Made available in DSpace on 2015-05-08T14:57:19Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1298323 bytes, checksum: 6a19c3b38cf846b711c2c52ac67ab30a (MD5) Previous issue date: 2014-11-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A thermoelectric generator is a solid-state temperature dependent device that provide power generation on thermoelectric conversion. For that, the thermoelectric modules needs a temperature difference to ensure the thermoelectric conversion process. However, being subject to temperature variations may compromise the thermoelectric generator lifetime. Thus, in order to evaluate the temperature variation (thermal cycling) that the thermoelectric generators are exposed, this work has proposed an experimental platform that submits the thermoelectric generators modules to thermal cycling. With the experimental platform proposed the parameters of the thermoelectric generators may be to investigate properly. To evaluate the degradation effects on TEG the parameters were evaluated before the thermal cycling and then the parameters were evaluated after the thermal cycling process. At the research end, the parameters are presented by a comparative table with parameters evaluation before the thermal cycling and parameters evaluation after thermal cycling which brings to the experimental platform reliability. / Objetivo: Os geradores termoelétricos são dispositivos de estado sólido que utilizam a diferença de temperatura para a conversão em energia elétrica. No entanto, submeter os geradores termoelétricos a variações de temperatura pode comprometer o tempo de vida desses dispositivos. Assim, com o objetivo de investigar a possível influência das variações de temperatura ciclos térmicos a que os módulos geradores termoelétricos (TEGs) estão expostos, este trabalho desenvolveu uma plataforma experimental capaz de submeter TEGs à influência de ciclos térmicos, permitindo assim que os TEGs possam ser avaliados. Para constatar os efeitos na degradação do TEG, alguns parâmetros foram avaliados antes da aplicação dos ciclos térmicos e após uma sequência de ciclos térmicos. Ao fim da pesquisa, as avaliações feitas nos parâmetros são apresentadas em uma tabela comparativa, em que são apresentados os valores obtidos antes da aplicação dos ciclos térmicos e os valores dos parâmetros após a aplicação dos ciclos térmicos.

Face à la raréfaction des énergies fossiles, l’industrie automobile se trouve dans l’obligation de réduire la consommation des véhicules. L’une des idées est de récupérer l’énergie perdue sous forme d’échauffements grâce à la thermoélectricité. L’objectif de ces travaux est l’implantation d’un module thermoélectrique au niveau du radiateur afin d’en récupérer la chaleur dans le cadre d’un projet de recherche financé par Valéo Systèmes Thermiques et l’ADEME. La conception des radiateurs nécessite des épaisseurs supérieures à la centaine de micromètres de matériaux thermoélectriques afin d’en optimiser l’espace disponible. L’électrodéposition est apparue comme la technologie la plus adaptée car elle permet de déposer les matériaux directement sur l’ailette. Cette étude est consacrée aux dépôts électrochimiques de chalcogénures de bismuth (Bi2Te3 et Bi0,5Sb1,5Te3), matériaux les plus performants aux températures de fonctionnement de l’échangeur thermique. La première partie de ces travaux concerne la faisabilité de l’obtention de films d’épaisseurs supérieures à 100 µm et leurs caractérisations : stœchiométrie, structures et propriétés thermoélectriques. L’utilisation originale d’une anode soluble permet l’obtention de films de Bi2Te3 de près de 400 µm. Pour le composé ternaire, la synthèse consiste en une succession de couches de composés différents (Bi0,25Sb0,75-Te0), avant de procéder à leur interdiffusion via un traitement thermique. La dernière partie concerne la réalisation d’un module thermoélectrique. Les multiples étapes de lithographie et de synthèses électrochimiques ont été étudiées afin d’obtenir un module adapté aux échangeurs thermiques. Les caractérisations préliminaires de leurs propriétés montrent des résistances élevées et plusieurs voies d’améliorations sont proposées / In order to face the rarefaction of fossil fuels, the automotive industry has to find new ways to reduce their vehicle consumption. One of the possible ideas is to recover the energy that is lost as heating by using thermoelectricity. The aim of this work is to set-up thermoelectric generators into the radiator in order to recover this lost heat in a frame of research project financially supported by Valéo Systèmes Thermiques and ADEME. The radiator design requires thermoelectric materials thicknesses up to hundred micrometers in order to optimize the available space. Electroplating seems to be the best way to synthesize those materials directly onto the radiator fins. This study focuses on the electroplating of the best thermoelectric materials adapted to the operating temperatures of the heat exchanger: bismuth chalcogenides (Bi2Te3 and Bi0,5Sb1,5Te3). Firstly, a study has been carried out in order to synthesize thick layers above 100 µm of those two materials. Stoichiometry and thermoelectric properties were also determined. The original use of a soluble anode permitted to obtain 400 µm thick Bi2Te3 films. For the ternary compound, the synthesis consisting in a succession of thin layers of Bi0,25Sb0,75 and Te0, before their interdiffusion by annealing, is also presented. Finally, the last part covers the study carried out on the realization of the thermoelectric generators. The multiple stages of lithography and electrochemical syntheses were studied in order to obtain a module adapted to the heat exchanger. The first characterizations evidence high internal resistances and different ways to improve them are also presented

