Polydentate Ligand Stabilizes Electrolyte and Interface Layer for Anti‐Corrosion and Selective‐Deposited Zn Metal Aqueous Batteries

Abstract Zinc anode suffers from tough issues such as dendrite, corrosion, and hydrogen evolution, which lead to premature battery failure and thus restrict the practical application of aqueous zinc‐metal batteries (ZMABs). Herein, a polydentate‐ligand tactic is introduced to reconstruct solvation structure, improve corrosion resistance, and trigger selective dendrite‐free deposition via β‐Alanyl‐L‐histidine (AH). With abundant amino, amide, carboxyl, and imidazolyl groups, AH shows a chelation effect, which partially substitutes solvated SO₄²⁻ and enters the Zn²⁺ solvation sheath to facilitate desolvation. Those groups also increase the strong H‐bond proportion of electrolyte, stabilizing water and suppressing corrosion and hydrogen evolution reactions. Moreover, with multisite coordination, the AH preferentially adsorbs on Zn(002) to induce a stable functional C, N, O, and S‐rich solid‐electrolyte interphase with zincophilic and hydrophobic properties. It homogenizes both the electric field and concentration field and guides preferential Zn growth along (002), realizing stable and dendrite‐free Zn anode. As a result, the obtained Zn anode with AH electrolyte exhibits a high CE of 99.28%, extended stability of over 6000 h, and a long lifespan of over 1000 cycles for Zn//MnO₂ batteries. This work offers a novel design strategy of additive toward stabilization of Zn anodes for practical ZMABs.