Effect of Ni(II) substitution on phase stabilization electrical properties of BICo(III)VOX.20 oxide-ion conductor

Abstract

The BICO0.20–xNIxVOX solid electrolyte was synthesized by the standard solid-state reaction. The effect of Ni(II) substitution for Co(III) on phase stabilization and oxide-ion performance has been investigated in the compositional range 0 ≤ x ≤ 0.20 using X-ray powder diffraction, differential thermal analysis and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.13 whose thermal stability increases with Ni content. The complex plane plots of impedance were typically represented at temperatures below 380 °C, suggesting a major contribution of polycrystalline grains to the overall electrical conductivity. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. Interestingly, the maximum ionic conductivity at lower temperatures (~2.56 × 10−4 S cm−1 at 300 °C) was observed for the composition with x = 0.13. The variation of low-temperature conductivity with Ni content was accompanied with a general drop in the corresponding values of ΔELT. However, the local minimum high-temperature conductivity, σ600 °C ~ 2.26 × 10−2 S cm−1 for x = 0.10, coupled with a local maximum value of ΔEHT ~ 0.48 eV was attributed to an increased defect trapping effect correlated with the V(V) → V(IV) reduction at elevated temperatures.