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Na2B10H10 exhibits exceptional superionic conductivity above ca. 360 K (e.g., ca. 0.01 S cm−1 at 383 K) concomitant with its transition from an ordered monoclinic structure to a face‐centered‐cubic arrangement of orientationally disordered B10H102− anions harboring a vacancy‐rich Na+ cation sublattice. This discovery represents a major advancement for solid‐state Na+ fast‐ion conduction at technologically...
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