Na ₂ B ₁₂ H ₁₂ exhibits dramatic Na ⁺ conductivity (on the order of 0.1 S cm ⁻¹ ) above its order-disorder phase transition at ≈529 K, rivaling that of current, solid-state, ceramic-based, Na-battery electrolytes.

Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing “geometric frustration” via the mixing of two different closo-polyborate anions, namely, 1-CB₉H₁₀^– and CB₁₁H₁₂^–, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambient to high temperatures. This result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.