AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Journal of Materiomics Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

Roles of concentration-dependent Cu doping behaviors on the thermoelectric properties of n-type Mg3Sb1.5Bi0.5

Xinxin Yanga, Heng Nia, Xiaotong Yua, Biao Caoa, Juanjuan Xinga, Qiyong Chenb, Lili Xib, Jiandang Liuc, Jiye Zhanga( ), Kai Guod,e,f( ), Jing-Tai Zhaog,h
School of Materials Science and Engineering, Shanghai University, 99 Shangda Road, Shanghai, 200444, China
Materials Genome Institute, Shanghai University, 99 Shangda Road, Shanghai, 200444, China
State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China, Hefei, Anhui, 230026, China
School of Physics and Materials Science, Guangzhou University, Guangzhou, 510006, China
Research Center for Advanced Information Materials (CAIM), Huangpu Research & Graduate School of Guangzhou University, Sino-Singapore Guangzhou Knowledge City, Huangpu District, Guangzhou, 510555, China
Key Lab of Si-based Information Materials & Devices and Integrated Circuits Design, Department of Education of Guangdong Province, China
School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin, 541004, China
Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin, 541004, China

Peer review under responsibility of The Chinese Ceramic Society.

Show Author Information

Graphical Abstract

Abstract

Large Seebeck coefficients induced by high degeneracy of conduction band minimum, and low intrinsic lattice thermal conductivity originated from large lattice vibrational anharmonicity render Mg3Sb2 as a promising n-type thermoelectric material. Herein, we demonstrated unique concentration-dependent occupation behaviors of Cu in Mg3.4Sb1.5Bi0.49Te0.01 matrix, evidenced by structural characterization and transport property measurements. It is found that Cu atoms prefer to enter the interstitial lattice sites in Mg3Sb2 host with low doping level (Mg3.4Sb1.5Bi0.49Te0.01 + x% Cu, x < 0.3%), acting as donors for providing additional electrons without deteriorating the carrier mobility. When x is larger than 0.3%, the excessive Cu atoms are inclined to substitute Mg atoms, yielding acceptors to decrease the electron concentration. As a result, the electrical conductivity of the Mg3.4Sb1.5Bi0.49Te0.01 + 0.3% Cu sample reaches 2.3 × 104 S/m at 300 K, increasing by 300% compared with that of the pristine sample. The figure of merit zT values in the whole measured temperature range are significantly improved by the synergetic improvement of power factor and reduction of thermal conductivity. An average zT ~1.07 from 323 K to 773 K has been achieved for the Mg3.4Sb1.5Bi0.49Te0.01 + 0.3% Cu sample, which is about 30% higher than that of the Mg3.4Sb1.5Bi0.49Te0.01 sample.

Keywords

Mg3Sb2Cu dopingConcentration-dependent occupationThermoelectric propertiesAverage zT

References

[1]

Martinez-Ripoll M, Haase A, Brauer G. The crystal structure of α-Mg3Sb2. Acta Crystallogr Sect B Struct Crystallogr Cryst Chem 1974;30:2006-9. https://doi.org/10.1107/S0567740874006285.
Crossref Google Scholar
[2]

Condron CL, Kauzlarich SM, Gascoin F, Snyder GJ. Thermoelectric properties and microstructure of Mg3Sb2. J Solid State Chem 2006;179:2252-7.
Crossref Google Scholar
[3]

Snyder GJ. Application of the compatibility factor to the design of segmented and cascaded thermoelectric generators. Appl Phys Lett 2004;84:2436-8. https://doi.org/10.1063/1.1689396.
Crossref Google Scholar
[4]

Snyder GJ, Toberer ES. Complex thermoelectric materials. Nat Mater 2008;7:105-14.
Crossref Google Scholar
[5]
Goldsmid HJ. Introduction to thermoelectricity. Springer; 2009.
Crossref
[6]

Weng T, Li Z, Li Y, Hu Y, Guo K, Liu T, et al. Cu vacancy engineering of cage-compound BaCu2Se2: realization of temperature-dependent hole concentration for high average thermoelectric figure-of-merit. Chem Eng J 2022;437:135320. https://doi.org/10.1016/j.cej.2022.135302.
Crossref Google Scholar
[7]

Wang H, Gibbs ZM, Takagiwa Y, Snyder GJ. Tuning bands of PbSe for better thermoelectric efficiency. Energy Environ Sci 2014;7:804-11.
Crossref Google Scholar
[8]

