Enhanced thermoelectric performance and mechanical strength in GeTe enable power generation and cooling
Jianglong Zhu, Fujie Zhang, Yilin Tai, Xiaobo Tan, Qian Deng, Pengfei Nan, Ruihuan Cheng, Chengliang Xia, Yue Chen, Binghui Ge, Ran Ang
Enhanced thermoelectric performance and mechanical strength in GeTe enable power generation and cooling
Finding a real thermoelectric (TE) material that excels in various aspects of TE performance, mechanical properties, TE power generation, and cooling is challenging for its commercialization. Herein, we report a novel multifunctional Ge0.78Cd0.06Pb0.1Sb0.06Te material with excellent TE performance and mechanical strength, which is utilized to construct candidate TE power generation and cooling devices near room temperature. Specifically, the effectiveness of band convergence, combined with optimized carrier concentration and electronic quality factor, distinctly boosts the Seebeck coefficient, thus greatly improving the power factor. Advanced electron microscopy observation indicates that complex multi-scale hierarchical structures and strain field distributions lead to ultra-low lattice thermal conductivity, and also effectively enhance mechanical properties. High ZT ~ 0.6 at 303 K, average ZTave ~ 1.18 from 303 to 553 K, and Vickers hardness of ~200 Hv in Ge0.78Cd0.06Pb0.1Sb0.06Te are obtained synchronously. Particularly, a 7-pair TE cooling device with a maximum ΔT of ~45.9 K at Th = 328 K, and a conversion efficiency of ~5.2% at Th = 553 K is achieved in a single-leg device. The present findings demonstrate a unique approach to developing superior multifunctional GeTe-based alloys, opening up a promising avenue for commercial applications.
cooling / GeTe / mechanical strength / power generation / thermoelectric
[1] |
Bell LE. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science. 2008;321(5895):1457-1461.
|
[2] |
Zhu J, Liu Z, Tong X, et al. Synergistic optimization of electrical–thermal–mechanical properties of the in-filled CoSb3 material by introducing Bi0.5Sb1.5Te3 nanoparticles. ACS Appl Mater Interfaces. 2021;13(20):23894-23904.
|
[3] |
Shi X-L, Zou J, Chen Z-G. Advanced thermoelectric design: from materials and structures to devices. Chem Rev. 2020;120(15):7399-7515.
|
[4] |
Pei Y, Shi X, LaLonde A, Wang H, Chen L, Snyder GJ. Convergence of electronic bands for high performance bulk thermoelectrics. Nature. 2011;473(7345):66-69.
|
[5] |
Li J, Zhang X, Chen Z, et al. Low-symmetry rhombohedral GeTe thermoelectrics. Joule. 2018;2(5):976-987.
|
[6] |
You L, Liu Y, Li X, et al. Boosting the thermoelectric performance of PbSe through dynamic doping and hierarchical phonon scattering. Energy Environ Sci. 1848;2018(7):11-1858.
|
[7] |
Heremans JP, Wiendlocha B, Chamoire AM. Resonant levels in bulk thermoelectric semiconductors. Energy Environ Sci. 2012;5(2):5510-5530.
|
[8] |
Biswas K, He J, Blum ID, et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature. 2012;489(7416):414-418.
|
[9] |
Vining CB. An inconvenient truth about thermoelectrics. Nat Mater. 2009;8(2):83-85.
|
[10] |
Li C, Ma S, Wei P, et al. Magnetism-induced huge enhancement of the room-temperature thermoelectric and cooling performance of p-type BiSbTe alloys. Energy Environ Sci. 2020;13(2):535-544.
|
[11] |
Zong P, Hanus R, Dylla M, et al. Skutterudite with graphene-modified grain-boundary complexion enhances zT enabling high-efficiency thermoelectric device. Energ Environ Sci. 2017;10(1):183-191.
|
[12] |
Zhang Q, Liao J, Tang Y, et al. Realizing a thermoelectric conversion efficiency of 12% in bismuth telluride/skutterudite segmented modules through full-parameter optimization and energy-loss minimized integration. Energy Environ Sci. 2017;10(4):956-963.
|
[13] |
Murugasami R, Vivekanandhan P, Kumaran S, Suresh Kumar R, John Tharakan T. Thermoelectric power factor performance of silicon-germanium alloy doped with phosphorus prepared by spark plasma assisted transient liquid phase sintering. Scr Mater. 2018;143:35-39.
|
[14] |
Murugasami R, Vivekanandhan P, Kumaran S, Suresh Kumar R, John Tharakan T. Simultaneous enhancement in thermoelectric performance and mechanical stability of p-type SiGe alloy doped with boron prepared by mechanical alloying and spark plasma sintering. J Alloy Compd. 2019;773:752-761.
|
[15] |
Yang J, Li G, Zhu H, et al. Next-generation thermoelectric cooling modules based on high-performance Mg3(Bi,Sb)2 material. Joule. 2022;6(1):193-204.
