| Summary: | Nanoconfinement is an effective strategy to tune the properties of the metal hydrides. It has been extensively employed to modify the ionic conductivity of LiBH<sub>4</sub> as an electrolyte for Li-ion batteries. However, the approach does not seem to be applicable to other borohydrides such as NaBH<sub>4</sub>, which is found to reach a limited improvement in ionic conductivity of 10<sup>−7</sup> S cm<sup>−1</sup> at 115 °C upon nanoconfinement in Mobil Composition of Matter No. 41 (MCM-41) instead of 10<sup>−8</sup> S cm<sup>−1</sup>. In comparison, introducing large cage anions in the form of Na<sub>2</sub>B<sub>12</sub>H<sub>12</sub> naturally formed upon the nanoconfinement of NaBH<sub>4</sub> was found to be more effective in leading to higher ionic conductivities of 10<sup>−4</sup> S cm<sup>−1</sup> at 110 °C.
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