Modulating Adsorption Intermediate Metastability for Tip‐Directed Zinc Stripping and Suppressed Vanadium Dissolution Toward Long‐Cycling Zinc–Vanadium Batteries

Abstract The metastable adsorbed intermediates formed during the lattice detachment of Zn atoms and V n + ions govern the reaction kinetics and interfacial morphology evolution during dissolution. Resultant inhomogeneous Zn stripping and progressive V dissolution synergistically promote dead Zn formation and cathode material degradation, substantially impeding the commercialization of Zn‐V batteries. Here, to facilitate Zn tip‐stripping electrochemistry and suppressed vanadium dissolution, a robust adhesion ionic liquid ([BVIM]Br) modified PAM gel electrolyte (PAM‐IL) was strategically designed. Leveraging steric hindrance of polymer segments and the directional coordination of anions and cations, the PAM‐IL electrolyte delocalizes charge accumulation and suppresses overstabilization of tip‐localized complexes, thereby reversing the adsorption asymmetry behavior (Δ G ads‐tip > Δ G ads‐root ) to achieve tip‐targeted zinc stripping. Concurrently, strong ion–dipole interactions within PAM‐IL elevate the activation barrier for V dissolution and combine with its butyl‐functionalized hydrophobic moieties to impede water molecule penetration and suppress vanadium dissolution. Therefore, the as‐prepared Zn||PAM‐IL||NH 4 V 4 O 10 batteries deliver a reversible capacity of 266.4 mAh g −1 at 1 A g −1 after 2000 cycles and retained a higher capacity retention (82.3%) after 250 cycles than aqueous electrolyte (28.1%) with extreme‐low current density of 0.2 A g −1 . Furthermore, the PAM‐IL exhibits exceptional cycling stability over a wide temperature range, from 0 °C to 60 °C.