Synergistic Enhancement Effect of Maxwell Polarization and Preferential Exposure of Zn (101) Plane toward Superhydrophobic Separator for Ah‐Level Zinc Metal Pouch Batteries

Interfacial instability in aqueous zinc metal batteries (AZMBs) leads to uncontrolled dendrite growth and water‐induced parasitic reactions, limiting their practical applications. In this work, a novel superhydrophobic HfO 2 ‐coated functionalized glass fiber separator is proposed. Characterized by its high dielectric constant, HfO 2 can autonomously generate an oriented electric field under external electric field stimulation, ensuring uniform distribution of the electric field and Zn 2+ flux at the interface. This strategy not only enhances Zn 2+ transport kinetics but also effectively suppresses the migration of SO 4 2− via electrostatic repulsion. Furthermore, the HfO 2 @GF separator promotes the deposition of Zn 2+ along the Zn (100) and Zn (002) crystal planes, facilitating the preferential exposure of the unique Zn (101) crystal plane. Additionally, its superhydrophobic property effectively inhibits interfacial side reactions. Therefore, the symmetrical cell exhibits an ultra‐long cycling life of 4660 h at 5 mA cm −2 and 1 mAh cm −2 , and maintains stable operation up to 5050 h at 10 mA cm −2 . The Zn||I 2 full battery maintains 87.75% of its initial capacity after 8000 cycles at 10C. Furthermore, the stacked Zn||I 2 pouch battery provides an Ah‐level capacity (1.64 Ah). This work provides a new insight into the construction of highly stable interfacial chemistry.