Solvation Reconfiguration and Controllable Zn(101) Deposition Enable Stable Zn Anodes

Deposition of Zn 2+ along the (002) crystal plane often leads to uneven deposition and dendrites, which increases the risk of short circuits and shortens battery lifespan. To address these challenges, a double‐network hydrogel electrolyte (denoted as PASH) is designed, which enables the preferential deposition of Zn 2+ along the (101) crystal plane through modulating its solvation structure and interfacial chemistry. The ‐COO − groups in PASH form coordination bonds with Zn 2+ , reconstructing the solvation structure and lowering the desolvation energy barrier, thereby promoting oriented Zn deposition and facilitating fast ion transport. By steering Zn 2+ deposition toward the (101) crystal plane, the PASH hydrogel electrolyte ensures uniform and compact plating, significantly enhancing the cycling stability and Coulombic efficiency. Therefore, the Zn||Zn symmetric cells achieved an ultra‐long stable cycling life of 8000 h, and both asymmetric cells and full cells exhibited high Coulombic efficiency.