Achieving Stable Orientational Zinc Deposition for Reversible Zinc Anode through Supramolecular Anchoring Mechanism

Aqueous zinc-ion batteries have been impeded by the hydrogen evolution reaction (HER), uncontrolled zinc dendrites, and side reactions on the Zn anode. In this work, a Zn–polyphenol supramolecular network is rationally designed for stabilizing Zn anodes (ZPN@Zn) even at high current density. Theoretical calculations and experiments show that the zinc–polyphenol supramolecular layer effectively inhibits the hydrogen evolution reaction by capturing water molecules through strong hydrogen bonding networks while also facilitating the rapid replenishment of Zn2+ ions at the interface through supramolecular anchoring. Additionally, it results in preferential deposition of Zn on the (002) plane, thereby contributing to nondendritic and highly reversible Zn plating/stripping behaviors even under high rates. Concomitantly, the ZPN@Zn achieves superior stability of nearly 1200 h at a high current density of 20 mA cm–2 and maintains a high CE efficiency of 99.86% after 3000 cycles at 1 mAh cm–2 and 5 mA cm–2. Remarkably, the full cell assembled with ZPN@Zn and NaV3O8 (NVO) endures 25 000 cycles at 20 A g–1, achieving an impressive performance for the realization of dendrite-free Zn anodes by supramolecular modulation.