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Title: Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation

Abstract

Complex Zintl phases, especially antimony (Sb)-based YbZn 0.4 Cd 1.6 Sb 2 with figure-of-merit ( ZT ) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic “electron–crystal, phonon–glass” nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg 2 Bi 2 with a record thermoelectric performance. Phase-pure EuMg 2 Bi 2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu 0.2 Yb 0.2 Ca 0.6 Mg 2 Bi 2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye–Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca,Yb,Eu)Mg 2 Bi 2 is better than the Sb-based Zintl phases.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1260848
Grant/Contract Number:  
FG02-13ER46917; SC0010831
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 29; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Shuai, Jing, Geng, Huiyuan, Lan, Yucheng, Zhu, Zhuan, Wang, Chao, Liu, Zihang, Bao, Jiming, Chu, Ching-Wu, Sui, Jiehe, and Ren, Zhifeng. Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation. United States: N. p., 2016. Web. doi:10.1073/pnas.1608794113.
Shuai, Jing, Geng, Huiyuan, Lan, Yucheng, Zhu, Zhuan, Wang, Chao, Liu, Zihang, Bao, Jiming, Chu, Ching-Wu, Sui, Jiehe, & Ren, Zhifeng. Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation. United States. doi:10.1073/pnas.1608794113.
Shuai, Jing, Geng, Huiyuan, Lan, Yucheng, Zhu, Zhuan, Wang, Chao, Liu, Zihang, Bao, Jiming, Chu, Ching-Wu, Sui, Jiehe, and Ren, Zhifeng. Wed . "Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation". United States. doi:10.1073/pnas.1608794113.
@article{osti_1260848,
title = {Higher thermoelectric performance of Zintl phases (Eu 0.5 Yb 0.5 ) 1−x Ca x Mg 2 Bi 2 by band engineering and strain fluctuation},
author = {Shuai, Jing and Geng, Huiyuan and Lan, Yucheng and Zhu, Zhuan and Wang, Chao and Liu, Zihang and Bao, Jiming and Chu, Ching-Wu and Sui, Jiehe and Ren, Zhifeng},
abstractNote = {Complex Zintl phases, especially antimony (Sb)-based YbZn 0.4 Cd 1.6 Sb 2 with figure-of-merit ( ZT ) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic “electron–crystal, phonon–glass” nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg 2 Bi 2 with a record thermoelectric performance. Phase-pure EuMg 2 Bi 2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu 0.2 Yb 0.2 Ca 0.6 Mg 2 Bi 2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye–Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca,Yb,Eu)Mg 2 Bi 2 is better than the Sb-based Zintl phases.},
doi = {10.1073/pnas.1608794113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 29,
volume = 113,
place = {United States},
year = {2016},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1608794113

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Cited by: 12 works
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