Polymer Coating with Balanced Coordination Strength and Ion Conductivity for Dendrite‐Free Zinc Anode

Abstract Decorating Zn anodes with functionalized polymers is considered as an effective strategy to inhibit dendrite growth. However, this normally brings extra interfacial resistance rendering slow reaction kinetics of Zn²⁺. Herein, a poly(2‐vinylpyridine) (P2VP) coating with modulated coordination strength and ion conductivity for dendrite‐free Zn anode is reported. The P2VP coating favors a high electrolyte wettability and rapid Zn²⁺ migration speed (Zn²⁺ transfer number, t_Zn²⁺ = 0.58). Electrostatic potential calculation shows that P2VP mildly coordinates with Zn²⁺ (adsorption energy = −0.94 eV), which promotes a preferential deposition of Zn along the (002) crystal plane. Notably, the use of partially (26%) quaternized P2VP (q‐P2VP) further reduces the interfacial resistance to 126 Ω, leading to a high ion migration speed (t_Zn²⁺ = 0.78) and a considerably low nucleation overpotential (18 mV). As a result of the synergistic effect of mild coordination and partial electrolysis, the overpotential of the q‐P2VP‐decorated Zn anode retains at a considerably low level (≈46 mV) over 1000 h at a high current density of 10 mA cm⁻². The assembled (NH₄)₂V₆O₁₆·1.5H₂O || glass fiber || q‐P2VP‐Zn full cell reveals a lower average capacity decay rate of only 0.018% per cycle within 500 cycles at 1 A g⁻¹.