Seebeck coefficient and electrical conductivity of BSCF (Ba0.5Sr0.5CoxFe1 − xO3 − δ, 0 ≤ x ≤ 0.8) as a function of temperature and partial oxygen pressure

The electrical conductivity and Seebeck coefficient of sintered BSCF ceramics (Ba0.5Sr0.5CoxFe1 − xO3 − δ, 0 ≤ x ≤ 0.8) were simultaneously measured as a function of pO2 (10− 5 ≤ pO2 ≤ 1 atm) at 500 °C, 700 °C and 900 °C. All samples exhibited a positive Seebeck coefficient over the range of pO2 and temperature examined, which indicates the predominance of p-type conduction. In all cases, conductivity increased with increasing pO2, ranging from a minimum of ~ 0.6 S/cm (x = 0, pO2 = 10− 5 atm, T = 900 °C) to a maximum of ~ 36 S/cm (x = 0.8, pO2 = 1 atm, and T = 900 °C). At low temperatures and high pO2, conductivity was approximately proportional to pO21/4, which was attributed to the reduction of B-site cations from their tetravalent to trivalent state. At low pO2 and high temperature, the conductivity exhibited positive deviations from the pO21/4 dependence. At 500 °C and x ≤ 0.6, the Seebeck coefficient (Q) decreased linearly with increasing log pO2. At 700 and 900 °C, Q vs. log pO2 curves exhibited maxima at 10− 3 < pO2 < 10− 1 atm, and the maxima shifted to higher pO2 as x increased. A simple p-type polaron hopping model, assuming negligible contribution from n-type or ionic carriers, was used to extract the carrier concentration of the x = 0.8 sample from the measured thermopower data. The calculated hole mobility for the x = 0.8 sample was less than 0.1 cm2/V-s, confirming a p-type polaron-hopping model. This analysis, as well as analysis of Jonker plots, suggested that hole mobility decreased with decreasing pO2.

► Conductivity and Seebeck coefficient of BSCF was measured.
► BSCF materials are p-type polaron conductors at 500 °C–900 °C and 10–5 < pO2 < 1 atm.
► Seebeck coefficient and oxygen non-stoichiometry used to calculate valence state of Bn+.
► Hole mobility decreases with decreasing pO2.