Abstract
The sintering properties, crystal structure and electrical conductivity of La1-xCaxNbO4-б (x=0, 0.005, 0.01, 0.015, 0.02 and 0.025), prepared by a conventional solid-state method, have been investigated using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). In 2.5% Ca doped samples, a small amount of impurities Ca2Nb2O7 were observed from the XRD patterns. Impedance spectra show that the grain boundary resistance increases with increasing Ca content, while the bulk resistance remains essentially constant below 550°C. Despite the higher degree of grain growth was observed for higher Ca-doping levels, the total conductivity of the La1-xCaxNbO4-б series decreases with increasing Ca content from 0.5 to 2.0 mol%. The activation energy for the total conductivity decreases with increasing Ca content from 0.71 eV (x=0) to 0.54 eV (x=0.01) for the high temperature tetragonal phase, then it increases to 0.60 eV for x=0.02. For the monoclinic phase, La0.995Ca0.005NbO4-б shows the lowest activation energy of 1.26 eV. These results imply that the solubility of CaO in LaNbO4 is in the range from 0.5 to 1.0 mol%. By increasing the sintering temperature from 1500°C to 1550°C, the proton conductivity of the Ca-doped LaNbO4 was improved with enlarged grain size due to a reduction in the resistive grain boundary contribution.