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Managing the thermal loads inside a non-airbreathing hypersonic vehicle is particularly difficult. The heat generated by the power electronics, avionics, etc. must be removed so that the components do not exceed their maximum temperatures. These vehicles cannot dump the waste heat into fuel or ram air because they carry no fuel and do not have provisions for ram air. This means that the thermal energy resulting from the heat generated must be dumped into an onboard heat sink. Existing solutions to this problem have been passive systems based on solid-liquid phase change materials (PCMs), which store thermal energy as they melt. Since space is at a premium, a heat sink must store a lot of energy per unit volume, while keeping components below their maximum temperature. In this project, three heat sink concepts are tested, i.e., one based on PCMs, a second on thermal to chemical (TTC) energy storage, and a third on a hybrid combination of the first two. For the first, three different PCMs are tested and for the second a single endothermic chemical reaction. The hybrid PCM/TTC concept consists of a single PCM which plays the dual role of PCM and reactant in the endothermic chemical reaction of the TTC energy storage. To enhance heat sink performance, the use of thermoelectric generators (TEGs) and a local coolant loop are investigated. The advantage of the former is that they transform waste heat into usable electricity, reducing the amount of thermal energy that needs to be stored by the heat sink. The advantage of the latter is that it results in a more uniform cooling of the heat source and more uniform heating of the heat sink. Prototypes of each of the heat sink concepts and the coolant loop are designed, built, and tested. Experimental results indicate that all the solutions tested in this project outperform widely used paraffin heat sink technologies on an energy per unit volume basis. Our experiments also show that a local coolant loop is indeed advantageous and that current off-the-shelf thermoelectric generators do not generate enough power to offset the power requirements of the coolant loop. Significant improvements in the ZT factor of the thermoelectric materials used by the TEG would be required. / Master of Science / All electronics produce waste heat and have a maximum operating temperature above which they fail due to overheating. Heat sinks absorb the waste heat and prevent overheating. Non-airbreathing hypersonic vehicles do not have natural heat sinks like intake air or liquid fuel which are commonly used as heat sinks in airbreathing vehicles. Heat cannot be transferred to the environment due to the high temperatures caused by the friction of hypersonic air travel. This means that all waste heat must absorbed by an onboard heat sink. Existing heat sinks in non-airbreathing hypersonic vehicles use paraffin based solid-liquid phase change materials (PCMs) which store thermal energy as they melt. Three novel heat sink options are evaluated in this project, hydrated salt PCMs which absorb energy as they melt, a chemical reaction which absorbs heat as it reacts, and a hybrid system which incorporates one of the hydrates salt PCM as a reactant in the chemical reaction. Because space is at a premium, these options are evaluated by the amount of energy they can absorb (kilojoules) per unit volume (in3) while keeping the electronics below their maximum temperature. To enhance heat sink performance, the use of thermoelectric generators (TEGs) and a local coolant loop are investigated. The advantage of the former is that they transform waste heat into usable electricity, reducing the amount of thermal energy that needs to be stored by the heat sink. The advantage of the latter is that it results in a more uniform cooling of the electronics and more uniform heating of the heat sink. Prototypes of each of the heat sink concepts and the coolant loop are designed, built, and tested. Experimental results indicate that all the solutions tested in this project outperform widely used paraffin heat sink technologies on an energy per unit volume basis. Our experiments also show that a local coolant loop is indeed advantageous and that current off-the-shelf thermoelectric generators do not generate enough power to offset the power requirements of the coolant loop. Significant improvements in the state of the art of thermoelectric materials would be required for TEGs to generate enough electricity from our waste heat load to power the local coolant loop.

