A General Interfacial‐Tuning Strategy for Synthesis of Delocalized Molybdenum Dioxide‐Based Rods Enables Efficient Na ⁺ Storage

Abstract Molybdenum dioxide (MoO 2 ), notable for its rich presence of heterogeneous junctions, is extensively utilized in a variety of battery applications. Herein, a comprehensive interface control strategy for synthesizing rod‐like MoO 2 ‐based materials possessing delocalization properties and exhibiting efficient Na + storage is presented. By meticulously managing the interface conditions during the synthesis process, Co, Cu, Mg, Fe, and Ni‐polyimide‐coated molybdenum trioxide (MoO 3 ) nanorods are successfully prepared, respectively, each displaying unique structural features. Specifically, the MoO 2 @Mo 3 NiS 4 nanorod composite obtained through a sulfurization process based on the model of nickel‐polyimide‐coated MoO 3 has a rich heterointerface and an optimized charge transfer path, thereby significantly improving the electrochemical activity. As a result, the composite electrode shows a high reversible capacity (665.1 mAh g −1 at 0.1 A g −1 after 100 cycles) and outstanding long‐cycle stability (decay of 0.08% per cycle following 1000 cycles at 5 A g −1 ). Furthermore, through theoretical calculations, electrochemical kinetic analysis, in situ Raman, and in situ X‐ray diffraction (XRD), the specific mechanisms of interface engineering and copper current collectors affecting the electrochemical properties of MoO 2 composite nanorods are deeply explored. This research offers fresh scientific perspectives and methodologies for the development of high‐performance anode materials for sodium‐ion batteries.