Al Doped into Si/P Sites of Na 3 Zr 2 Si 2 PO 12 with Conducted Na 3 PO 4 Impurities for Enhanced Ionic Conductivity.

Natrium superionic conductor (NASICON) is a promising solid-state electrolyte because of its high stability under air as well as its safety. Doping is an effective way to improve its ionic conductivity, but there is limited information about the explanation of the doping sites. In this work, Al-doped NASICONs are designed. When Al doping is 0.3 (NAl 0.3 ZSP), the ionic conductivity is the highest and is 5.08 × 10 -5 S cm -1 at 30 °C, which is 3.3 times that of undoped NASICON. NAl 0.3 ZSP consists of a NASICON structure (monoclinic and rhombohedral phases), an amorphous glassy phase, and Na 3 PO 4 impurities. After Al doping, more Si/P sites are occupied by Al; thus, the ratio of Na 3 PO 4 impurities increases. Na 3 PO 4 at the grain boundary is beneficial for grain boundary resistance decrease, contributing to the decrease of the total resistance. Our work first provides a detailed explanation of doped-Al sites and interprets their effects on ionic conductivity.