Pei YL, Wu H, Wu D, Zheng F, He J. High thermoelectric performance realized in a BiCuSeO system by improving carrier mobility through 3D modulation doping. J Am Chem Soc 2014;136:13902-8.
Crossref Google Scholar
[9]

Zhao LD, Wu HJ, Hao SQ, Wu CI, Zhou XY, Biswas K, et al. All-scale hierarchical thermoelectrics: MgTe in PbTe facilitates valence band convergence and suppresses bipolar thermal transport for high performance. Energy Environ Sci 2013;6:3346-55.
Crossref Google Scholar
[10]

Kajikawa T, Kimura N, Yokoyama T. Ieee. Thermoelectric properties of intermetallic compounds: Mg3Bi2 and Mg3Sb2 for medium temperature range thermoelectric elements. Twenty-Second International Conference on Thermoelectrics. Proceedings Ict 2003;3:305-8.
Crossref Google Scholar
[11]

Chen C, Li X, Li S, Wang X, Zhang Z, Sui J, et al. Enhanced thermoelectric performance of p-type Mg3Sb2 by lithium doping and its tunability in an anionic framework. J Mater Sci 2018;53:16001-9.
Crossref Google Scholar
[12]

Shuai J, Wang Y, Kim HS, Liu Z, Sun J, Chen S, et al. Thermoelectric properties of Na-doped Zintl compound: Mg3-xNaxSb2. Acta Mater 2015;93:187-93.
Crossref Google Scholar
[13]

Kim I, Jang K-W, Kim I-H. Thermoelectric properties of Mg3-xZnxSb2 fabricated by mechanical alloying. Korean J Mater Res 2013;23:98-103.
Crossref Google Scholar
[14]

Bhardwaj A, Chauhan NS, Goel S, Singh V, Pulikkotil JJ, Senguttuvan TD, et al. Tuning the carrier concentration using Zintl chemistry in Mg3Sb2, and its implications for thermoelectric figure-of-merit. Phys Chem Chem Phys 2016;18:6191-200.
Crossref Google Scholar
[15]

Fu Y, Zhang X, Liu H, Tian J, Zhang J. Thermoelectric properties of Ag-doped compound: Mg3-xAgxSb2. J Materiomics 2018;4:75-9.
Crossref Google Scholar
[16]

Song L, Zhang J, Iversen BB. Thermal stability of p-type Ag-doped Mg3Sb2 thermoelectric materials investigated by powder X-ray diffraction. Phys Chem Chem Phys 2019;21:4295-305.
Crossref Google Scholar
[17]

Zhang KX, Qin XY, Xin HX, Li HJ, Zhang J. Transport and thermoelectric properties of nanocrystal substitutional semiconductor alloys (Mg1-xCdx)3Sb2 doped with Ag. J Alloys Compd 2009;484:498-504.
Crossref Google Scholar
[18]

Bhardwaj A, Misra DK. Enhancing thermoelectric properties of a p-type Mg3Sb2-based Zintl phase compound by Pb substitution in the anionic framework. RSC Adv 2014;4:34552-60.
Crossref Google Scholar
[19]

Bhardwaj A, Chauhan NS, Misra DK. Significantly enhanced thermoelectric figure of merit of p-type Mg3Sb2-based Zintl phase compounds via nanostructuring and employing high energy mechanical milling coupled with spark plasma sintering. J Mater Chem 2015;3:10777-86.
Crossref Google Scholar
[20]

Kim SH, Kim CM, Hong Y-K, Sim KI, Kim JH, Onimaru T, et al. Thermoelectric properties of Mg3Sb2-xBix single crystals grown by Bridgman method. Mater Res Express 2015;2:055903.
Crossref Google Scholar
[21]

Zhang J, Song L, Pedersen SH, Yin H, Le Thanh H, Iversen BB. Discovery of high-performance low-cost n-type Mg3Sb2-based thermoelectric materials with multi-valley conduction bands. Nat Commun 2017;8:13901.
Crossref Google Scholar
[22]

Kim S, Kim C, Hong Y-K, Onimaru T, Suekuni K, Takabatake T, et al. Thermoelectric properties of Mn-doped Mg-Sb single crystals. J Mater Chem 2014;2:12311-6.
Crossref Google Scholar
[23]

Tamaki H, Sato HK, Kanno T. Isotropic conduction network and defect chemistry in Mg3+δSb2-based layered zintl compounds with high thermoelectric performance. Adv Mater 2016;28:10182-7.
Crossref Google Scholar
[24]