|
[16] |
Liu Z, Gao W, Oshima H, Nagase K, Lee C-H, Mori T. Maximizing the performance of n-type Mg3Bi2 based materials for room-temperature power generation and thermoelectric cooling. Nat Commun. 2022;13(1):1120.
|
[17] |
Bu Z, Zhang X, Shan B, et al. Realizing a 14% single-leg thermoelectric efficiency in GeTe alloys. Sci Adv. 2021;7:eabf2738.
|
[18] |
Xing T, Song Q, Qiu P, et al. High efficiency GeTe-based materials and modules for thermoelectric power generation. Energy Environ Sci. 2021;14(2):995-1003.
|
[19] |
Duan S, Xue W, Yao H, et al. Achieving high thermoelectric performance by NaSbTe2 alloying in GeTe for simultaneous suppression of Ge vacancies and band tailoring. Adv Energy Mater. 2022;12(3):2103385.
|
[20] |
Qi X, Yu Y, Xu X, et al. Enhanced thermoelectric performance in GeTe-Sb2Te3 pseudo-binary via lattice symmetry regulation and microstructure stabilization. Mater Today Phys. 2021;21:100507.
|
[21] |
Jiang Y, Dong J, Zhuang H-L, et al. Evolution of defect structures leading to high ZT in GeTe-based thermoelectric materials. Nat Commun. 2022;13(1):6087.
|
[22] |
Acharyya P, Roychowdhury S, Samanta M, Biswas K. Ultralow thermal conductivity, enhanced mechanical stability, and high thermoelectric performance in (GeTe)1–2x(SnSe)x(SnS)x. J Am Chem Soc. 2020;142(48):20502-20508.
|
[23] |
Liu C, Zhang Z, Peng Y, et al. Charge transfer engineering to achieve extraordinary power generation in GeTe-based thermoelectric materials. Sci Adv. 2023;9(17):eadh0713.
|
[24] |
Zhang X, Bu Z, Shi X, et al. Electronic quality factor for thermoelectrics. Sci Adv. 2020;6(46):eabc0726.
|
[25] |
Li J, Zhang X, Wang X, et al. High-performance GeTe thermoelectrics in both rhombohedral and cubic phases. J Am Chem Soc. 2018;140(47):16190-16197.
|
[26] |
Perumal S, Roychowdhury S, Negi DS, Datta R, Biswas K. High thermoelectric performance and enhanced mechanical stability ofp-type Ge1–xSbxTe. Chem Mater. 2015;27(20):7171-7178.
|
[27] |
Lee HS, Kim B-S, Cho C-W, et al. Herringbone structure in GeTe-based thermoelectric materials. Acta Mater. 2015;91:83-90.
|
[28] |
Li J, Li W, Bu Z, et al. Thermoelectric transport properties of CdxBiyGe1–x–yTe alloys. ACS Appl Mater Interfaces. 2018;10(46):39904-39911.
|
[29] |
Yu Y, Xie L, Pennycook SJ, Bosman M, He J. Strain-induced van der Waals gaps in GeTe revealed by in situ nanobeam diffraction. Sci Adv. 2022;8(45):eadd7690.
|
[30] |
Yu Y, Xu X, Wang Y, et al. Tunable quantum gaps to decouple carrier and phonon transport leading to high-performance thermoelectrics. Nat Commun. 2022;13(1):5612.
|
[31] |
Zhang F, Wu D, He J. Emerging quantum dots spotlight on next-generation photovoltaics. Mater Lab. 2022;1:20220012.
|
[32] |
Li J, Chen Z, Zhang X, Sun Y, Yang J, Pei Y. Electronic origin of the high thermoelectric performance of GeTe among the p-type group IV monotellurides. NPG Asia Mater. 2017;9(3):e353.
|
[33] |
Li J, Zhang X, Lin S, Chen Z, Pei Y. Realizing the high thermoelectric performance of GeTe by Sb-doping and Se-alloying. Chem Mater. 2017;29(2):605-611.
|
[34] |
Jin Y, Wang D, Hong T, et al. Outstanding CdSe with multiple functions leads to high performance of GeTe thermoelectrics. Adv Energy Mater. 2022;12(10):2103779.
|
[35] |
Hong M, Wang Y, Liu W, et al. Arrays of planar vacancies in superior thermoelectric Ge1−x−yCdxBiyTe with band convergence. Adv Energy Mater. 2018;8(30):1801837.
|
[36] |
Li M, Sun Q, Xu S, et al. Optimizing electronic quality factor toward high-performance Ge1−x−yTaxSbyTe thermoelectrics: the role of transition metal doping. Adv Mater. 2021;33(40):2102575.
|
[37] |
Hong M, Wang Y, Feng T, et al. Strong phonon–phonon interactions securing extraordinary thermoelectric Ge1–xSbxTe with Zn-alloying-induced band alignment. J Am Chem Soc. 2019;141(4):1742-1748.
