A General Strategy for Electrolyte‐Interphase Reconstruction via Molybdenum‐Driven Catalytic Engineering

Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) is a considered cathode material for sodium‐ion batteries (SIBs) due to its high operating voltage and substantial capacity. However, its deployment is hindered by low conductivity and poor interfacial stability at high voltage. Herein, we report a rational structural modulation strategy by introducing high‐valence Mo dopants into the NVPF lattice. The substitution of V with Mo not only induces local electric field reconstruction but also plays a pivotal catalytic role in promoting controlled electrolyte decomposition. This catalysis accelerates the formation of a uniform and robust cathode‐electrolyte interphase (CEI). Consequently, the Mo‐NVPF@rGO delivers an enhanced rate capability (85.7 mAh g −1 at 10 C), long‐term cycling stability (87% capacity retention after 500 cycles at 5 C), and reliable performance over a wide temperature range. Coupled with commercial hard carbon, the Mo‐NVPF@rGO||CHC full battery delivered 121.8 mAh g −1 at 0.2 C with a high energy density of 468 Wh kg −1 . DFT calculations further reveal that Mo doping catalyzes the decomposition of electrolyte, promoting the formation of a fluorine‐rich CEI. This work highlights the dual function of aliovalent doping in tuning bulk electronic/ionic properties and enabling interfacial engineering via catalytic CEI formation, offering a generalizable, scalable strategy for high‐performance electrodes for SIBs.