Zincophilic Sites Enriched Hydrogen‐bonded Organic Framework as Multifunctional Regulating Interfacial Layers for Stable Zinc Metal Batteries

To construct an efficient regulating layer for Zn anodes that can simultaneously address the issues of dendritic growth and side reactions is highly demanded for stable zinc metal batteries (ZMBs). Herein, we fabricate a hydrogen‐bonded organic framework (HOF) enriched with zincophilic sites as a multifunctional layer to regulate Zn anodes with controlled spatial ion flux and stable interfacial chemistry (MA‐BTA@Zn). The framework with abundant H‐bonds helps capture H2O and remove the solvated shells on [Zn(H2O)6]2+, leading to suppressed side reactions. The HOF layer also helps form electrolyte‐philic surfaces and expose Zn (002) crystal planes which benefit for rapid conduction and uniform deposition of Zn2+, and weakened sides reactions. Additionally, the electrochemically active zincophilic sites (C=O, ‐NH2 and triazine groups) favor the targeted guidance and penetration of Zn2+ and provide advantageous sites for uniform Zn deposition. High Young’s modulus of the HOF layer further contributes to a high interfacial flexibility and stability against Zn plating‐associated stress. The MA‐BTA@Zn symmetric cells thereby obtain a substantially extended battery life over 1000 h at 4 mA cm‐2. The MA‐BTA@Zn||Cu half‐cell demonstrates a highly reversible Zn stripping/plating process over 1500 cycles with impressive average Coulombic efficiency (CE) of 99.5% at 10 mA cm‐2.