|
[38] |
Zheng Z, Su X, Deng R, et al. Rhombohedral to cubic conversion of GeTe via MnTe alloying leads to ultralow thermal conductivity, electronic band convergence, and high thermoelectric performance. J Am Chem Soc. 2018;140(7):2673-2686.
|
[39] |
Sun Q, Li M, Shi X, et al. Versatile vanadium doping induces high thermoelectric performance in GeTe via band alignment and structural modulation. Adv Energy Mater. 2021;11(20):2100544.
|
[40] |
Zhang X, Li J, Wang X, et al. Vacancy manipulation for thermoelectric enhancements in GeTe alloys. J Am Chem Soc. 2018;140(46):15883-15888.
|
[41] |
Zhang C, Yan G, Wang Y, et al. Grain boundary complexions enable a simultaneous optimization of electron and phonon transport leading to high-performance gete thermoelectric devices. Adv Energy Mater. 2023;13(3):2203361.
|
[42] |
Jiang B, Wang W, Liu S, et al. High figure-of-merit and power generation in high-entropy GeTe-based thermoelectrics. Science. 2022;377(6602):208-213.
|
[43] |
Xu X, Huang Y, Xie L, Wu D, Ge Z, He J. Realizing improved thermoelectric performance in BiI3-doped Sb2Te3(GeTe)17 via introducing dual vacancy defects. Chem Mater. 2020;32(4):1693-1701.
|
[44] |
Hong M, Chen Z, Yang L, et al. Realizing zT of 2.3 in Ge1−x−ySbxInyTe via reducing the phase-transition temperature and introducing resonant energy doping. Adv Mater. 2018;30(11):1705942.
|
[45] |
Cahill DG, Watson SK, Pohl RO. Lower limit to the thermal conductivity of disordered crystals. Phys Rev B. 1992;46(10):6131-6140.
|
[46] |
Callaway J, von Baeyer HC. Effect of point imperfections on lattice thermal conductivity. Phys Rev. 1960;120(4):1149-1154.
|
[47] |
Bao D, Sun Q, Huang L, et al. Thermoelectric performance of p-type (Bi,Sb)2Te3 incorporating amorphous Sb2S3 nanospheres. Chem Eng J. 2022;430:132738.
|
[48] |
Liu Z, Wang Y, Gao W, et al. The influence of doping sites on achieving higher thermoelectric performance for nanostructured α-MgAgSb. Nano Energy. 2017;31:194-200.
|
[49] |
Pan Y, Wei T-R, Cao Q, Li J-F. Mechanically enhanced p- and n-type Bi2Te3-based thermoelectric materials reprocessed from commercial ingots by ball milling and spark plasma sintering. Mater Sci Eng B. 2015;197:75-81.
|
[50] |
Zhao L-D, Zhang B-P, Li J-F, Zhou M, Liu W-S, Liu J. Thermoelectric and mechanical properties of nano-SiC-dispersed Bi2Te3 fabricated by mechanical alloying and spark plasma sintering. J Alloy Compd. 2008;455(1-2):259-264.
|
[51] |
Banik A, Vishal B, Perumal S, Datta R, Biswas K. The origin of low thermal conductivity in Sn1−xSbxTe: phonon scattering via layered intergrowth nanostructures. Energ Environ Sci. 2011;2016(6):9-2019.
|
[52] |
Perumal S, Roychowdhury S, Biswas K. Reduction of thermal conductivity through nanostructuring enhances the thermoelectric figure of merit in Ge1−xBixTe. Inorg Chem Front. 2016;3(1):125-132.
|
[53] |
Davidow J, Gelbstein Y. A comparison between the mechanical and thermoelectric properties of three highly efficient p-type GeTe-rich compositions: TAGS-80, TAGS-85, and 3% Bi2Te3-doped Ge0.87Pb0.13Te. J Electron Mater. 2013;42(7):1542-1549.
|
[54] |
Cai B, Zhuang H-L, Pei J, et al. Spark plasma sintered Bi-Sb-Te alloys derived from ingot scrap: maximizing thermoelectric performance by tailoring their composition and optimizing sintering time. Nano Energy. 2021;85:106040.
|
[55] |
Zhuang H, Pei J, Cai B, et al. Thermoelectric performance enhancement in BiSbTe alloy by microstructure modulation via cyclic spark plasma sintering with liquid phase. Adv Funct Mater. 2021;31(15):2009681.
|
[56] |
Zheng Y, Slade TJ, Hu L, et al. Defect engineering in thermoelectric materials: what have we learned? Chem Soc Rev. 2021;50(16):9022-9054.
|
[57] |
Liang Z, Xu C, Shang H, et al. High thermoelectric energy conversion efficiency of a unicouple of n-type Mg3Bi2 and p-type Bi2Te3. Mater Today Phys. 2021;19:100413.
|
[58] |
Lu T, Wang B, Li G, et al. Synergistically enhanced thermoelectric and mechanical performance of Bi2Te3 via industrial scalable hot extrusion method for cooling and power generation applications. Mater Today Phys. 2023;32:101035.
|
/
〈 | 〉 |