| Summary: | Sodium super ionic conductor (NASICON)-type Na<sub>3</sub>Zr<sub>2</sub>Si<sub>2</sub>PO<sub>12</sub> (NZSP) with the advantages of the high ionic conductivity, stability and safety is one of the most famous solid-state electrolytes. NZSP, however, requires the high sintering temperature about 1200 °C and long sintering time in the conventional solid-state reaction (SSR) method. In this study, the liquid-phase sintering (LPS) method was applied to synthesize NZSP with the use of NaPO<sub>3</sub> glass with a low glass transition temperature of 292 °C. The formation of NZSP was confirmed by X-ray diffraction analyses in the samples obtained by the LPS method for the mixture of Na<sub>2</sub>ZrSi<sub>2</sub>O<sub>7</sub>, ZrO<sub>2</sub>, and NaPO<sub>3</sub> glass. The sample sintered at 1000 °C for 10 h exhibited a higher Na<sup>+</sup> ion conductivity of 1.81 mS/cm at 100 °C and a lower activation energy of 0.18 eV compared with the samples prepared by the SSR method. It is proposed that a new LPE method is effective for the synthesis of NZSP and the NaPO<sub>3</sub> glass has a great contribution to the Na<sup>+</sup> diffusion at the grain boundaries.
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