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      Entropy engineering promotes thermoelectric performance in p-type chalcogenides

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          Abstract

          We demonstrate that the thermoelectric properties of p-type chalcogenides can be effectively improved by band convergence and hierarchical structure based on a high-entropy-stabilized matrix. The band convergence is due to the decreased light and heavy band energy offsets by alloying Cd for an enhanced Seebeck coefficient and electric transport property. Moreover, the hierarchical structure manipulated by entropy engineering introduces all-scale scattering sources for heat-carrying phonons resulting in a very low lattice thermal conductivity. Consequently, a peak zT of 2.0 at 900 K for p-type chalcogenides and a high experimental conversion efficiency of 12% at Δ T = 506 K for the fabricated segmented modules are achieved. This work provides an entropy strategy to form all-scale hierarchical structures employing high-entropy-stabilized matrix. This work will promote real applications of low-cost thermoelectric materials.

          Abstract

          The synergism of entropy engineering and the typical optimization mechanisms in high-entropy-stabilized chalcogenide is unknown. Here, the authors find high-entropy-stabilized composition works as a promising matrix of applying synergistic effect to realize high thermoelectric performance.

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          Most cited references64

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          Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes

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            Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals.

            The thermoelectric effect enables direct and reversible conversion between thermal and electrical energy, and provides a viable route for power generation from waste heat. The efficiency of thermoelectric materials is dictated by the dimensionless figure of merit, ZT (where Z is the figure of merit and T is absolute temperature), which governs the Carnot efficiency for heat conversion. Enhancements above the generally high threshold value of 2.5 have important implications for commercial deployment, especially for compounds free of Pb and Te. Here we report an unprecedented ZT of 2.6 ± 0.3 at 923 K, realized in SnSe single crystals measured along the b axis of the room-temperature orthorhombic unit cell. This material also shows a high ZT of 2.3 ± 0.3 along the c axis but a significantly reduced ZT of 0.8 ± 0.2 along the a axis. We attribute the remarkably high ZT along the b axis to the intrinsically ultralow lattice thermal conductivity in SnSe. The layered structure of SnSe derives from a distorted rock-salt structure, and features anomalously high Grüneisen parameters, which reflect the anharmonic and anisotropic bonding. We attribute the exceptionally low lattice thermal conductivity (0.23 ± 0.03 W m(-1) K(-1) at 973 K) in SnSe to the anharmonicity. These findings highlight alternative strategies to nanostructuring for achieving high thermoelectric performance.
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              Convergence of electronic bands for high performance bulk thermoelectrics.

              Thermoelectric generators, which directly convert heat into electricity, have long been relegated to use in space-based or other niche applications, but are now being actively considered for a variety of practical waste heat recovery systems-such as the conversion of car exhaust heat into electricity. Although these devices can be very reliable and compact, the thermoelectric materials themselves are relatively inefficient: to facilitate widespread application, it will be desirable to identify or develop materials that have an intensive thermoelectric materials figure of merit, zT, above 1.5 (ref. 1). Many different concepts have been used in the search for new materials with high thermoelectric efficiency, such as the use of nanostructuring to reduce phonon thermal conductivity, which has led to the investigation of a variety of complex material systems. In this vein, it is well known that a high valley degeneracy (typically ≤6 for known thermoelectrics) in the electronic bands is conducive to high zT, and this in turn has stimulated attempts to engineer such degeneracy by adopting low-dimensional nanostructures. Here we demonstrate that it is possible to direct the convergence of many valleys in a bulk material by tuning the doping and composition. By this route, we achieve a convergence of at least 12 valleys in doped PbTe(1-x)Se(x) alloys, leading to an extraordinary zT value of 1.8 at about 850 kelvin. Band engineering to converge the valence (or conduction) bands to achieve high valley degeneracy should be a general strategy in the search for and improvement of bulk thermoelectric materials, because it simultaneously leads to a high Seebeck coefficient and high electrical conductivity. ©2011 Macmillan Publishers Limited. All rights reserved
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                Author and article information

                Contributors
                hejq@sustech.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                28 May 2021
                28 May 2021
                2021
                : 12
                : 3234
                Affiliations
                [1 ]GRID grid.263817.9, Shenzhen Key Laboratory of Thermoelectric Materials, Department of Physics, , Southern University of Science and Technology, ; Shenzhen, China
                [2 ]GRID grid.216417.7, ISNI 0000 0001 0379 7164, College of Chemistry and Chemical Engineering, , Central South University, ; Changsha, China
                [3 ]GRID grid.263817.9, Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices, , Southern University of Science and Technology, ; Shenzhen, China
                [4 ]GRID grid.263817.9, Key Laboratory of Energy Conversion and Storage Technologies, , Southern University of Science and Technology, Ministry of Education, ; Shenzhen, China
                Author information
                http://orcid.org/0000-0001-5337-8945
                http://orcid.org/0000-0003-3954-6003
                Article
                23569
                10.1038/s41467-021-23569-z
                8163856
                34050188
                4d1dfe16-af82-4905-8f32-6612f88a4781
                © The Author(s) 2021

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 18 March 2021
                : 5 May 2021
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                © The Author(s) 2021

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                thermoelectric devices and materials,thermoelectrics
                Uncategorized
                thermoelectric devices and materials, thermoelectrics

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