Thesis advisor: Cyril P. Opeil / Thermoelectric (TE) energy conversion is an all-solid-state technology which can convert waste thermal energy into useful electric power and cool ambience without using harmful gases like CFC. Due to their several advantages over traditional energy conversion technologies, thermoelectric generators (TEG) and coolers (TEC) have drawn enormous research efforts. The objective of this work is to find promising materials for thermoelectric cooling applications and optimize their thermoelectric performances. Finding a material with a good value for the thermoelectric figure-of-merit (ZT) at cryogenic temperatures, specifically below 77 K, has been of great interest. This work demonstrates that FeSb2, CeCu6 and CeAl3, all belonging to a class of materials with strongly correlated electron behavior; exhibit promising thermoelectric properties below 77 K. In general, ZT of a TE material can be increased using two basic approaches: lattice thermal conductivity reduction and power factor (PF) enhancement. The results of this study indicate that nanostructuring effectively decreases the thermal conductivity of FeSb2, CeCu6 and CeAl3 leading to improved ZT. The approach of introducing point-defect scattering to further reduce the thermal conductivity is successfully implemented for Te-substituted FeSb2 nanostructured samples. A semiconductor/metal interface has long been proposed to exhibit enhanced thermoelectric properties. We use this technique by introducing Ag-nanoparticles in the host FeSb2 which further increases ZT by 70%. Additionally, a detailed investigation is made on the phonon-drag effect as a possible mechanism responsible for the large value of the Seebeck coefficient of FeSb2. We show that the phonon-drag mechanism contributes significantly to the large Seebeck effect in FeSb2 and hence this effect cannot be minor as was proposed in literatures previously. A model based on Kapitza-resistance and effective medium approach (EMA) is used to analyze the thermal conductivities of nanostructured FeSb2 samples. We find a notably large value for Kapitza length at low temperatures indicating the dominance of inter-grain thermal resistance over bulk thermal resistance in determining the thermal properties of FeSb2. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Current fossil fuel based energy sources have a huge shortcoming when one discusses their efficiency. The conversion efficiency of fossil fuel-based technologies is less than 40% in best cases. Therefore, until the renewable energy section is mature enough to handle all the energy demand one has to research and develop the technologies available to harvest the energy from the waste heat generated in fossil fuel-based supply sources. One of these emerging technologies is the use of thermoelectric (TE) devices to achieve this goal, which are solid-state devices capable of directly interconverting between heat and electrical energy. In the past decade there has been a significant scientific and financial investment within the field to enhance their properties and result in time/energy efficient fabrication processes of TE materials and devices for a more sustainable environment. In this thesis with use of chemical synthesis routes for nanostructured bulk thermoelectric materials iron antimonide (FeSb2), skutterudites (based on general formula of RzMxCo1-xSb3-yNy) and copper selenide (Cu2Se) are developed. These materials are promising candidates for use in thermoelectric generators (TEG) or for sensing applications. Using chemical synthesis routes such as chemical co-precipitation, salt melting in marginal solvents and thermolysis, fabrication of these TE materials with good performance can be performed with high degree of reproducibility, in a much shorter time, and easily scalable manner for industrial processes. The TE figure of merit ZT of these materials is comparable to, or better than their conventional method counterparts to ensure the applicability of these processes in industrial scale. Finally, through thorough investigation, optimized consolidation parameters were generated for compaction of each family of materials using Spark Plasma Sintering technique (SPS). As each family of TE nanomaterial investigated in this thesis had little to no prior consolidation literature available, specific parameters had to be studied and generated. The aim of studies on compaction parameters were to focus on preservation of the nanostructured features of the powder while reaching a high compaction density to have positive effects on the materials TE figure of merit. / Dagens fossilbränslebaserade energikällor har en enorm brist gällande effektivitet. Effektiviteten av fossilbränslebaserade teknologiers omvandling är mindre än 40 % i bästa fall. Därför tills förnybar energi är mogen nog att hantera alla energibehov, måste man forska och utveckla teknik för att skörda energi från spillvärme i fossilbränslebaserade försörjningskällor. En av dessa nya tekniker är tillämpning av termoelektriska (TE) material för att uppnå målet. Nämnde material är Soldi-State materialer som kan transformera mellan värme och elektrisk energi. Under det senaste decenniet har det pågått en stor vetenskaplig och ekonomisk investering inom området för att förbättra termoelektriska materials egenskaper. Dessutom ville man ta fram tid/energieffektiva TE material och komponenter för en mer hållbar miljö. I denna avhandling utvecklades och producerades termoelektriska material såsom järn antimonid (FeSb2), skutterudit (baserat på allmänna formeln RzMxCo1-xSb3-YNY) och koppar selenid (Cu2Se) med hjälp av kemiska syntesmetoder. Genom att Använda kemiska syntesmetoder som kemisk samutfällning, salt smältning i marginella lösningsmedel och termolys, kan material med hög grad av reproducerbarhet och ställbar för industriella processer tillverkas.   Termoelektrisk omvandling effektivitet hos uppnådde material är betydligt högre än resultat av andra studier. I och med detta kan man säga att materialet kan användas inom industri. Slutligen, genom en grundlig undersökning optimerades packningsparametrar som genererades för packning av varje materialgrupp med hjälp av Spark Plasma Sintring teknik (SPS). Eftersom ingen relevant studie finns för varje grupp av termoelektriska nanomaterial som undersökts i denna avhandling, studerades och genererades dessa specifika parametrar. Syftet med studien är att fokusera på bevarande av nanostrukturerade egenskaperna hos pulvret och att samtidigt nå en hög packningstäthet för att ha positiva effekter på materialens termoelektriska omvandlingseffektivitet. / <p>QC 20160503</p> / NEXTEC / SCALTEG