Electrical conduction and thermoelectric properties of perovskite-type BaBi1−xSbxO3

To elucidate the thermoelectric properties at high temperatures, the electrical conductivity and Seebeck coefficient were measured at temperatures between 423 K and 973 K for perovskite-type ceramics of BaBi1−xSbxO3 solid solutions with x=0.0–0.5. All the ceramics exhibit p-type semiconducting behaviors and electrical conduction is attributed to hopping of small polaronic holes localized on the pentavalent cations. Substitution of Bi with Sb causes the electrical conductivity σ and cell volume to decrease, but the Seebeck coefficient S to increase, suggesting that the Sb atoms are doped as Sb5+ and replace Bi5+, reducing 6s holes conduction from Bi5+(6s0) to Bi3+ (6s2). The thermoelectric power factor S2σ has values of 6×10−8–3×10−5 W m−1 K−2 in the measured temperature range, and is maximized for an Sb-undoped BaBiO3−δ, but decreases upon Sb doping due to the decreased σ values.

► Electrical conductivity and Seebeck coefficient are measured at high temperatures.
► All ceramics exhibit p-type semiconducting behaviors.
► Sb atoms are doped as Sb5+ to reduce 6s holes.
► Thermoelectric power factors are maximized for Sb-undoped BaBiO3−δ.