Commercially available high-performance thermoelectric materials are often rare or toxic and therefore unsustainable. The present thesis work makes a case for eco-friendly, earth-abundant, and non-toxic p-type ceramic Cu2SnS3 (CTS, hereafter) and, in general, the use of disordered materials for thermoelectric applications. The detailed study of polymorphism, synthesis conditions, porosity, grain size, and doping provides a systematic and in-depth experimental and computational analysis of thermoelectric properties and stability of CTS. These results can be generalized for numerous thermoelectric materials and other applications. Moreover, a case for functioning thermoelectric generators using non-toxic and cost-effective materials is also presented. The thesis begins with a brief introduction to thermoelectricity, followed by a literature review and justification of the choice of the subject. The second chapter puts forward a novel approach to stabilize a disordered CTS polymorph without any chemical alteration through high-energy reactive ball milling. The third chapter deals with the stability of disordered samples under different synthesis and sintering conditions, highlighting the effect of synthesis environment, microstructure, and porosity. The fourth chapter employed a novel, facile, and cost-effective two-step synthesis method (high-energy ball milling combined with spark plasma sintering) to synthesize CTS bulk samples. The two-step synthesis method was able to constrain the CTS grain growth in the nanometric range, revealing the conductive nature of the CTS surfaces. The next chapter explores combining the two-step synthesis method with Ag substitution at the Sn lattice site to improve CTS's thermoelectric performance further. In the final stages of the thesis work, thin film thermoelectric generators were fabricated using CTS and similar chalcogenides, demonstrating power output comparable to existing thermoelectric materials used in the medium temperature range. The final chapter summarizes outlooks and future perspectives stemming from this research work.

The effects of greenhouse gases have seen a significant rise in recent years due to the use of fossil fuels like gasoline and diesel. Conversion of the energy stored in these fossil fuels to mechanical work is an extremely inefficient process which results in a high amount of energy rejected in the form of waste heat. Thermoelectric materials are able to harness this waste heat energy and convert it to electrical power. Thermoelectric devices work on the principle of the Seebeck effect, which states that if two junctions of dissimilar materials are at different temperatures, an electrical potential is developed across them. Even though these devices have small efficiencies, they are still an extremely effective way of converting low grade waste heat to usable electrical power. These devices have the added advantage of having no moving parts (solid state) which contributes to a long life of the device without needing much maintenance. The performance of thermoelectric generators is dependent on a non-dimensional figure of merit, ZT. Extensive research, both past and ongoing, is focused on improving the thermoelectric generator's (TEG's) performance by improving this figure of merit, ZT, by way of controlling the material properties. This research is usually incremental and the high performance materials developed can be cost prohibitive. The focus of this study has been to improve the performance of thermoelectric generator by way of improving the heat transfer from the exhaust gases to the TEG and also the heat transfer from TEG to the coolant. Apart from the figure of merit ZT, the performance of the TEG is also a function of the temperature difference across it, By improving the heat transfer between the TEG and the working fluid, a higher temperature gradient can be achieved across it, resulting in higher heat flux and improved efficiency from the system. This area has been largely neglected as a source of improvement in past research and has immense potential to be a low cost performance enhancer in such systems. Improvements made through this avenue, also have the advantage of being applicable regardless of the material in the system. Thus these high performance heat exchangers can be coupled with high performance materials to supplement the gains made by improved figure of merits. The heat exchanger designs developed and studied in this work have taken into account several considerations, like pressure drop, varying engine speeds, location of the system along the fuel path, system stability etc. A comprehensive treatment is presented here which includes 3D conjugate heat transfer modeling with RANS based turbulence models on such a system. Various heat transfer enhancement features are implemented in the system and studied numerically as well as experimentally. The entire system is also studied experimentally in a scaled down setup which provided data for validation of numerical studies. With the help of measured and calculated data like temperature, ZT etc, predictions are also presented about key metrics of system performance. / Ph. D.

