One‐Dimensional Crystalline Zn2+ Conduction by Labile Tetrahedral Motifs

Abstract Switching from liquid electrolytes to solid‐state electrolytes (SSEs) overcome irreversible issues encountered in energy‐dense electrodes through mechanically and ionically stable solid–solid redox reactions. Most advances are achieved by the discoveries on monovalent‐cation conduction behaviors in SSEs, whereas practically feasible divalent‐cation conduction is formidably challenging in solids, essentially due to the lack of tailored anionic frameworks tolerating charge‐dense cations. Here, through a precise design of coordination geometry controlled by highly polarizable anionic ligands, a specialized single‐crystal framework containing continuous Zn 2+ ‐conducting channels is engineered with mitigated Coulombic penalties. The ordered 1D architecture with tailored tetrahedral ZnI 4 2− integrating labile Zn 2+ ‐I − interplays and anionic disordering dynamics induces enhanced Zn 2+ diffusion in a “pulley block” manner, achieving a conductivity of 6.44 × 10 −5 S cm −1 (at 30 °C) surpassing conventional Zn 2+ ‐conducting SSEs by three orders of magnitude. This work establishes a new paradigm for multivalent‐cation conducting solid frameworks based on simultaneous anion modulation and coordination engineering, unlocking pathways toward energy‐dense post‐Li batteries.