Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications
Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoe...
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MDPI AG
2023-01-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/2/366 |
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| author | Himanshu Nautiyal Ketan Lohani Binayak Mukherjee Eleonora Isotta Marcelo Augusto Malagutti Narges Ataollahi Ilaria Pallecchi Marina Putti Scott T. Misture Luca Rebuffi Paolo Scardi |
| author_facet | Himanshu Nautiyal Ketan Lohani Binayak Mukherjee Eleonora Isotta Marcelo Augusto Malagutti Narges Ataollahi Ilaria Pallecchi Marina Putti Scott T. Misture Luca Rebuffi Paolo Scardi |
| author_sort | Himanshu Nautiyal |
| collection | DOAJ |
| description | Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu<sub>2</sub>SnS<sub>3</sub> (CTS), Cu<sub>2</sub>ZnSnS<sub>4</sub> (CZTS), and Cu<sub>2</sub>ZnSnSe<sub>4</sub> (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass–electron-crystal behavior—a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs. |
| first_indexed | 2024-03-09T11:32:13Z |
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| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-09T11:32:13Z |
| publishDate | 2023-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-0779c4041b5142b0b4daf7789f7e3fb02023-11-30T23:48:54ZengMDPI AGNanomaterials2079-49912023-01-0113236610.3390/nano13020366Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric ApplicationsHimanshu Nautiyal0Ketan Lohani1Binayak Mukherjee2Eleonora Isotta3Marcelo Augusto Malagutti4Narges Ataollahi5Ilaria Pallecchi6Marina Putti7Scott T. Misture8Luca Rebuffi9Paolo Scardi10Department of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyDepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyDepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyDepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyDepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyDepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyConsiglio Nazionale delle Ricerche—SuPerconducting and Other INnovative Materials and Devices Institute (CNR-SPIN), Department of Physics, Via Dodecaneso 33, 16146 Genova, ItalyDepartment of Physics, University of Genova, Via Dodecaneso 33, 16146 Genova, ItalyDepartment of Materials Science & Engineering, Alfred University, Alfred, NY 14802, USAArgonne National Laboratory, 9700 South Cass Avenue, Lemont, IL 60439, USADepartment of Civil, Environmental and Mechanical Engineering, University of Trento, Via Mesiano 77, 38123 Trento, ItalyCopper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu<sub>2</sub>SnS<sub>3</sub> (CTS), Cu<sub>2</sub>ZnSnS<sub>4</sub> (CZTS), and Cu<sub>2</sub>ZnSnSe<sub>4</sub> (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass–electron-crystal behavior—a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs.https://www.mdpi.com/2079-4991/13/2/366Cu-based ternaries and quaternariesthermoelectricityCu<sub>2</sub>ZnSnS<sub>4</sub>Cu<sub>2</sub>ZnSnSe<sub>4</sub>Cu<sub>2</sub>SnS<sub>3</sub>mechanochemistry |
| spellingShingle | Himanshu Nautiyal Ketan Lohani Binayak Mukherjee Eleonora Isotta Marcelo Augusto Malagutti Narges Ataollahi Ilaria Pallecchi Marina Putti Scott T. Misture Luca Rebuffi Paolo Scardi Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications Nanomaterials Cu-based ternaries and quaternaries thermoelectricity Cu<sub>2</sub>ZnSnS<sub>4</sub> Cu<sub>2</sub>ZnSnSe<sub>4</sub> Cu<sub>2</sub>SnS<sub>3</sub> mechanochemistry |
| title | Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications |
| title_full | Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications |
| title_fullStr | Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications |
| title_full_unstemmed | Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications |
| title_short | Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu<sub>2</sub>SnS<sub>3</sub>, Cu<sub>2</sub>ZnSnS<sub>4</sub>, and Cu<sub>2</sub>ZnSnSe<sub>4</sub> Chalcogenides for Thermoelectric Applications |
| title_sort | mechanochemical synthesis of sustainable ternary and quaternary nanostructured cu sub 2 sub sns sub 3 sub cu sub 2 sub znsns sub 4 sub and cu sub 2 sub znsnse sub 4 sub chalcogenides for thermoelectric applications |
| topic | Cu-based ternaries and quaternaries thermoelectricity Cu<sub>2</sub>ZnSnS<sub>4</sub> Cu<sub>2</sub>ZnSnSe<sub>4</sub> Cu<sub>2</sub>SnS<sub>3</sub> mechanochemistry |
| url | https://www.mdpi.com/2079-4991/13/2/366 |
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