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.