Orientational disorder, glass/crystal transition and superionic conductivity in nasicon

Abstract

The relations between the orientational disorder of SiO 4(PO 4) tetrahedra and fast sodium diffusion in superionic NASICON have been studied by conductivity (complex impedance method), DSC, X-ray powder difraction and vibrational spectroscopy (IR and Raman). Sol-gel routes allow to obtain pure glassy NASICON (Na 1+ x Zr 2Si x P 3- x O 12 x≅2) in the 500−700°C temperature range. Tetragonal zirconia nucleates above 700°C and disappears at about 900°C when the isolated tetrahedra framework is formed: a high orientational static disorder of tetrahedra exists and the symmetry is rhombohedral at all studied temperatures (20−600 K). Thermal treatment above 1100°C induces a drastic decrease of the static orientational disorder and nucleation of monoclinic zirconia. The resulting compound exhibits a monoclinic symmetry at R.T. and three phase transitions, two diffuse at about 60 K and 520 K and the 423 K monoclinic-rhombohedral transition associated with the superionic conducting state. An increase in dynamic disorder (broad Rayleigh wing up to 500 cm -1 is simultaneously observed. The lower the static disorder at low temperature, the higher the dynamic orientational disorder and the phase transitions, and the lower the activation energy of conductivity at high temperature.