Crystalline‐Amorphous Phase and Oxygen Vacancies Synergistically Regulate Vanadium Electronic States for Unleashing Zinc‐Ion Storage Performance

Abstract Zinc‐ion capacitors (ZICs) are emerging as a compelling choice for energy storage in future, promising high power and energy densities coupled with eco‐friendly characteristics. This work presents a novel approach to enhance the performance of ZICs by employing a one‐step solvothermal synthesis to growth V‐MOF on the surface of V 2 CT X ‐MXene, followed by annealing to fabricate a 3D cross‐linked VO X /V 2 CT X ‐MXene‐x(VO X /MXene‐x) composite. The unique structure demonstrates excellent conductivity and high redox reaction activity, which significantly shortens the Zn 2+ diffusion path. Moreover, the intertwined crystalline‐amorphous structure efficiently suppresses lattice volume expansion during Zn 2+ (de)intercalation. Density functional theory (DFT) reveals that the amorphous V 2 O 5 enhances conductivity, lowers the Zn 2+ capture energy barrier, and improves charge transfer efficiency. The introduction of oxygen vacancies further enhances the electronic transport. The VO X /MXene‐4 composite exhibits a specific capacity of 336.39 mAh g −1 at 1 A g −1 , maintaining 213.06 mAh g −1 at 10 A g −1 , indicating outstanding rate performance, along with an energy density of 356.27 Wh kg −1 and a power density of 1280 W kg −1 . This work offers novel insights for the design of electrode materials that feature intertwined crystalline‐amorphous phases, providing valuable insights into ion transport mechanisms and strategies to enhance Zn 2+ diffusion kinetics.