Decoupling Electronic and Crystal Structure Effects to Overcome the Capacity‐Stability Trade‐Off for High‐Performance Aqueous Zinc‐Ion Batteries

Aqueous zinc‐ion batteries (ZIBs) with high capacity and long cycling stability are largely hindered by sluggish Zn 2+ diffusion kinetics and irreversible cathode dissolution. Herein, electron delocalization is manipulated in vanadium oxides intercalated with organic tetrabutylammonium (TBA + ) and inorganic Zn 2+ cations, decoupling the relationship between electronic/crystal structure and electrochemical property, effectively unlocking the intrinsic trade‐off between capacity and cycling stability. The synergistic intercalation of TBA + and Zn 2+ generates V─O─TBA and V─O─Zn coordination bonds, inducing charge redistribution and delocalizing electrons in the V 3 d −O 2 p hybridized orbitals, thereby optimizing the electronic structure and facilitating charge transport. Furthermore, TBA + intercalating expands the interlayer spacing, reducing the Zn 2+ diffusion energy barrier and activation energy, while Zn 2+ incorporation alleviates lattice strain through strong Zn 2+ −O 2− interaction, stabilizing the layered structure during cycling. Thus, such a promising cathode delivers a high discharge specific capacity of 424 mAh g −1 at 0.1 A g −1 , exceptional rate capability (320 mAh g −1 at 5 A g −1 ), and 89% retention after 3000 cycles. The study provides a design framework for synergistic regulations of electronic and ionic properties in layered oxides, advancing the development of high‐performance ZIBs cathodes.