Oriented Zn Deposition for Stable Anodes via Long-Chain Molecular Interfacial Engineering

Uncontrolled dendrite growth and parasitic reactions severely degrade Zn anodes. To address this, we introduce a long-chain molecular additive that orchestrates interfacial engineering at the electrode-electrolyte interface. The molecule enables biased adsorption on Zn surfaces, tailors the solvation sheath, and contributes to a ZnS-containing organic/inorganic SEI. This coupled adsorption-SEI regulation promotes early-stage Zn(002)-preferred deposition and subsequently stabilizes Zn²⁺ transport, thereby suppressing dendrites and side reactions. This synergistic regulation achieves highly oriented Zn deposition, significantly suppressing dendrites and hydrogen evolution. Consequently, the symmetric cell delivers exceptional cycling stability exceeding 2900 h at 1.0 mA cm^-2 and 1.0 mAh cm^-2, and an average Coulombic efficiency of 99.81% over 3500 cycles in asymmetric cells. High-loading Zn||NH₄V₄O₁₀ full cell (DOD_Zn ≈ 25%) exhibits a capacity retention rate exceeding 94% for 1000 stable cycles at 1 A g^-1. This work provides a fundamental insight into molecular design principles for regulating metal electrodeposition behavior.