High Li-Ion Conductivity in Pyrochlore-Type Solid Electrolyte Li_2–<i>x</i>La_{(1+<i>x</i>)/3}M₂O₆F (M = Nb, Ta)

Abstract

All-solid-state Li-ion batteries featuring both a high energy density and safety are desirable. Sulfide-based solid electrolytes with high conductivities have been actively studied. However, such electrolytes easily react with moisture in air to generate toxic H2S. Therefore, non-sulfide-based solid electrolytes with high ionic conductivity are needed. In this study, we discovered high ionic conductivity in pyrochlore-type oxyfluoride Li2–xLa(1+x)/3M2O6F (M = Nb, Ta), which was stable in air. Li1.25La0.58Nb2O6F exhibited a bulk ionic conductivity of 7.0 mS cm–1 and a total ionic conductivity of 3.9 mS cm–1 at room temperature (∼298 K), which are higher than those of any previously reported oxide solid electrolytes. The conduction path of pyrochlore-type structure covers the F ions located in the tunnels created by MO6 octahedra. The conduction mechanism is the sequential movement of Li ions while changing bonds with F ions. Li ions move to the nearest Li position always passing through metastable positions. Immobile La3+ bonded to the F ion inhibits the Li-ion conduction by blocking the conduction path and vanishing the surrounding metastable positions. We not only successfully synthesized a Li-ion conductor with high conductivity and stability in air but also pioneered a new class of superionic conductors with a pyrochlore-type oxyfluoride.