Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance
In this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu<sub>12</sub>Sb<sub>4−x</sub>Bi<sub>x</sub>S<sub>13</sub> (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-ene...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-05-01
|
| Series: | Nanomaterials |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2079-4991/11/6/1386 |
| _version_ | 1797532826470449152 |
|---|---|
| author | Peter Baláž Emmanuel Guilmeau Marcela Achimovičová Matej Baláž Nina Daneu Oleksandr Dobrozhan Mária Kaňuchová |
| author_facet | Peter Baláž Emmanuel Guilmeau Marcela Achimovičová Matej Baláž Nina Daneu Oleksandr Dobrozhan Mária Kaňuchová |
| author_sort | Peter Baláž |
| collection | DOAJ |
| description | In this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu<sub>12</sub>Sb<sub>4−x</sub>Bi<sub>x</sub>S<sub>13</sub> (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> (71–87%) and famatinite Cu<sub>3</sub>SbS<sub>4</sub> (13–21%), together with small amounts of skinnerite Cu<sub>3</sub>SbS<sub>3</sub>, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi<sup>0</sup> and Bi<sup>3+</sup> are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity (<i>κ</i>) with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of <i>κ</i> was achieved for x = 0.2 (1.1 W m<sup>−1</sup> K<sup>−1</sup> at 675 K). However, this sample also manifests the lowest electrical conductivity <i>σ</i>, combined with relatively unchanged values for the Seebeck coefficient (<i>S</i>) compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions. |
| first_indexed | 2024-03-10T11:05:49Z |
| format | Article |
| id | doaj.art-daa017b6c65941cebf84d06c493b23c3 |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-10T11:05:49Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-daa017b6c65941cebf84d06c493b23c32023-11-21T21:12:53ZengMDPI AGNanomaterials2079-49912021-05-01116138610.3390/nano11061386Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric PerformancePeter Baláž0Emmanuel Guilmeau1Marcela Achimovičová2Matej Baláž3Nina Daneu4Oleksandr Dobrozhan5Mária Kaňuchová6Institute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, SlovakiaCRISMAT, CNRS, Normandy University, ENSICAEN, UNICAEN, 14000 Caen, FranceInstitute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, SlovakiaInstitute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, SlovakiaJozef Stefan Institute, SI-1000 Ljubljana, SloveniaDepartment of Electronics and Computer Technology, Sumy State University, 40007 Sumy, UkraineInstitute of Earth Resources, Technical University Košice, 04001 Košice, SlovakiaIn this study, we demonstrate the feasibility of Bi-doped tetrahedrite Cu<sub>12</sub>Sb<sub>4−x</sub>Bi<sub>x</sub>S<sub>13</sub> (x = 0.02–0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub> (71–87%) and famatinite Cu<sub>3</sub>SbS<sub>4</sub> (13–21%), together with small amounts of skinnerite Cu<sub>3</sub>SbS<sub>3</sub>, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi<sup>0</sup> and Bi<sup>3+</sup> are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity (<i>κ</i>) with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of <i>κ</i> was achieved for x = 0.2 (1.1 W m<sup>−1</sup> K<sup>−1</sup> at 675 K). However, this sample also manifests the lowest electrical conductivity <i>σ</i>, combined with relatively unchanged values for the Seebeck coefficient (<i>S</i>) compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions.https://www.mdpi.com/2079-4991/11/6/1386tetrahedritedopingbismuthhigh-energy millingthermoelectricity |
| spellingShingle | Peter Baláž Emmanuel Guilmeau Marcela Achimovičová Matej Baláž Nina Daneu Oleksandr Dobrozhan Mária Kaňuchová Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance Nanomaterials tetrahedrite doping bismuth high-energy milling thermoelectricity |
| title | Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance |
| title_full | Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance |
| title_fullStr | Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance |
| title_full_unstemmed | Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance |
| title_short | Bismuth Doping in Nanostructured Tetrahedrite: Scalable Synthesis and Thermoelectric Performance |
| title_sort | bismuth doping in nanostructured tetrahedrite scalable synthesis and thermoelectric performance |
| topic | tetrahedrite doping bismuth high-energy milling thermoelectricity |
| url | https://www.mdpi.com/2079-4991/11/6/1386 |
| work_keys_str_mv | AT peterbalaz bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT emmanuelguilmeau bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT marcelaachimovicova bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT matejbalaz bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT ninadaneu bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT oleksandrdobrozhan bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance AT mariakanuchova bismuthdopinginnanostructuredtetrahedritescalablesynthesisandthermoelectricperformance |