Hierarchically porous Ca3Co4O9 ceramics prepared by freeze casting: Emerging ultra‐low thermal conductivity and apparent anisotropy

Abstract

AbstractThe freeze‐casting method shows great potential for environmentally friendly and industrial scale‐up application in thermoelectric materials due to low cost, low toxicity, and pore control. The porous Ca3Co4O9 ceramics with anisotropic thermoelectric performance were fabricated by the freeze‐casting method. High porosities, hierarchical pores, and three‐dimensional (3D) networks significantly contributed to the suppressed thermal conductivity. An ultralow total thermal conductivity of 0.21 W/(m·K) was obtained. The optimized freeze‐casting conditions gave rise to a Seebeck coefficient of 232.3 µV/K. In addition, the ZT value of 0.39 was obtained at 800°C due to the manipulation of hierarchically connected pores and small portions of isolated hexagonal pores. This work provides a new route to form the 3D pores network in oxide thermoelectric ceramics, leading to a decrease in thermal conductivity and optimized thermoelectric performance parallel to the freeze‐casting direction.