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Development of half-Heusler type thermoelectrical materials in a range of temperature from 300 to 500 ° C

Abstract : The search for alternative energy technologies has taken an accelerated pace in the last 50 years due to an increasing concern about climate change. In this quest to find new energy sources, it is interesting to point out that a lot of energy is wasted as heat released into the environment. As a potential solution, thermoelectric power generators could be used to transform the waste heat into useful electrical energy.Thermoelectric generators are converting directly heat into electricity and vice versa. They consist in an assembly of n and p-type semiconducting legs connected electrically in series and thermally in parallel. An applied temperature difference between n and p-sides drives charge carriers displacement in the material from the hot side to the cold one. Therefore a current flow is generated through the circuit. Thermoelectric devices have attracted interest because of their advantages over conventional power generator: no moving part, no liquid involved, reliability, noiseless, long life time without maintenance and also low environmental impact.Over the last several decades, the increased energy demand combined to the environmental concerns, leads to another potential use of thermoelectricity as an alternative energy source by recovering the huge amount of heat lost in industrial or domestic applications. Presently, wasted-heat recovery in cars and trucks and wasted-heat in industry (metallurgy/nuclear…) are becoming a major concern. Both recovery problematics may be addressed using thermoelectric devices efficient in the 300-500 °C temperature range.Numerous thermoelectric materials couples have been investigated and developed over the last 20 years. Most of the already known class of thermoelectric materials have been improved and new classes have been developed, leading to a significant improvement of ZT values being optimum in different temperature ranges. In order to be efficient and to be viable for large scale manufacturing of power generators, a thermoelectric material has to fulfill several requirements. First, the raw materials chosen have to be non-toxic, cheap and abundant. Secondly, the manufacturing process should be robust and compatible to the production of a high volume of materials per day. Last but not least, the elaborated materials have to exhibit acceptable thermoelectric properties in the temperature range of interest for the final application. They must also have a long-term thermal stability in different kinds of environments and good mechanical properties.Half-Heusler materials have been shown to be good candidates in the 300 to 600 °C temperature range. Indeed, due to their semiconductor like band structure, they exhibit a large Seebeck coefficient and high electrical conductivity. Unfortunately, half-Heusler’s thermal conductivity is rather high when compared to other thermoelectric materials. Therefore, the main research efforts on half-Heusler formulations, devoted to be used for thermoelectric applications, have been focused on decreasing the thermal conductivity, while keeping a good electronic transport.Accordingly the main objective of the PhD thesis was to investigate the link between the microstructure and the thermoelectric properties of n and p-type half-Heusler alloys from the generic compositions MNiSn (n-type) and MCoSb (p-type), with M being Ti, Zr and Hf. All investigated compositions have been elaborated by a three step process: (i) ingots synthesis using cold crucible levitation melting, (ii) subsequent ball milling to obtain a calibrated powder and (iii) sintering by spark plasma sintering to obtain dense polycrystalline pellets that are characterized regarding their microstructure and thermoelectric properties from room temperature to 500-600 °C.
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Alizée Visconti. Development of half-Heusler type thermoelectrical materials in a range of temperature from 300 to 500 ° C. Thermics [physics.class-ph]. Université Grenoble Alpes, 2017. English. ⟨NNT : 2017GREAI112⟩. ⟨tel-01796818⟩

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