Citation: Kai GUO, Hao-Jie HUO, Jun LUO. Point Defect Engineering Boosting the Thermoelectric Properties of Layered 122 Zintl Compounds[J]. Chinese Journal of Structural Chemistry, ;2020, 39(5): 815-820. doi: 10.14102/j.cnki.0254–5861.2011–2830 shu

Point Defect Engineering Boosting the Thermoelectric Properties of Layered 122 Zintl Compounds

Kai GUO ^a ,
Hao-Jie HUO ^a ,
Jun LUO ^{a, b,,}

a.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
b.
Materials Genome Institute, Shanghai University, Shanghai 200444, China

Corresponding author: Jun LUO, junluo@shu.edu.cn
Received Date: 30 March 2020
Accepted Date: 5 May 2020

Fund Project: the National Key Research and Development Program of China 2018YFA0702100the National Natural Science Foundation of China 21771123the National Natural Science Foundation of China 51772186the National Natural Science Foundation of China 51632005the Program of Introducing Talents of Discipline to Universities D16002

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The layered 122 Zintl compounds have become an intriguing class of thermoelectric materials due to the promising electronic transport properties and inherently low thermal conductivity, showing the typical characteristics of "phonon-glass electron-crystal". Owing to the unprecedented performance tunability, the thermoelectric properties of the layered-structure compounds are completive with some traditional thermoelectric materials. Point defects involving vacancy, aliovalent doping and equivalent alloying atoms have been introduced to further enhance the thermoelectric properties. This review emphasizes the effects of various point defects on the thermoelectric parameters, and provides perspective on the strategies for increasing the thermoelectric figure of merit zT, which are believed to be applicable for improving the thermoelectric properties of many other compounds.
- layered structure,
- 122 Zintl phase,
- point defect,
- orbital alignment,
- phonon scattering,
- thermoelectric properties
1. [1]
  Bell, L. E. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science 2008, 321, 1457-1461. doi: 10.1126/science.1158899
2. [2]
  Snyder, G. J.; Toberer, E. S. Complex thermoelectric materials. Nat. Mater. 2008, 7, 105-114. doi: 10.1038/nmat2090
3. [3]
  Slack, G. A.; Rowe, D. M. ed. CRC Handbook of thermoelectrics. Boca Raton: CRC Press 1995, 407-440.
4. [4]
  Sales, B. C.; Mandrus, D.; Williams, R. K. Filled skutterudite antimonides: a new class of thermoelectric materials. Science 1996, 272, 1325-1328. doi: 10.1126/science.272.5266.1325
5. [5]
  Shi, X.; Yang, J.; Salvador, J. R.; Chi, M.; Cho, J. Y.; Wang, H.; Bai, S.; Yang, J.; Zhang, W.; Chen, L. Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports. J. Am. Chem. Soc. 2011, 133, 7837-7846. doi: 10.1021/ja111199y
6. [6]
  Toberer, E. S.; May, A. F.; Melot, B. C.; Flage-Larsen, E.; Snyder, G. J. Electronic structure and transport in thermoelectric compounds AZn₂Sb₂ (A = Sr, Ca, Yb, Eu). Dalton Trans. 2010, 39, 1046-1054. doi: 10.1039/B914172C
7. [7]
  Guo, K.; Cao, Q. G.; Zhao, J. T. Zintl phase compounds AM₂Sb₂ (A = Ca, Sr, Ba, Eu, Yb; M = Zn, Cd) and their substitution variants: a class of potential thermoelectric materials. J. Rare Earth 2013, 31, 1029-1038. doi: 10.1016/S1002-0721(12)60398-6
8. [8]
  Pomrehn, G. S.; Zevalkink, A.; Zeier, W. G.; Walle, A. V. D.; Snyder, G. J. Defect-controlled electronic properties in AZn₂Sb₂ Zintl phases. Angew. Chem. Int. Ed. 2014, 53, 3422-3426. doi: 10.1002/anie.201311125
9. [9]
  Peng, W. Y.; Chanakian, S.; Zevalkink, A. Crystal chemistry and thermoelectric transport of layered AM₂X₂ compounds. Inorg. Chem. Front. 2018, 5, 1744-1759. doi: 10.1039/C7QI00813A
10. [10]
  Zhang, X.; Gu, H.; Zhang, Y.; Guo, L.; Yang, J.; Luo, S.; Lu, X.; Chen, K.; Chai, H.; Wang, H.; Zhang, X.; Zhou, X. Enhanced thermoelectric properties of YbZn₂Sb_2-xBi_x through a synergistic effect via Bi-doping. Chem. Eng. J. 2019, 374, 589–595. doi: 10.1016/j.cej.2019.05.206
11. [11]
  Zheng, L.; Li, W.; Sun, C.; Shi, X.; Zhang, X.; Pei, Y. Ternary thermoelectric AB₂C₂ Zintls. J. Alloys Compd. 2020, 821, 153497. doi: 10.1016/j.jallcom.2019.153497
