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The argyrodite compounds ( A(12n)/mm+Bn+X62(Am+ = Li+, Cu+, and Ag+; Bn+ = Ga3+, Si4+, Ge4+, Sn4+, P5+, and As5+; and X2-= S2-, Se2-, or Te2-)) have attracted great attention as excellent thermoelectric (TE) materials due to their extremely low lattice thermal conductivity (κl). Among them, Ag8SnSe6-based TE materials have high potential for TE applications. However, the pristine Ag8SnSe6 materials have low carrier concentration (< 1017 cm-3), resulting in low power factors. In this study, a hydrothermal method was used to synthesize Ag8SnSe6 with high purity, and the introduction of SnBr2 into the pristine Ag8SnSe6 powders has been used to simultaneously increase the power factor and decrease the thermal conductivity (κ). On the one hand, a portion of the Br- ions acted as electrons to increase the carrier concentration, increasing the power factor to a value of ~698 μW·m-1·K-2 at 736 K. On the other hand, some of the dislocations and nanoprecipitates (SnBr2) were generated, resulting in a decrease of κl (~0.13 W·m-1·K-1) at 578 K. As a result, the zT value reaches ~1.42 at 735 K for the sample Ag8Sn1.03Se5.94Br0.06, nearly 30% enhancement in contrast with that of the pristine sample (~1.09). The strategy of synergistic manipulation of carrier concentration and microstructure by introducing halogen compounds could be applied to the argyrodite compounds to improve the TE properties.


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Carrier and microstructure tuning for improving the thermoelectric properties of Ag8SnSe6 via introducing SnBr2

Show Author's information Zhonghai YUXiuxia WANGChengyan LIU( )Yiran CHENGZhongwei ZHANGRuifan SIXiaobo BAIXiaokai HUJie GAOYing PENGLei MIAO( )
Guangxi Key Laboratory of Information Materials, Electronical Information Materials and Devices Engineering Research Center of Ministry of Education, School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China

† Zhonghai Yu and Xiuxia Wang contributed equally to this work.

Abstract

The argyrodite compounds ( A(12n)/mm+Bn+X62(Am+ = Li+, Cu+, and Ag+; Bn+ = Ga3+, Si4+, Ge4+, Sn4+, P5+, and As5+; and X2-= S2-, Se2-, or Te2-)) have attracted great attention as excellent thermoelectric (TE) materials due to their extremely low lattice thermal conductivity (κl). Among them, Ag8SnSe6-based TE materials have high potential for TE applications. However, the pristine Ag8SnSe6 materials have low carrier concentration (< 1017 cm-3), resulting in low power factors. In this study, a hydrothermal method was used to synthesize Ag8SnSe6 with high purity, and the introduction of SnBr2 into the pristine Ag8SnSe6 powders has been used to simultaneously increase the power factor and decrease the thermal conductivity (κ). On the one hand, a portion of the Br- ions acted as electrons to increase the carrier concentration, increasing the power factor to a value of ~698 μW·m-1·K-2 at 736 K. On the other hand, some of the dislocations and nanoprecipitates (SnBr2) were generated, resulting in a decrease of κl (~0.13 W·m-1·K-1) at 578 K. As a result, the zT value reaches ~1.42 at 735 K for the sample Ag8Sn1.03Se5.94Br0.06, nearly 30% enhancement in contrast with that of the pristine sample (~1.09). The strategy of synergistic manipulation of carrier concentration and microstructure by introducing halogen compounds could be applied to the argyrodite compounds to improve the TE properties.

Keywords: lattice thermal conductivity, hydrothermal method, Ag8SnSe6, thermoelectric (TE) performance, SnBr2 introduction

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Publication history

Received: 19 January 2022
Revised: 13 April 2022
Accepted: 15 April 2022
Published: 02 July 2022
Issue date: July 2022

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© The Author(s) 2022.

Acknowledgements

This work was supported by the Guangxi Natural Science Foundation of China (Grant Nos. 2020GXNSFAA159111, AD20159006, 2020GXNSFAA159107, AD19245160, AD21220056, and AD19110020), the National Key R&D Program of China (Grant No. 2017YFE0198000), and the National Natural Science Foundation of China (Grant Nos. 52061009, U21A2054, and 51961011).

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