Synergistic Phase and Structural Engineering for Enhanced Zinc Storage in V2O3@N‐Doped Carbon Nanofibers

Vanadium‐based oxide cathodes are promising energy‐storage systems for aqueous zinc‐ion batteries (AZIBs) because of their high energy density and safety, and low cost. However, their limited ion/electron transfer rates and rapid capacity decay pose challenges to their practical application. To overcome these limitations, V2O3 nanoparticles are developed with surface oxygen vacancies integrated with N‐doped carbon nanofibers (V2O3@NCNFs), using an electrospinning method combined with an in situ oxidation/reduction strategy. By precisely controlling the reaction atmosphere, synergistic regulation of the phase transition and structural evolution of vanadium oxide are achieved. The unique combination of oxygen vacancies and N‐doped carbon nanofibers enhances the zinc storage capacity, rate capability, and cycle stability of the V2O3@NCNFs electrode, achieving high reversible capacities of 554.6 mAh g−1 at 0.1 A g−1 with a high loading mass of ≈2.0–2.5 mg cm−2. Moreover, the V2O3@NCNFs electrode can achieve a high initial capacity of 434.3 and 266.6 mAh g−1 even at high current densities of 1.0 and 5.0 A g−1, respectively, with minimal capacity decay rates of 0.012% per cycle over 500 cycles and 0.003% per cycle over 2000 cycles. More importantly, this innovative approach can be universally applied to the design of novel nanostructured Mn‐ and V‐based oxide cathodes, which is promising for the development of advanced electrodes for high‐performance energy storage devices.