Combined Effects of Anion Substitution and Nanoconfinement on the Ionic Conductivity of Li-Based Complex Hydrides

[Image: see text] Solid-state electrolytes are crucial for the realization of safe and high capacity all-solid-state batteries. Lithium-containing complex hydrides represent a promising class of solid-state electrolytes, but they exhibit low ionic conductivities at room temperature. Ion substitution and nanoconfinement are the main strategies to overcome this challenge. Here, we report on the synthesis of nanoconfined anion-substituted complex hydrides in which the two strategies are effectively combined to achieve a profound increase in the ionic conductivities at ambient temperature. We show that the nanoconfinement of anion substituted LiBH(4) (LiBH(4)–LiI and LiBH(4)–LiNH(2)) leads to an enhancement of the room temperature conductivity by a factor of 4 to 10 compared to nanoconfined LiBH(4) and nonconfined LiBH(4)–LiI and LiBH(4)-LiNH(2), concomitant with a lowered activation energy of 0.44 eV for Li-ion transport. Our work demonstrates that a combination of partial ion substitution and nanoconfinement is an effective strategy to boost the ionic conductivity of complex hydrides. The strategy could be applicable to other classes of solid-state electrolytes.