Polarity-Matched Organic–Inorganic Interphase Directs Planar Zinc Deposition toward Highly Reversible Zn Anodes

Artificial organic-inorganic interphases offer a promising route to suppress dendrite growth and parasitic reactions in aqueous Zn-ion batteries, yet maintain interfacial integrity and control Zn crystallographic deposition. Here, we develop a polarity-matched Nafion-Zn(Ac)₂ (NFCZn@Zn) interphase that self-assembles on Zn anodes. The acetate-rich Zn(Ac)₂ sublayer provides strong Zn²⁺ binding and robust interaction with Nafion, preventing electrolyte-induced delamination. The hybrid interphase promotes planar zinc deposition while mitigating corrosion and byproduct formation. As a result, NFCZn@Zn symmetric cells achieve over 3000 h of stable cycling at 5 mA cm^-2, withstand harsh conditions of 10 mA cm^-2 and 10 mAh cm^-2, and deliver high Coulombic efficiency. In full cells paired with VO₂ cathodes, NFCZn@Zn enhances rate performance, reduces self-discharge, and improves long-term capacity retention compared with bare Zn anodes. This work provides a simple and scalable strategy to direct Zn²⁺ planar (002) deposition, enabling highly reversible and durable Zn-metal anodes.