12. [12]
  Guo, M. C.; Guo, F. K.; Zhu, J. B.; Yin, L.; Qin, H. X.; Zhang, Q.; Cai, W.; Sui, J. H. Enhanced thermoelectric properties of p-type CaMg₂Bi₂ via a synergistic effect originated from Zn and alkali-metal Co-doping. ACS Appl. Mater. Interfaces 2020, 12, 6015-6021. doi: 10.1021/acsami.9b22333
13. [13]
  Zhou, T.; Feng, Z.; Mao, J.; Jiang, J.; Zhu, H.; Singh, D. J.; Wang, C. Ren, Z. Thermoelectric properties of Zintl phase YbMg₂Sb₂. Chem. Mater. 2020, 32, 776-784. doi: 10.1021/acs.chemmater.9b04131
14. [14]
  Yang, X.; Gu, Y. Y.; Li, Y. P.; Guo, K.; Zhang, J. Y.; Zhao, J. T. The equivalent and aliovalent dopants boosting the thermoelectric properties of YbMg₂Sb₂. Sci. China Mater. 2020, 63, 437-443. doi: 10.1007/s40843-019-1199-4
15. [15]
  Toberer, E. S.; May, A. F.; Snyder, G. J. Zintl chemistry for designing high efficiency thermoelectric materials. Chem. Mater. 2010, 22, 624-634. doi: 10.1021/cm901956r
16. [16]
  Kauzlarich, S. M.; Brown, S. R.; Snyder, G. J. Zintl phases for thermoelectric devices. Dalton Trans. 2007, 21, 2099-2107.
17. [17]
  Zevalkink, A.; Zeier, W. G.; Cheng, E.; Snyder, J.; Fleurial, J. P.; Bux, S. Nonstoichiometry in the Zintl phase Yb_1-δZn₂Sb₂ as a route to thermoelectric optimization. Chem. Mater. 2014, 26, 5710-5717. doi: 10.1021/cm502588r
18. [18]
  Takagiwa, Y.; Sato, Y.; Zevalkink, A.; Kanazawa, I.; Kimura, K.; Isoda, Y.; Shinohara, Y. Thermoelectric properties of EuZn₂Sb₂ Zintl compounds: zT enhancement through Yb substitution for Eu. J. Alloys Compd. 2017, 703, 73-79. doi: 10.1016/j.jallcom.2017.01.350
19. [19]
  Guo, K.; Lin, J.; Li, Y.; Zhu, Y.; Li, X.; Yang, X.; Xing, J.; Yang, J.; Luo J.; Zhao, J. T. Suppressing the dynamic precipitation and lowering the thermal conductivity for stable and high thermoelectric performance in BaCu₂Te₂ based materials. J. Mater. Chem. A 2020, 8, 5323-5331. doi: 10.1039/D0TA00245C
20. [20]
  Wang, X.; Li, W.; Zhou, B.; Sun, C.; Zheng, L.; Tang, J.; Shi, X.; Pei, Y. Experimental revelation of multiband transport in heavily doped BaCd₂Sb₂ with promising thermoelectric performance. Mater. Today Phys. 2019, 8, 123-127. doi: 10.1016/j.mtphys.2019.03.002
21. [21]
  Kunioka, H.; Kihou, K.; Nishiate, H.; Yamamoto, A.; Usui, H.; Kurokib, K.; Lee, C. H. Thermoelectric properties of (Ba, K)Cd₂As₂ crystallized in the CaAl₂Si₂-type structure. Dalton Trans. 2018, 47, 16205-16210. doi: 10.1039/C8DT02955E
22. [22]
  Sun, C.; Shi, X.; Zheng, L.; Chen, B.; Li, W. Transport properties of p-type CaMg₂Bi₂ thermoelectrics. J. Mater. 2019, 5, 567-573.
23. [23]
  Wang, X.; Li, W.; Wang, C.; Li, J.; Zhang, X. Y.; Zhou, B. Q.; Chen, Y.; Pei, Y. Z. Single parabolic band transport in p-type EuZn₂Sb₂ thermoelectrics. J. Mater. Chem. A 2017, 5, 24185-24192. doi: 10.1039/C7TA08869H
24. [24]
  Pei, Y.; Shi, X.; LaLonde, A.; Wang, H.; Chen, L.; Snyder, G. J. Convergence of electronic bands for high performance bulk thermoelectrics. Nature 2011, 473, 66-69. doi: 10.1038/nature09996
25. [25]
  Zhang, J.; Song, L.; Madsen, G. K. H.; Fischer, K. F. F.; Zhang W.; Shi X.; Iversen, B. B. Designing high-performance layered thermoelectric materials through orbital engineering. Nat. Commun. 2016, 7, 10892. doi: 10.1038/ncomms10892
26. [26]
  Zheng, L.; Li, W.; Wang, X.; Pei, Y. Alloying for orbital alignment enables thermoelectric enhancement of EuCd₂Sb₂. J. Mater. Chem. A 2019, 7, 12773-12778. doi: 10.1039/C9TA03502H
27. [27]
  Wang, X.; Li, J.; Wang, C.; Zhou, B.; Zheng, L.; Gao, B.; Chen, Y.; Pei, Y. Orbital alignment for high performance thermoelectric YbCd₂Sb₂ alloys. Chem. Mater. 2018, 30, 5339-5345 doi: 10.1021/acs.chemmater.8b02155
28. [28]
  Saparamadu, U.; Tan, X.; Song, S.; Ren, Z.; Sun, J.; Singh, D. J.; Shuai, J.; Jiang J.; Ren, Z. Achieving high-performance p-type SmMg₂Bi₂ thermoelectric materials through band engineering and alloying effects. J. Mater. Chem. A 2020, accepted. doi.org/10.1039/C9TA13224D.
29. [29]
  Callaway, J.; von Baeyer, H. C. Effect of point imperfections on lattice thermal conductivity. Phys. Rev. 1960, 120, 1149-1154. doi: 10.1103/PhysRev.120.1149
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