Aqueous Zn anodes have been revisited for their intrinsic safety, low cost, and high volumetric capacity; however, deep-seated issues of dendrite growth and intricate side-reactions hindered their rejuvenation. Herein, a “brightener-inspired” polyamide coating layer which elevates the nucleation barrier and restricts Zn²⁺ 2D diffusion is constructed to effectively regulate the aqueous Zn deposition behavior. Importantly, serving as a buffer layer that isolates active Zn from bulk electrolytes, this interphase also suppresses free water/O₂-induced corrosion and passivation. With this synergy effect, the polymer-modified Zn anode produces reversible, dendrite-free plating/stripping with a 60-fold enhancement in running lifetime (over 8000 hours) compared to the bare Zn, and even at an ultrahigh areal capacity of 10 mA h cm⁻² (10 mA cm⁻² for 1 h, 85% depth of discharge). This efficient rechargeability for Zn anodes enables a substantially stable full-cell paired with a MnO₂ cathode. The strategy presented here is straightforward and scalable, representing a stark, but promising approach to solve the anode issues in advanced Zn batteries.

The surface chemistry of solid electrolyte interphase is one of the critical factors that govern the cycling life of rechargeable batteries. However, this chemistry is less explored for zinc anodes, owing to their relatively high redox potential and limited choices in electrolyte. Here, we report the observation of a zinc fluoride-rich organic/inorganic hybrid solid electrolyte interphase on zinc anode, based on an acetamide-Zn(TFSI)₂ eutectic electrolyte. A combination of experimental and modeling investigations reveals that the presence of anion-complexing zinc species with markedly lowered decomposition energies contributes to the in situ formation of an interphase. The as-protected anode enables reversible (~100% Coulombic efficiency) and dendrite-free zinc plating/stripping even at high areal capacities (>2.5 mAh cm^‒2), endowed by the fast ion migration coupled with high mechanical strength of the protective interphase. With this interphasial design the assembled zinc batteries exhibit excellent cycling stability with negligible capacity loss at both low and high rates.