Synthesis and electric conductivity of solid electrolyte of NASICON type

The sequences of solid-phase reactions during synthesis of solid electrolyte corresponding to Na3Zr2Si2PO12 stoichiometric composition are studied. It is shown that solid-phase reaction of ZrO(NO3)2x2H2O, Na2CO3, NH4H2PO4 and amorphous SiO2 proceeds through stages of nitrate-zirconium oxide dehydration, ammonium dihydrophosphate decomposition, formation and decomposition of ammonium and sodium. Intermediate reaction products are sodium and zirconium phosphates, and some of ZrO2 takes part in the reaction in the form of amorphous or metastable tetragonal modification and another part transforms into a stable monoclinic one. NASICON formation starts at 1000 deg C, only at this stage silicon dioxide begins to react, which is already transformed from amorphous phase into a mixture of tridymite and α-crystobalyte. After annealing at 1230 deg C a single-phase solid electrolyte Na3Zr2Si2PO12 having conductivity 0.14 S/cm at 300 deg C and 0.00028 S/cm at 25 deg C