Oxide ion conductivity in doped bismuth gallate mullite type oxide, Bi2Ga4O9

Abstract

Mullite-phase bismuth gallate (Bi2Ga4O9) was successfully synthesized with partial substitution of bismuth with alkaline-earth cation, Mg2+, Ca2+, Sr2+, and Ba2+. The effect of this substitution on the electrical conductivity was investigated. In this study, substitution with Ca2+ of Bi site was further studied for increasing the ionic conductivity as well as the phase stability in reducing atmospheres. Substitution with Ca2+ was found to be the most effective and with 12.5 mol% of Ca2+ as the optimized doping amount. Conductivity and stability in reducing atmospheres was increased down to pO2 ≤ 10−19 atm while keeping the conductivity of σ = 2.6 × 10−2 S·cm−1 at 973 K largely independent of oxygen partial pressure. Oxygen permeation analysis estimates 76% of theoretical oxygen permeation rate at 973 K suggesting main charge carrier is oxide ion. Partial electronic conductivity was measured with the ion blocking method. Oxide ion conductivity is dominated over wide pO2 range excepting for hole conduction at high pO2. Density functional theory (DFT) analysis on oxide ion diffusion route suggests oxygen hoping through lattice vacancy is main pathway for oxide ion conductivity in this doped Bi2Ga4O9. Despite the low oxide ion conductivity in Mullite-phase oxide, it was found that Ca doped Bi2Ga4O9 shows good oxide ion conductivity over wide pO2 range.