Publicação
Tetrahedrites for Thermoelectric Applications Data Mining Insights and Copper substitution Strategies for Stable High-Performance Tetrahedrites
| Resumo: | Compounds with the general formula Cu12-xMxSb4S13 (M = transitional metal), known as tetrahedrites, are promising thermoelectric materials due to their earth-abundant elemental composition and intrinsically low thermal conductivity. In base-metal extractive metallurgy (e.g., copper and zinc), mineral tetrahedrite is typically discarded as waste; reclaiming this sulphosalt offers a direct route to upcycling gangue minerals into thermoelectric devices. Although numerous studies report Cu-substituted tetrahedrites with relatively high dimensionless figure of merit (zT), a consolidated analysis to guide future research has been lacking. This work presents a comprehensive review of the thermoelectric behaviour of bulk synthetic tetrahedrites produced by powder-processing routes (mechanochemical synthesis followed by pressure-assisted sintering). A dataset exceeding 8,000 data points has been compiled from 60 publications—extracted using manual and AI-assisted methods—covering Seebeck coefficient, electrical conductivity, thermal conductivity, zT and processing metadata. The influence of substitution elements and sintering techniques on transport properties was assessed. In addition, the role of Cu substitution in enhancing thermal stability has been investigated, focusing on mitigating oxidation and sulphur volatilization under service conditions (350 ºC in air). A systematic screening of a tetrahedrite series with M = Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Zr, Nb, Mo, and W, was conducted using thermal gravimetry, X-ray diffraction, and electron microscopy. Zn- and Ni-doped samples exhibited the most stable behaviour, and, under well-sintered conditions, achieved record zT values of ≈1.5 at 350 °C. Overall, the present results indicate that dopant choice is less critical than commonly assumed in the literature, while sintering parameters likely play a more significant role in determining the thermoelectric behaviour of bulk synthetic tetrahedrites. |
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| Autores principais: | Quitério, Catarina Maia |
| Assunto: | Thermoelectric properties Tetrahedrites Data mining Doping Thermal stability |
| Ano: | 2025 |
| País: | Portugal |
| Tipo de documento: | dissertação de mestrado |
| Tipo de acesso: | acesso embargado |
| Instituição associada: | Universidade Nova de Lisboa |
| Idioma: | inglês |
| Origem: | Repositório Institucional da UNL |
| Resumo: | Compounds with the general formula Cu12-xMxSb4S13 (M = transitional metal), known as tetrahedrites, are promising thermoelectric materials due to their earth-abundant elemental composition and intrinsically low thermal conductivity. In base-metal extractive metallurgy (e.g., copper and zinc), mineral tetrahedrite is typically discarded as waste; reclaiming this sulphosalt offers a direct route to upcycling gangue minerals into thermoelectric devices. Although numerous studies report Cu-substituted tetrahedrites with relatively high dimensionless figure of merit (zT), a consolidated analysis to guide future research has been lacking. This work presents a comprehensive review of the thermoelectric behaviour of bulk synthetic tetrahedrites produced by powder-processing routes (mechanochemical synthesis followed by pressure-assisted sintering). A dataset exceeding 8,000 data points has been compiled from 60 publications—extracted using manual and AI-assisted methods—covering Seebeck coefficient, electrical conductivity, thermal conductivity, zT and processing metadata. The influence of substitution elements and sintering techniques on transport properties was assessed. In addition, the role of Cu substitution in enhancing thermal stability has been investigated, focusing on mitigating oxidation and sulphur volatilization under service conditions (350 ºC in air). A systematic screening of a tetrahedrite series with M = Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Zr, Nb, Mo, and W, was conducted using thermal gravimetry, X-ray diffraction, and electron microscopy. Zn- and Ni-doped samples exhibited the most stable behaviour, and, under well-sintered conditions, achieved record zT values of ≈1.5 at 350 °C. Overall, the present results indicate that dopant choice is less critical than commonly assumed in the literature, while sintering parameters likely play a more significant role in determining the thermoelectric behaviour of bulk synthetic tetrahedrites. |
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