Bottom-up Engineering of Chalcogenide Thermoelectric Nanomaterials

Download or read book Bottom-up Engineering of Chalcogenide Thermoelectric Nanomaterials written by Yu Liu and published by . This book was released on 2018 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt: In this thesis, it is detailed the bottom-up production and characterization of thermoelectric (TE) nanomaterials with significant enhanced performance by using colloidal nanocrystals (NCs) as building blocks. The production of TE nanomaterials with significant improved figure of merit (ZT), has to do, not only with the precise control of the NCs properties, but also with the further fine control over the crystallographic alignment of nanograins of highly anisotropic materials. The first part of the thesis correspond to the study of synthetic routes to produce high quality chalcogenide NCs that are doped during the NC synthesis, in order to control the charge carrier concentration. The system studied was I−V−VI chalcogenide semiconductor, specifically it was produced the materials: AgSbSe2 and Cu3SbSe4. A low-cost, high-yield and scalable synthesis route to produce monodisperse of AgSbSe2 and Cu3SbSe4 NCs was obtained. After ligand displacement, the NCs were used as building blocks to produce TE nanomaterials. Additionally, by means of substitutional doping, a large increment in the power factor and relatively lower thermal conductivities were observed. The optimization of the doping concentration resulted in ZT values of 1.10 at 640 K for AgSb0.98Bi0.02Se2, and of 1.26 at 673 K for Cu3Sb0.88Sn0.10Bi0.02Se4, which represents a significant increase beyond the state of the art in Te-free multinary Ag/Cu-based chalcogenide materials. In the second part of the thesis, the work about PbS-metal (Cu and Sn) nanocomposites produced by blending procedure is presented. The low work function metal is able to inject electrons to the intrinsic PbS matrix, which is another strategy to control the charge carrier concentration. The power factor is dramatically enhanced due to the increase of the electrical conductivity in the nanocomposites. Consequently, the ZTmax was remarkably enhanced by two times as compared with the pristine PbS. Furthermore, we also compared the TE performance of microcrystalline composites with the same composition as in nanocrystalline composites; commercial PbS host with Cu particles. The results revealed that with the same metal addition, higher electrical conductivities were obtained in the nanocomposite, but higher Seebeck coefficients were maintained in the microcomposite. Moreover, higher thermal conductivities were also obtained in the microcomposite. Finally, the figure of merit ZT were higher for the microcomposite system in the low temperature range, but much lower in the higher temperature range compared with the nanocomposites system. In the last block, the process of production of crystallographically textured materials is presented. We face here the challenge of bottom-up approaches to control the crystallographic alignment of nanograins. The production of nanostructured Bi2Te3-based alloys is presented. This can be done with controlled stoichiometry by solution-processing, and crystallographic texture by liquid-phase sintering using multiple pressure and release steps at 480 °C, above the tellurium melting point. Additionally, we explain the possible mechanism to produce the highly textured nanomaterials. This strategy results in record TE figures of merit: ZT=1.83 at 420 K for Bi0.5Sb2.5Te3 and ZT=1.31 for Bi2Te2.7Se0.3 at 440 K when averaged over 5 materials in the c direction, respectively. These high figures of merit extended over a wide temperature range, which results in energy conversion efficiencies a 50% higher than commercial ingots in the similar temperature range. In summary, different strategies to improve the TE performance of bulk nanostructured materials produced by bottom-up engineering of NCs, have been studied and confirmed in this thesis. Additionally, it has been proven that the solution-processed synthesis approach is low-cost, compatible with the scale-up engineering, and also versatile in tuning the size, shape, composition, and microstructure, among others parameters of different nanomaterials to optimize their TE properties.