Ionic conductivity and crystal structure relationships in Ti/Cu substituted Bi4V2O11

Crystal structure and oxide ion conductivity of a series of Ti and Ti-Cu double substituted Bi₄V₂O₁₁ compounds, Bi₂V_(1–x)Ti _x O_(11–x)/2 (0.085 x 0.15), and Bi₂V_0.9Cu_(0.1–x)TixO_5.35+x (0 x 0.1), were investigated using X-ray powder diffraction and ac impedance spectroscopy in the temperature and frequency range of 100–700°C and 10^–2–10⁷ Hz, respectively.Structural phase transitions, and , occur as a function of composition in Ti substituted compounds for which the is evidenced to be stable at room temperature when x exceeds 0.125. For all Ti-Cu double substituted compounds studied, the room temperature phase was identified to be phase.The required amount of Ti for phase stabilization at room temperature was significantly reduced and the conductivity improved when Cu substituted a part of Ti. Therefore, for the Bi₂V_0.9Cu_(0.1–x)Ti _x O_5.35+x (0 x 0.075) compounds the ionic conductivity increased and activation energy decreased with decreasing x. At low temperature, the highest ion conductivity was obtained for Bi₂V_0.9Cu_0.1O_5.35. At high temperature (T>500°C), a different behavior was observed. The total conductivity increased at first with decreasing x values down to x = 0.05 and then decreased. The maximum conductivity was obtained for Bi₂V_0.9Cu_0.05Ti_0.05O_5.4, and the activation energy decreased with decreasing x values, such as what happened at low temperature.