Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System
For the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide–copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, whic...
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MDPI AG
2021-05-01
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| author | Andrzej Mikuła Krzysztof Mars Paweł Nieroda Paweł Rutkowski |
| author_facet | Andrzej Mikuła Krzysztof Mars Paweł Nieroda Paweł Rutkowski |
| author_sort | Andrzej Mikuła |
| collection | DOAJ |
| description | For the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide–copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, which indicate the instability of Sb-doped copper chalcogenide, the Cu<sub>1.97</sub>S–Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> and Cu<sub>2−x</sub>Se–Cu<sub>3</sub>SbSe<sub>3</sub> composites are obtained using melt-solidification techniques, with the tetrahedrite phase concentration varying from 1 to 10 wt.%. Room temperature structural analysis (XRD, SEM) indicates the two-phase structure of the materials, with ternary phase precipitates embed within the copper chalcogenide matrix. The proposed solution allows for successful blocking of excessive Cu migration, with stable electrical conductivity and Seebeck coefficient values over subsequent thermal cycles. The materials exhibit a p-type, semimetallic character with high stability, represented by a near-constant power factor (PF)—temperature dependences between individual cycles. Finally, the thermoelectric figure-of-merit ZT parameter reaches about 0.26 (623 K) for the Cu<sub>1.97</sub>S–Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> system, in which case increasing content of tetrahedrite is a beneficial effect, and about 0.44 (623 K) for the Cu<sub>2−x</sub>Se–Cu<sub>3</sub>SbSe<sub>3</sub> system, where increasing the content of Cu<sub>3</sub>SbSe<sub>3</sub> negatively influences the thermoelectric performance. |
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| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-10T11:18:27Z |
| publishDate | 2021-05-01 |
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| series | Materials |
| spelling | doaj.art-cedab2299d344bbd9ce33cd7eaecef752023-11-21T20:13:55ZengMDPI AGMaterials1996-19442021-05-011410263510.3390/ma14102635Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide SystemAndrzej Mikuła0Krzysztof Mars1Paweł Nieroda2Paweł Rutkowski3Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, PolandFaculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, PolandFaculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, PolandFaculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow, PolandFor the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide–copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, which indicate the instability of Sb-doped copper chalcogenide, the Cu<sub>1.97</sub>S–Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> and Cu<sub>2−x</sub>Se–Cu<sub>3</sub>SbSe<sub>3</sub> composites are obtained using melt-solidification techniques, with the tetrahedrite phase concentration varying from 1 to 10 wt.%. Room temperature structural analysis (XRD, SEM) indicates the two-phase structure of the materials, with ternary phase precipitates embed within the copper chalcogenide matrix. The proposed solution allows for successful blocking of excessive Cu migration, with stable electrical conductivity and Seebeck coefficient values over subsequent thermal cycles. The materials exhibit a p-type, semimetallic character with high stability, represented by a near-constant power factor (PF)—temperature dependences between individual cycles. Finally, the thermoelectric figure-of-merit ZT parameter reaches about 0.26 (623 K) for the Cu<sub>1.97</sub>S–Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> system, in which case increasing content of tetrahedrite is a beneficial effect, and about 0.44 (623 K) for the Cu<sub>2−x</sub>Se–Cu<sub>3</sub>SbSe<sub>3</sub> system, where increasing the content of Cu<sub>3</sub>SbSe<sub>3</sub> negatively influences the thermoelectric performance.https://www.mdpi.com/1996-1944/14/10/2635compositecopper chalcogenidetetrahedritethermoelectrics |
| spellingShingle | Andrzej Mikuła Krzysztof Mars Paweł Nieroda Paweł Rutkowski Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System Materials composite copper chalcogenide tetrahedrite thermoelectrics |
| title | Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System |
| title_full | Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System |
| title_fullStr | Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System |
| title_full_unstemmed | Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System |
| title_short | Copper Chalcogenide–Copper Tetrahedrite Composites—A New Concept for Stable Thermoelectric Materials Based on the Chalcogenide System |
| title_sort | copper chalcogenide copper tetrahedrite composites a new concept for stable thermoelectric materials based on the chalcogenide system |
| topic | composite copper chalcogenide tetrahedrite thermoelectrics |
| url | https://www.mdpi.com/1996-1944/14/10/2635 |
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