Thermoelectric generators are very attractive devices for waste heat energy harvesting as they transform a temperature difference into electrical power. However, commercially available generators show poor power density and limited operation temperatures. Research focuses on high‐temperature materials and innovative generator designs. Finding the optimal design for a given material system is challenging. Here, a theoretical framework is provided that allows appropriate generator design selection based on the particular material properties. For high‐temperature thermoelectric oxides, it can be clearly deduced that unileg multilayer generators have the highest potential for effective energy harvesting. Based on these considerations, prototype unileg multilayer generators from the currently best thermoelectric oxide Ca3Co4O9 are manufactured for the first time by industrially established ceramic multilayer technology. These generators exhibit a power density of 2.2 mW/cm² at a temperature difference of 260 K, matching simulated values and confirming the suitability of the technology. Further design improvements increase the power density by a factor of 22 to facilitate practicable power output at temperature differences as low as 7 K. This work demonstrates that reasonable energy harvesting at elevated temperatures is possible with oxide materials and appropriate multilayer design.
In this work, the thermoelectric material calcium cobaltite Ca3Co4O9 (CCO), a promising p-type conducting thermoelectric oxide with anisotropic properties, was processed by the powder aerosol deposition method (PAD) to form a dense ceramic CCO film with a thickness in the µm range. The prepared films were characterized regarding their microstructure and thermoelectric properties between room temperature and 900 °C. After heat treatment at 900 °C, the CCO PAD film in-plane shows excellent properties in terms of electrical conductivity (280 S/cm at 900 °C) and Seebeck coefficient (220 µV/K at 900 °C). The calculated power factor in-plane (ab) reaches with 1125 µW/(m K2) 40 % of the single crystal value, surpassing the known-properties of CCO bulk ceramics. Examination of the microstructure shows a strong fiber texture of the film as well as a strong coarsening of the grains during the first heat treatment up to 900 °C.