Research in sustainable energy sources has become the interest of many studies due to the increasing energy demand and the amount of wasted energy released from existing methods, along with their effect on climate change and environment sustainability. Thermo-Electric Generators (TEGs) are a potential solution that is being studied and implemented as they can convert low grade thermal energy to useful electrical energy at various operating conditions. The integration of a TEG within a heat exchanger (TEG/HX) system connected to an electrical DC micro-grid, using a Maximum Power Point Tracking (MPPT) system is the focus of this study. Using a numerical TEG/HX model from a previous study and a developed DC micro-grid model the interaction between the thermal and electrical aspects were investigated with the focus on the electrical performance of the system. The main concern of this study is to investigate the effect of the sub components of the DC micro-grid on the overall available energy. An analytic model was developed to estimate the power loss in the electrical circuit of the micro-grid, the model utilizes the equations for switching and conduction losses which have been used by several studies. Other variables such as the battery characteristics and electrical load profiles were also investigated by simulating several case studies including changing operating conditions. This study shows the effect of a TEG configuration on the power loss in an electrical system using power loss curves in comparison with the Open Circuit Voltage (OCV) of such configuration. It also covers important modes of operation for the battery, loads and MPPT for a stable and reliable operation of an isolated DC micro-grid system were TEGs are the only source of power. The result of the study presented is a system design that is able to maximize the electrical energy harvested from the TEGs to extend the operation of the dc-micro-grid first by applying a suitable TEG configuration and consequently a suitable electrical circuit. Secondly, by adapting to the changing operating conditions of the TEGs and the loads; and compensating for these changes using the battery storage system. / Thesis / Master of Applied Science (MASc)

To support the growing global demand for energy, new sustainable solutions are needed both economically and environmentally. Thermoelectric waste heat recovery and energy harvesting could contribute by increasing industrial process efficiency, as well as powering stand-alone devices, microgenerators, and small body appliances.The structural complexity of quaternary chalcogenide materials provides an opportunity for engineering defects and disorder, to modify and possibly improve specific properties. Cu2ZnSnS4 (CZTS, often kesterite), valued for the abundance and non-toxicity of the raw materials, seems particularly suited to explore these possibilities, as it presents several structural defects and polymorphic phase transformations. The aim of this doctoral work is to systematically investigate the effects of structural polymorphism, disorder, and defects on the thermoelectric properties of CZTS, with particular emphasis to their physical origin. A remarkable case is the order-disorder transition of tetragonal CZTS, which is found responsible for a sharp enhancement in the Seebeck coefficient due to a flattening and degeneracy of the electronic energy bands. This effect, involving a randomization of Cu and Zn cations in certain crystallographic planes, is verified in bulk and thin film samples, and applications are proposed to exploit the reversible dependence of electronic properties on disorder. Low-temperature mechanical alloying is instead discovered stabilizing a novel polymorph of CZTS, which disordered cubic structure is studied in detail, and proposed deriving from sphalerite-ZnS. The total cation disorder in this compound provides an uncommon occurrence in thermoelectricity: a concurrent optimization of Seebeck coefficient, electrical and thermal conductivity. These findings, besides providing new and general understanding of CZTS, can cast light on profitable mechanisms to enhance the thermoelectric performance of semiconducting chalcogenides, as well as delineate alternative and fruitful applications.