Lithium-ion Mobility in Li₆ B₁₈ (Li₃ N) and Li Vacancy Tuning in the Solid Solution Li₆ B₁₈ (Li₃ N)_1-x (Li₂ O)_x

All-solid-state batteries are promising candidates for safe energy-storage systems due to non-flammable solid electrolytes and the possibility to use metallic lithium as an anode. Thus, there is a challenge to design new solid electrolytes and to understand the principles of ion conduction on an atomic scale. We report on a new concept for compounds with high lithium ion mobility based on a rigid open-framework boron structure. The host-guest structure Li₆ B₁₈ (Li₃ N) comprises large hexagonal pores filled with $$ Li₇ N] strands that represent a perfect cutout from the structure of α-Li₃ N. Variable-temperature ⁷ Li NMR spectroscopy reveals a very high Li mobility in the template phase with a remarkably low activation energy below 19 kJ mol^-1 and thus much lower than pristine Li₃ N. The formation of the solid solution of Li₆ B₁₈ (Li₃ N) and Li₆ B₁₈ (Li₂ O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li₃ N and Li₂ O.