Beyond Bulk Transport: Interfacial Atomic Regulation for Practical Ah‐Scale Zinc Anodes

ABSTRACT Achieving high‐capacity dendrite‐free zinc deposition has been persistently challenged by the trade‐off between interfacial stabilization and ion transport. Conventional electrolyte designs improve interfacial stability at the expense of bulk ion mobility, resulting in rapid failure under high‐capacity operation. Herein, we present a strategy that uses a viscous glycidyl ether‐based additive to suppress bulk ion diffusion while enabling ultrafast surface transport on Zn (002) planes. In situ electrochemical atomic force microscopy captures epitaxial deposition mediated by rapid adatom diffusion and lattice incorporation, effectively decoupling interfacial kinetics from bulk transport limitations. A dual‐functional hydrophobic and zincophilic interface, which suppresses both dendrites and hydrogen evolution, is quantitatively confirmed by quartz crystal microbalance and differential electrochemical mass spectrometry. Consequently, Zn||Zn cells achieve 7800‐h stability (1.0 mA cm −2 , 1.0 mAh cm −2 ) and a record 1 Ah single‐discharge capacity in pouch cells (1.0 mA cm −2 , 10 mAh cm −2 ). Zn||AlVOH full cells deliver a 1.25‐Ah capacity (4.2 mAh cm −2 ) and retain 83.2% of their capacity after 300 cycles at 0.1 A g −1 , illustrating a viable route to practical high‐energy aqueous zinc batteries.