Bidentate Coordination by Graphene Oxide‐Enhanced γ‐Cyclodextrin for Synergistic Solvation and Stabilization of the Zn Anode

ABSTRACT With the rapid development of the energy storage industry, aqueous zinc‐ion batteries (AZIBs) have attracted considerable attention in the field of energy storage because of their inherent advantages, thereby emerging as a promising research direction with significant potential. However, secondary reactions, such as dendrite formation and surface corrosion, significantly restrict the cycle life and practical applicability of this material. Therefore, we have proposed a new strategy, adding γ‐cyclodextrin (γ‐CD) and graphene oxide (GO) as bifunctional composite synergistic additives to the Zn sulfate electrolyte, so as to achieve the solvation structure reorganization of the electrolyte and the interface regulation of the Zn anode. The calculations demonstrate that γ‐CD restricts the free movement of H2O molecules because of its large cavity size and hydrophobic internal environment. The presence of a bidentate binding motif enables γ‐CD to coordinate with Zn 2+ , thereby further regulating the deposition behavior of Zn 2+ . Meanwhile, the composite system of γ‐CD and GO forms a stable synergistic adsorption network through its adsorption energy, and the strong interfacial interaction between the composite and Zn 2+ optimizes the ion transport pathway. Consequently, the composite additive demonstrates superior electrochemical performance, achieving a cycle life exceeding 7600 h. Moreover, the Zn//V 2 O 5 full cell retains 84% of its initial capacity even after 2000 cycles, demonstrating exceptional cycling stability. This study emphasizes the pivotal role of supramolecular coordination and conductive two‐dimensional material‐based composite structures in the rational design of additives, offering a promising strategy for the development of high‐performance ZIBs.