Imasato K, Kang SD, Ohno S, Snyder GJ. Band engineering in Mg3Sb2 by alloying with Mg3Bi2 for enhanced thermoelectric performance. Mater Horiz 2018;5:59-64.
Crossref Google Scholar
[25]

Zhang J, Iversen BB. Fermi surface complexity, effective mass, and conduction band alignment in n-type thermoelectric Mg3Sb2-xBix from first principles calculations. J Appl Phys 2019;126:085104.
Crossref Google Scholar
[26]

Wang Y, Zhang X, Liu Y-Q, Zhang J-X, Yue M. Significant role of nanoscale Bi-rich phase in optimizing thermoelectric performance of Mg3Sb2. Chin Phys B 2020;29:067201.
Crossref Google Scholar
[27]

Imasato K, Kang SD, Snyder GJ. Exceptional thermoelectric performance in Mg3Sb0.6Bi1.4 for low-grade waste heat recovery. Energy Environ Sci 2019;12:965-71.
Crossref Google Scholar
[28]

Zhang JW, Song LR, Madsen GKH, Fischer KFF, Zhang WQ, Shi X, et al. Designing high-performance layered thermoelectric materials through orbital engineering. Nat Commun 2016;7:10892.
Crossref Google Scholar
[29]

Liu Z, Sato N, Gao W, Yubuta K, Kawamoto N, Mitome M, et al. Demonstration of ultrahigh thermoelectric efficiency of ~7.3% in Mg3Sb2/MgAgSb module for low-temperature energy harvesting. Joule 2021;5:1196-208.
Crossref Google Scholar
[30]

Mao J, Zhu H, Ding Z, Liu Z, Gamage GA, Chen G, et al. High thermoelectric cooling performance of n-type Mg3Bi2 -based materials. Sci China-Mater 2019;365:495-8.
Crossref Google Scholar
[31]

Gorai P, Ortiz BR, Toberer ES, Stevanovic V. Investigation of n-type doping strategies for Mg3Sb2. J Mater Chem 2018;6:13806-15.
Crossref Google Scholar
[32]

Zhang J, Song L, Borup KA, Jorgensen MRV, Iversen BB. New insight on tuning electrical transport properties via chalcogen doping in n-type Mg3Sb2-based thermoelectric materials. Adv Energy Mater 2018;8:1702776.
Crossref Google Scholar
[33]

Gorai P, Toberer ES, Stevanovic V. Effective n-type doping of Mg3Sb2 with group-3 elements. J Appl Phys 2019;125:025105.
Crossref Google Scholar
[34]

Li J, Zhang S, Zheng S, Zhang Z, Wang B, Chen L, et al. Defect chemistry for N-type doping of Mg3Sb2-based thermoelectric materials. J Phys Chem C 2019;123:20781-8.
Crossref Google Scholar
[35]

Wang Y, Zhang X, Liu Y, Wang Y, Liu H, Zhang J. Enhanced electrical transport performance through cation site doping in Y-doped Mg3.2Sb2. J. Mater 2020;6:216-23.
Crossref Google Scholar
[36]

Xia C, Cui J, Chen Y. Effect of group-3 elements doping on promotion of in-plane Seebeck coefficient of n-type Mg3Sb2. J Materiomics 2020;6:274-9.
Crossref Google Scholar
[37]

Imasato K, Wood M, Kuo JJ, Snyder GJ. Improved stability and high thermoelectric performance through cation site doping in n-type La-doped Mg3Sb1.5Bi0.5. J Mater Chem 2018;6:19941-6.
Crossref Google Scholar
[38]

Zhang F, Chen C, Li S, Yin L, Yu B, Sui J, et al. Enhanced thermoelectric performance in N-type Mg3.2Sb1.5Bi0.5 by La or Ce doping into Mg. Adv. Electron. Mater. 2020;6:1901391.
Crossref Google Scholar
[39]

Shi X, Sun C, Zhang X, Chen Z, Lin S, Li W, et al. Efficient Sc-doped Mg3.05-xScxSbBi thermoelectrics near room temperature. Chem Mater 2019;31:8987-94.
Crossref Google Scholar
[40]

Mao J, Shuai J, Song S, Wu Y, Dally R, Zhou J, et al. Manipulation of ionized impurity scattering for achieving high thermoelectric performance in n-type Mg3Sb2-based materials. Proc Natl Acad Sci USA 2017;114:10548-53.
Crossref Google Scholar
[41]

