Influence of pressure assisted sintering and reaction sintering on microstructure and thermoelectric properties of bi-doped and undoped calcium cobaltite

Abstract

Calcium cobaltite (Ca3Co4O9) is considered as one of the most promising thermoelectric p-type oxides for energy harvesting applications at temperatures above 500 °C. It is challenging to sinter this material as its stability is limited to 920 °C. To facilitate a practicable and scalable production of Ca3Co4O9 for multilayer generators, a systematic study of the influence of powder calcination, Bi doping, reaction sintering, and pressure-assisted sintering (PAS) on microstructure and thermoelectric properties is presented. Batches of doped, undoped, calcined, and not calcined powders were prepared, tape-cast, and sintered with and without uniaxial pressure at 900 °C. The resulting phase compositions, microstructures, and thermoelectric properties were analyzed. It is shown that the beneficial effect of Bi doping observed on pressureless sintered samples cannot be transferred to PAS. Liquid phase formation induces distortions and abnormal grain growth. Although the Seebeck coefficient is increased to 139 μV/K by Bi doping, the power factor is low due to poor electrical conductivity. The best results were achieved by PAS of calcined powder. The dense and textured microstructure exhibits a high power factor of 326 μW/m K2 at 800 °C but adversely high thermal conductivity in the relevant direction. The figure of merit is higher than 0.08 at 700 °C.