Lithium-ion Mobility in Li6B18(Li3N) and Li Vacancy Tuning in the Solid Solution Li6B18(Li3N)1−x(Li2O)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 Li₆B₁₈(Li₃N) comprises large hexagonal pores filled with Li₇N] strands that represent a perfect cutout from the structure of α-Li₃N. Variable-temperature ⁷Li 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 Li₃N. The formation of the solid solution of Li₆B₁₈(Li₃N) and Li₆B₁₈(Li₂O) over the complete compositional range allows the tuning of lithium defects in the template structure that is not possible for pristine Li₃N and Li₂O.