Zhang F, Chen C, Yao H, Bai F, Yin L, Li X, et al. High-performance N-type Mg3Sb2 towards thermoelectric application near room temperature. Adv Funct Mater 2020;30:1906143.
Crossref Google Scholar
[42]

Zhang J, Song L, Mamakhel A, Jorgensen MRV, Iversen BB. High-performance low-cost n-type Se-doped Mg3Sb2-based zintl compounds for thermoelectric application. Chem Mater 2017;29:5371-83.
Crossref Google Scholar
[43]

Liu W-S, Zhang Q, Lan Y, Chen S, Yan X, Zhang Q, et al. Thermoelectric property studies on Cu-doped n-type CuxBi2Te2.7Se0.3 nanocomposites. Adv Energy Mater 2011;1:577-87.
Crossref Google Scholar
[44]

Li S, Zhao W, Cheng Y, Chen L, Xu M, Guo K, et al. Thermoelectric performance enhancement in commercial Bi0.5Sb1.5Te3 materials by introducing gradient Cu-doped grain boundaries. ACS Appl Mater Interfaces 2023;15:1167-74.
Crossref Google Scholar
[45]

Cui JL, Yan YM, Fu H, Zhang XJ, Gao YL, Deng Y. Cu addition and its role in thermoelectric properties and nanostructuring in the series compounds (InSb)nCum. Curr Appl Phys 2012;12:69-74.
Crossref Google Scholar
[46]

Jeong M, Tak J-Y, Lee S, Seo W-S, Cho HK, Lim YS. Effects of Cu incorporation as an acceptor on the thermoelectric transport properties of CuxBi2Te2.7Se0.3 compounds. J Alloys Compd 2017;696:213-9.
Crossref Google Scholar
[47]

Xiao Y, Wu H, Li W, Yin M, Pei Y, Zhang Y, et al. Remarkable roles of Cu to synergistically optimize phonon and carrier transport in n-type PbTe-Cu2Te. J Am Chem Soc 2017;139:18732-8.
Crossref Google Scholar
[48]

You L, Liu Y, Li X, Nan P, Ge B, Jiang Y, et al. Boosting the thermoelectric performance of PbSe through dynamic doping and hierarchical phonon scattering. Energy Environ Sci 2018;11:1848-58.
Crossref Google Scholar
[49]

Xiao Y, Wu Y, Nan P, Dong H, Chen Z, Chen Z, et al. Cu interstitials enable carriers and dislocations for thermoelectric enhancements in n-PbTe0.75Se0.25. Chem 2020;6:523-37.
Crossref Google Scholar
[50]

Hou Z, Wang D, Hong T, Qin Y, Peng S, Wang G, et al. Boosting thermoelectric performance of n-type PbS through synergistically integrating in resonant level and Cu dynamic doping. J Phys Chem Solid 2021;148:109640.
Crossref Google Scholar
[51]

Liu Z, Gao W, Oshima H, Nagase K, Lee CH, Mori T. Maximizing the performance of n-type Mg3Bi2 based materials for room-temperature power generation and thermoelectric cooling. Nat Commun 2022;13:1120.
Crossref Google Scholar
[52]

Baroni S, Gironcoli SD, Corso AD, Giannozzi P. Phonons and related crystal properties from density-functional perturbation theory. Rev Mod Phys 2001;73:515-62. https://https://doi.org/10.1103/RevModPhys.73.515.
Crossref Google Scholar
[53]

Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 1996;54:11169-86. https://https://doi.org/10.1103/PhysRevB.54.11169.
Crossref Google Scholar
[54]

Blöchl PE. Projector augmented-wave method. Phys Rev B 1994;50:17953-79. https://https://doi.org/10.1103/physrevb.50.17953.
Crossref Google Scholar
[55]

Sun JW, Ruzsinszky A, Perdew JP. Strongly constrained and appropriately normed semilocal density functional. Phys Rev Lett 2015;115:036402. https://https://doi.org/10.1103/PhysRevLett.115.036402.
Crossref Google Scholar
[56]

Anisimov VI, Aryasetiawan F, Lichtenstein AI. First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA+ U method. J Phys Condens Matter 1997;9:767.
Crossref Google Scholar
[57]
Dean JA. Lange's handbook of chemistry. McGraw-Hill Book Co; 1999.
[58]

