An Adaptable Structure of Metal‐Organic Framework Glass Interlayer Enables Superior Performance in Aqueous Zinc‐Ion Batteries

Abstract The practical application of safe and cost‐effective aqueous zinc‐ion batteries is enhanced by the metal‐organic frameworks (MOFs), which possess tunable porous structures and chemical compositions that can facilitate the desolvation and transport of Zn²⁺ ions at the anode interface. However, ensuring the structural stability and operational life of crystalline MOFs in batteries remains a challenge. Here, a breakthrough is presented in tackling this dilemma. A MOF glass interlayer, specifically the ZIF‐62 glass interlayer, is designed and fabricated for the Zn anode. The integration of this interlayer endows the Zn anode with a remarkable cyclic lifespan. It also achieves outstanding cyclability in Zn||MnO₂ full‐cell with limited Zn excess, showing no capacity decay after 600 cycles at 0.5 A g⁻¹, and in a Zn||iodine pouch battery with a mass loading of 12.85 mg cm⁻². This superior cyclicity is attributed to the ease of distortion of Zn[ligand]₄ tetrahedra and the reduced likelihood of disconnection between adjacent tetrahedra within the glass interlayer, as compared to its crystalline counterpart. The unique structure of ZIF‐62 glass provides an increased degree of configurational freedom, allowing it to withstand mechanical stress and extend the Zn²⁺ ion diffusion pathway. This ensures high cycling stability and rapid interfacial diffusion kinetics.