Supramolecular Metal–Organic Framework for the High Stability of Aqueous Rechargeable Zinc Batteries

Aqueous rechargeable Zn batteries (AZBs) are considered to be promising next-generation battery systems. However, the growth of Zn dendrites and water-induced side reactions have hindered their practical application, especially with regard to long-term cyclability. To address these challenges, we introduce a supramolecular metal-organic framework (SMOF) coating layer using an α-cyclodextrin-based MOF (α-CD-MOF-K) and a polymeric binder. The plate-like α-CD-MOF-K particles, combined with the polymeric binder create dense and homogeneous Zn²⁺ ion conductive pore channels that can vertically transport Zn²⁺ ions through the cavity while restricting the contact of water molecules. Molecular dynamics (MD) simulation verifies that Zn²⁺ ions can reversibly migrate through the pores of α-CD-MOF-K by partial dehydration. The uniform Zn deposition/dissolution promotes a smooth solid-electrolyte interface layer on the Zn metal anode and effectively suppresses side reactions with free water molecules. The α-CD-MOF-K@Zn symmetric cell exhibits stable cycling and a small polarization voltage of 70 mV for 800 h at 5 mA cm^-2, and the α-CD-MOF-K@Zn|α-MnO₂ full cell shows only 0.12% capacity decay per cycle at a rate of 1 A g^-1.