Jiang F, Feng T, Zhu Y, Han Z, Shu R, Chen C, et al. Extraordinary thermoelectric performance, thermal stability and mechanical properties of n-type Mg3Sb1.5Bi0.5 through multi-dopants at interstitial site. Mater. Today Phys 2022;27:100835.
Crossref Google Scholar
[59]

Jorgensen LR, Zhang J, Zeuthen CB, Iversen BB. Thermal stability of Mg3Sb1.475Bi0.475Te0.05 high performance n-type thermoelectric investigated through powder X-ray diffraction and pair distribution function analysis. J Mater Chem 2018;6:17171-6.
Crossref Google Scholar
[60]

Mao J, Wu Y, Song S, Zhu Q, Shuai J, Liu Z, et al. Defect engineering for realizing high thermoelectric performance in n-type Mg3Sb2-based materials. ACS Energy Lett 2017;2:2245-50.
Crossref Google Scholar
[61]

Song SW, Mao J, Bordelon M, He R, Wang YM, Shuai J, et al. Joint effect of magnesium and yttrium on enhancing thermoelectric properties of n-type Zintl Mg3+δY0.02Sb1.5Bi0.5. Mater. Today Phys 2019;8:25-33.
Crossref Google Scholar
[62]

Shuai J, Mao J, Song S, Zhu Q, Sun J, Wang Y, et al. Tuning the carrier scattering mechanism to effectively improve the thermoelectric properties. Energy Environ Sci 2017;10:799-807.
Crossref Google Scholar
[63]

Harvey Brooks. Theory of the electrical properties of germanium and silicon. Adv Electron Electron Phys 1955;7:85-182. https://doi.org/10.1016/S0065-2539(08)60957-9.
Crossref Google Scholar
[64]

Long D, Myers J. Ionized-impurity scattering mobility of electrons in silicon. Phys Rev 1963;115:1107-18. https://doi.org/10.1103/PhysRev.115.1107.
Crossref Google Scholar
[65]

Chattopadhyay D, Queisser HJ. Electron scattering by ionized impurities in semiconductors. Rev Mod Phys 1981;53:745. https://doi.org/10.1103/RevModPhys.53.745.
Crossref Google Scholar
[66]

Debye PP, Conwell EM. Electrical properties of N-type germanium. Phys Rev 1954;93:693-706. https://doi.org/10.1103/PhysRev.93.693.
Crossref Google Scholar
[67]

Hartman Robert. Temperature dependence of the low-field galvanomagnetic coefficients of bismuth. Phys Rev 1969;181:1070-86. https://doi.org/10.1103/PhysRev.181.1070.
Crossref Google Scholar
[68]

Eivari HA, Sohbatzadeh Z, Mele P, Assadi MHN. Low thermal conductivity: fundamentals and theoretical aspects in thermoelectric applications. Mater. Today Energy 2021;21:100744.
Crossref Google Scholar
[69]

Guo K, Weng T, Jiang Y, Zhu Y, Li H, Yuan S, et al. Unveiling the origins of low lattice thermal conductivity in 122-phase Zintl compounds. Mater Today Phys 2021;21:100480.
Crossref Google Scholar
[70]
Zhu Y, Xia Y, Wang Y, Sheng Y, Yang J, Fu C, et al. Violation of the T-1 relationship in the lattice thermal conductivity of Mg3Sb2 with locally asymmetric vibrations, vol. 2020. Research (Wash D C); 2020, 4589786. https://10.34133/2020/4589786.
Crossref
[71]

Li A, Hu C, He B, Yao M, Fu C, Wang Y, et al. Demonstration of valley anisotropy utilized to enhance the thermoelectric power factor. Nat Commun 2021;12:5408.
Crossref Google Scholar
Journal of Materiomics
Volume 10 Issue 1,
January 2024
Pages 154-162
DOI: 10.1016/j.jmat.2023.05.004
Cite this article:
Yang X, Ni H, Yu X, et al. Roles of concentration-dependent Cu doping behaviors on the thermoelectric properties of n-type Mg3Sb1.5Bi0.5. Journal of Materiomics, 2024, 10(1): 154-162. https://doi.org/10.1016/j.jmat.2023.05.004

182

Views

5

Crossref

4

Web of Science

5

Scopus

Altmetrics
Received: 14 March 2023
Revised: 05 May 2023
Accepted: 09 May 2023
Published: 09 June 2023
© 2023 The Authors.

This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Return