“…Indeed, few studies have investigated the inuences of excess Na + in NaSICONs 90,91,[131][132][133] revealing that conductivity increases and activation energy decreases, based on the increase in Na + charge carrier 91,133 and enhanced mobility by the widening of the bottlenecks. 90,133 The amount of Na + charge carrier can also be modied when the M 4+ and P 5+ sites are substituted with cations with various valence. As shown in this study, the substitution with subvalent cations leads not only to the increase in Na + concentration but also to the decrease in Na + ion migration energy due to the lower electrostatic repulsion with the migrating Na + ions.…”