Dendrite growth and parasitic reactions of a Zn metal anode in aqueous media hinder the development of up-and-coming Zn-ion batteries. Optimizing the crystal growth after Zn nucleation is promising to enable stable cyclic performance of the anode, but directly regulating specific crystal plane growth for homogenized Zn electrodeposition remains highly challenging. Herein, a perfluoropolymer (Nafion) is introduced into an aqueous electrolyte to activate a thermodynamically ultrastable Zn/electrolyte interface for long-term Zn-ion batteries. The low adsorption energy (-2.09 eV) of Nafion molecules on Zn metal ensures the in situ formation of a Nafion-nanofilm during the first charge process. This ultrathin artificial solid electrolyte interface with zincophilic -SO3- groups guides the directional Zn2+ electrodeposition along the (002) crystal surface even at high current density, yielding a dendrite-free Zn anode. The synergic Zn/electrolyte interphase electrochemistry contributes an average coulombic efficiency of 99.71% after 4500 cycles for Zn‖Cu cells, and Zn‖Zn cells achieve an ultralong lifespan of over 7000 h at 5 mA cm-2. Besides, Zn‖MnO2 cells operate well over 3000 cycles. Even at -40 °C, Zn‖Zn cells achieve stable Zn2+ plating/stripping for 1200 h.
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