Abstract

AbstractSodium cobaltite (NaxCoO2) is one of the most renowned and thermoelectrically promising p‐type cobalt oxide materials, showing exceptional performance in this domain. Nonetheless, its thermal instability in air renders it unsuitable for high‐temperature applications such as energy harvesting from industrial waste heat. To utilize the beneficial properties of NaxCoO2, microscale NaxCoO2 template particles of significantly larger size were effectively embedded within a thermally stable Ca3Co4−yO9+δ–NaxCoO2–Bi2Ca2Co2O9 triple‐phase matrix. This approach additionally aimed to enhance the texture and boost the thermoelectric performance of the ceramic composite. Highly textured p‐type ceramic composites were fabricated via uniaxial cold‐pressing and pressureless sintering in air. The unique hexagonal NaxCoO2 template particles, produced through molten‐flux synthesis, allowed precise control over their shape and dimensions, while the matrix was synthesized via a sol–gel synthesis. The integrated NaxCoO2 particles of the textured composite exhibited increased thermal stability, showing no sign of decomposition at 1173 K in air, whereas the sole template particles decomposed at 1073 K during sintering. A 20 wt% template particle content in the textured composites resulted in a remarkably high and nearly temperature‐independent power factor of 8.8 µW cm−1 K2, corresponding to an improvement of 13% compared to that of the pure matrix material.

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