In Situ Carbon Insertion in Laminated Molybdenum Dioxide by Interlayer Engineering Toward Ultrastable “Rocking‐Chair” Zinc‐Ion Batteries

Abstract Aqueous zinc‐ion batteries (ZIBs) have attracted significant attention due to their intrinsic safety, cost‐effectiveness, and environmental friendliness. However, the common zinc metal anode suffers from zinc dendrite formation, self‐corrosion, and surface passivation, which impede the further application of aqueous ZIBs. Herein, carbon‐inserted molybdenum dioxide (MoO 2 ) materials with laminated structure are designed as novel intercalation‐type anodes for ZIBs by combination of interlayer engineering and in situ carbonization of aniline guest in molybdenum trioxide interlayers. The uniform dispersion of carbon layers in laminated MoO 2 not only provide fast transportation paths for electron but also strengthen the framework of MoO 2 , leading to high structural integration during high‐rate cycling. Benefiting from the unique structural design, the carbon‐inserted MoO 2 electrode exhibits high initial Coulombic efficiency, excellent cycling stability, and outstanding rate capability. Multiple ex situ characterizations reveal its excellent electrochemical stability is derived from reversible intercalation mechanism and ultrastable structural framework. Furthermore, the rocking‐chair zinc‐ion full battery assembled with the zinc pre‐intercalated Na 3 V 2 (PO 4 ) 2 O 2 F cathode presents excellent stability and ultralong lifespan with a high capacity retention of 91% over 8000 cycles.