Ion Substitution-Induced Distorted MOF Lattice with Deviated Energy and Dielectric Properties for Quasi-Solid-State Ion Conductor

Solid-state electrolytes are currently receiving increasing interest due to their high mechanical strength and chemical stability for safe battery construction. However, their poor ion conduction and unclear conduction mechanism need further improvement and exploration. This study focuses on a hybrid solid-state electrolyte containing MOF-based scaffolds, using metal salts as the conductor. In this paper, we employ an ion substitution strategy to manipulate the scaffold structure at the lattice level by replacing hydrogen with larger alkali cations. The research systematically presents how changes in the lattice affect the physical and chemical properties of MOFs and emphasizes the role of scaffold–salt interactions in the evolution of ion conduction. The results reveal that long range-ordered structural distortion can enhance permittivity at 1 Hz, from 58 ohms to more than 10 M ohms, which can boost ion pairs dissociation and improve the transference number from 4.7% to 22.6%. Defects in the lattice can help stabilize the intermediate state in the charge transfer process and lower the corresponding impedance from 2.6 MΩ to 559 Ω.