Crystal Orientation Regulation and Dynamic Protection via Dual Interface Engineering for Dendrite‐Free Zinc Deposition

The rampant dendrite and parasitic reactions in aqueous zinc‐ion batteries seriously hinder its practical application. Herein, a novel organic/inorganic dual interface layer is developed by in‐situ constructing of zinc hydroxide sulfate hydrate (ZHS) under the induction of a di‐pentaerythritol (DPE) pre‐coating. This design achieves dendrite‐free Zn deposition through the synergistic integration of crystallographic orientation regulation and dynamic self‐adaptive protection. The crystallographic orientation includes two dimensions: 1) Hydrogen‐bond‐guided horizontal growth of zinc hydroxide sulfate hydrate (ZHS) along the (001) crystal plane, and 2) ZHS‐induced epitaxial alignment of Zn deposition on the (002) plane. This dual crystallographic modulation achieves uniform interfacial ion flux distribution and suppresses the formation of dendrites. Simultaneously, the dynamic evolution of the DPE/ZHS interphase adaptively alleviates mechanical stress during plating/stripping cycles, ensuring conformal interfacial contact and effectively mitigating water‐induced side reactions. As a result, the engineered Zn anode exhibits exceptional cycling stability, surpassing 4500 h at 1 mA cm −2 with a coulombic efficiency of 99.79%, while full cells paired with V 2 O 5 cathodes retain nearly 100% capacity after 3000 cycles at 5 A g −1 . This work provided a novel perspective on regulating interfacial byproducts to stabilize Zn anodes.