PDOL polymeric protective layer with regulated ion migration channels enables ultrastable cycling of aqueous zinc...

The practical deployment of aqueous zinc-ion batteries (AZIBs) is severely hindered by disordered zinc deposition and water-induced parasitic reactions, which degrade the long-term cycling stability of Zn anodes. Herein, a poly(1,3-dioxolane) (PDOL) protective layer is rationally constructed on the zinc surface via a facile one-step pre-polymerization strategy. The abundant ether oxygen sites of PDOL can strongly coordinate with Zn²⁺ to reorganize the solvation sheath, effectively weakening water competition and suppressing the hydrogen evolution reaction (HER). Meanwhile, the PDOL interlayer homogenizes interfacial Zn²⁺ flux and alleviates localized current concentration, inducing preferential growth of the Zn (002) crystal plane and restraining dendrite proliferation caused by the tip effect. Furthermore, a robust organic-inorganic hybrid SEI film enriched with Zn-O/Zn-F inorganic phases is in-situ generated during cycling, which further accelerates interfacial ion kinetics and passivates the reactive zinc surface. Benefiting from the synergistic effects of solvation modulation, water confinement, and interfacial reconstruction, the PDOL@Zn symmetric cell achieves an ultra-long lifespan of over 2000 h at 10 mA cm^-2 (1 mAh cm^-2). Both coin and pouch full cells deliver prominently enhanced cycling durability. This work provides a facile and reliable interfacial engineering strategy toward high-stability aqueous zinc-ion batteries.