Impedance spectroscopy study on the ionic conductivity processes of the novel LiFeVO4 phase

The recently discovered compound LiFeVO₄ was prepared by solid-state reaction at 570 °C during a 7-h period. The X-ray diffraction pattern revealed an orthorhombic crystal structure. Thermogravimetric measurements revealed a reversible mechanism which was attributed to absorption–desorption of humidity. Impedance spectroscopy measurements were carried out at 25 °C steps in the temperature range from 25 to 500 °C and equivalent circuits were drawn to fit the impedance measurement results at each temperature level. The elements of the equivalent circuits were assigned to bulk, grain boundary, and along grain boundary conductivity. All three conduction mechanisms were found to be humidity sensitive. Arrhenius plots were plotted for the bulk and grain boundary conductivity processes. The activation energy for the bulk conductivity process was calculated to be 0.25 eV over the temperature range from 175 to 500 °C and the activation energy for the grain boundary conductivity process was calculated to be 0.41 eV from 300 to 500 °C and 0.20 eV from 175 to 275 °C. An explanation for the existence of these two grain boundary activation energies is attempted. The dependence of the material conductivity mechanisms on humidity suggests that LiFeVO4 could be used as a humidity sensor.