Pristine NASICON Electrolyte: A High Ionic Conductivity and Enhanced Dendrite Resistance Through Zirconia (ZrO₂) Impurity‐free Solid‐Electrolyte Design

Sodium batteries are considered a promising candidate for large-scale grid storage at tropical climate zone, and solid-state sodium metal batteries have a strong proposition as high energy density battery. The main challenge is to develop ultra-pure solid-state ceramic electrolyte and compatible metal interface. Here, a scalable and energy-efficient synthesis strategy of sodium (Na) Super Ionic CONductor, Na_1+xZr₂Si_xP_3-xO₁₂ (x = 2, NZSP) solid electrolyte, has been introduced with the complete removal of unreacted zirconium oxide (ZrO₂) impurities. Additionally, the reaction mechanism for the formation of pure phase NZSP is reported for the first time. The NZSP prepared by utilizing the Zr precursor, i.e., tetragonal zirconium oxide (t-ZrO₂) derived from the Zr(OH)₄ gets quickly and completely consumed in the synthesis process leaving no unreacted monoclinic ZrO₂ impurities. The synthesis process only needs a minimum stay of 4 h, which is three times less than the conventional synthesis method. The elimination of ZrO₂ impurities results in a 2.5-fold reduction in grain boundary resistivity, showcasing a total ionic conductivity of 1.75 mS cm^-1 at room temperature and a relative density of 98%. The prepared electrolyte demonstrates remarkable resistance to dendrite formation, as evidenced by a high critical current density value of 1.4 mA cm^-2.