Improving ionic conductivity of von-Alpen-type NASICON ceramic electrolytes via magnesium doping

NASICON (sodium (Na) superionic conductor) compounds have attracted considerable attention as promising solid electrolyte materials for advanced Na-based batteries. In this study, we investigated the improvement in ionic conductivities of von-Alpen-type NASICON (vA-NASICON) ceramic electrolytes by introducing a magnesium ion (Mg2+) as a heterogeneous element. The optimal Mg-doped vA-NASICON exhibited a high ionic conductivity of 3.64x10(-3) S.cm(-1), which was almost 80% higher than that of un-doped vA-NASICON. The changes in physicochemical properties of the vA-NASICONs through the Mg introduction were systematically analyzed, and their effects on the ionic conductivities of the vA-NASICON were studied in detail. When the optimal ratio of Mg2+ was used in a synthetic process, the relative density (96.6%) and grain boundary ionic conductivity (sgb) were maximized, which improved the total ionic conductivity (st) of the vA-NASICON. However, when Mg2+ was introduced in excess, the ionic conductivity decreased because of the formation of an undesired sodium magnesium phosphate (NaxMgyPO4) secondary phase. The results of this study are expected to be effectively applied in the development of advanced sodium-based solid electrolytes with high ionic conductivities.