Processing, Structure and Properties of High Temperature Thermoelectric Oxide Materials

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Virginia Tech

High temperature thermal energy harvesting has attracted much attention recently. In order to achieve stable operation at high temperatures there is emerging need to develop efficient and oxidation-resistant materials. Most of the well-known materials with high dimensionless figure of merit (ZT) values such as Bi2Te3, PbTe, skutterudites, and half-Heusler alloys, are not thermally stable at temperatures approaching 500°C or higher, due to the presence of volatile elements. Oxide thermoelectric materials are considered to be potential candidates for high temperature applications due to their robust thermal and chemical stability in oxidizing atmosphere along with the reduced toxicity, relatively simpler fabrication, and cost. In this dissertation, nanoscale texturing and interface engineering were utilized for enhancing the thermoelectric performance of oxide polycrystalline Ca3Co4O9 materials, which were synthesized using conventional sintering and spark plasma sintering (SPS) techniques. In order to tailor the electrical and thermal properties, Lu and Ga co-doping was investigated in Ca3Co4O9 system. The effect of co-doping at Ca and Co sites on the thermoelectric properties was quantified and the anisotropic behavior was investigated. Because of the effective scattering of phonons by doping-induced defects, lower thermal conductivity and higher ZT were achieved. The layered structure of Ca3Co4O9 has strong anisotropy in the transport properties. For this reason, the thermoelectric measurements were conducted for the samples along both vertical and horizontal directions. The ZT value along the vertical direction was found to be 3 to 4 times higher than that along the horizontal direction. Metallic inclusions along with ionic doping were also utilized in order to enhance the ZT of Ca3Co4O9. The texturing occurring in the nanostructured Ca3Co4O9 through ion doping and Ag inclusions was studied using microscopy and diffraction analysis. Multi-length scale inclusions and heavier ion doping in Ca3Co4O9 resulted in higher electrical conductivity and reduced thermal conductivity. The maximum ZT of 0.25 at 670°C was found in the spark plasma sintered Ca2.95Ag0.05Co4O9 sample. In literature, limited number of studies have been conducted on understanding the anisotropic thermoelectric performance of Ca3Co4O9, which often results in erroneous estimation of ZT. This study addresses this limitation and provides systematic evaluation of the anisotropic response with respect to platelet microstructure. Textured Ca3Co4O9/Ag nanocomposites were fabricated using spark plasma sintering (SPS) technique and utilized for understanding the role of microstructure towards anisotropic thermoelectric properties. The thermoelectric response was measured along both vertical and horizontal direction with respect to the SPS pressure axis. In order to achieve enhanced degree of texturing and increase electrical conductivity along ab planes, a two-step SPS method was developed. Ag nanoinclusions was found to increase the overall electrical conductivity and the thermoelectric power factor because of improved electrical connections among the grains. Through two-step SPS method, 28% improvement in the average ZT values below 400°C and 10% improvement above 400°C in Ca3Co4O9/Ag nanocomposites was achieved.

Lastly, this dissertation provides significant progress towards understanding the effect of synthesis method on thermoelectric properties and evolution of textured microstructure. The anisotropy resulting from the crystal structure and microstructural features is systematically quantified. Results reported in this study will assist the continued progress in developing Ca3Co4O9 materials for practical thermoelectric applications.

thermoelectric, doping, nanostructure, texturing, anisotropy, nanoinclusion