂ heterostructure is developed via sequential ion‐exchange followed by in situ hydrothermal treatment. The existence of MoS ₂ 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@MoS ₂ 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 MoS ₂ 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).