Ionic conductivity of Zr1−xIn2xO2−x

As x in Zr(In)O_2?x is increased from 0.08 to 0.16 (9–19 mole per cent In₂O₃) the activation energy E(x) for ionic conduction increases from 1.05 to 1.51 eV; the concuctivity decreases from 2 × 10^?5 to 3 × 10^?6Ω^?1cm^?1at 400°C, is composition-independent at about 580°C, and increases from 1 × 10^?2 to 4 × 10^?2Ω^?1cm^?1 at 800°C. The pre-exponential term of the Boltzmann-type conductivity equation depends exponentially on E(x), a much stronger dependence on x than theoretically expected with a model for ionic conductivity that includes nearest-neighbor defect interactions. Analysis of reported conductivity data for Zr(M)O_2?x (M = Sc, Y, Ca and rare earth metals) and other doped oxide electrolytes with fluorite-type structure reveals that the same relationship is observed with these materials when x γ0.08. It is shown that ionic conduction in these oxides is consistent with nearest neighbor vacancy-cation defect interaction forx < 0.08 but that an additional complex interaction with composition-dependent free energy ΔG(x) occurs when xγ 0.08.The lattice constant of Zr(In)O_2?x with the cubic fluorite-type structure is independent of composition, 5.114 ± 0.002 Å, in agreement with ionic size considerations.