Global “Interface‐Space” Dual‐Modulation by Functional Supramolecules Organic Frameworks on Aqueous Zinc‐Ion Batteries

Abstract The uneven zinc‐ion flux and interfacial contact between the anode and electrolyte trigger malignant dendrites and byproducts, significantly hindering the practical application of zinc‐metal batteries. Herein, a H‐bonded supramolecular organic framework (HSOF) is proposed to help regulate Zn 2+ flux and stabilize interfacial chemistry. The self‐assembled supermolecule structures by in‐plane H‐bond networks firmly trap water molecules to assist Zn 2+ de‐solvation and block interfacial corrosion. The abundant polar groups provide strong guidance for Zn 2+ distribution, ensuring homogeneous, and rapid ion transport‐deposition kinetics. Meanwhile, the π – π stacked space‐layout structure affords preferred Zn(002) plane stacking for smooth and flat growth. Benefiting from these advantages, the HSOFs are employed on Zn surface for interfacial adjustment and on separator decoration for spatial manipulation, successfully realizing an overall “interface‐space” dual‐regulation effect. It delivers over 3000 h for the HSOF@Zn anode in symmetric cell and up to 5000 h for HSOF‐decorated separator in Zn||Zn symmetric cell, respectively. The HSOF@Zn||V 2 O 5 full cell with the HSOF‐decorated separator demonstrates enhanced capacity retention of 92.7% after 2500 cycles at 5 A g −1 . The full cell can be easily scaled up into a pouch cell, which still has a capacity retention rate of 94% after 1000 cycles.