Dynamic Covalent Bonds Regulate Zinc Plating/Stripping Behaviors for High‐Performance Zinc Ion Batteries

Abstract Artificial interfaces provide a comprehensive approach to controlling zinc dendrite and surface corrosion in zinc‐based aqueous batteries (ZABs). However, due to consistent volume changes during zinc plating/stripping, traditional interfacial layers cannot consistently adapt to the dendrite surface, resulting in uncontrolled dendrite growth and hydrogen evolution. Herein, dynamic covalent bonds exhibit the Janus effect towards zinc deposition at different current densities, presenting a holistic strategy for stabilizing zinc anode. The PBSC intelligent artificial interface consisting of dynamic B−O covalent bonds is developed on zinc anode to mitigate hydrogen evolution and restrict dendrite expansion. Owing to the reversible dynamic bonds, PBSC exhibits shape self‐adaptive characteristics at low current rates, which rearranges the network to accommodate volume changes during zinc plating/stripping, resisting hydrogen evolution. Moreover, the rapid association of B−O dynamic bonds enhances mechanical strength at dendrite tips, presenting a shear‐thickening effect and suppressing further dendrite growth at high current rates. Therefore, the assembled symmetrical battery with PBSC maintains a stable cycle of 4500 hours without significant performance degradation and the PBSC@Zn||V 2 O 5 pouch cell demonstrates a specific capacity exceeding 170 mAh g −1 . Overall, the intelligent interface with dynamic covalent bonds provides innovative approaches for zinc anode interfacial engineering and enhances cycling performance.