Shuo Zhao, Shuyue Luo, Yangming Zhang, Rongyan Xie, Zhen Liu, Zhengyin Yao, Xianru He, Jiangbo Li, Xiangdong Yao, Zhou Zhou, Dongbai Sun, Peng Zhang
Abstract The development of stable zinc anodes is critical for advancing high‐rate, long‐life aqueous zinc batteries. Here a tape‐inspired anode modification is reported using a poly (methyl methacrylate)‐grafted natural rubber (NRAc) copolymer as a conformal protective coating. The microphase‐separated architecture integrates elastic, hydrophobic NR domains with Zn 2+ ‐coordinating PMMA nanodomains, forming mechanically adaptive and ion‐selective channels. Density functional theory and microscopy reveal that Zn 2+ preferentially binds to PMMA, lowering desolvation barriers and biasing deposition toward the stable (002) facet. This dual mechanical‐chemical regulation suppresses dendrite growth and parasitic hydrogen evolution, while maintaining intimate interfacial contact under dynamic cycling. As a result, NRAc@Zn symmetric cells achieve unprecedented cycling lifetimes exceeding 32,000 cycles, while Zn||V 2 O 5 full cells deliver stable operation at current densities up to 10 A g −1 . Scaling to a 1.5 Ah pouch cell demonstrates the practical feasibility of the approach. This work establishes polymer microphase engineering, inspired by the multifunctionality of adhesive tapes, as a versatile strategy to stabilize Zn anodes and advance the deployment of aqueous Zn batteries for large‐scale energy storage.