熵工程在热电材料中的应用

doi:10.15541/jim20200417

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 347-354.DOI: 10.15541/jim20200417

所属专题：能源材料论文精选(2021)；【虚拟专辑】热电材料(2020~2021)；【结构材料】高熵陶瓷；【能源环境】热电材料

熵工程在热电材料中的应用

杨青雨¹^,²(), 仇鹏飞¹^,², 史迅¹^,²(), 陈立东¹^,²

1.中国科学院上海硅酸盐研究所, 上海 200050
2.中国科学院大学材料科学与光电技术学院, 北京 100049

收稿日期:2020-07-27 修回日期:2020-09-14 出版日期:2021-04-20 网络出版日期:2020-09-20
通讯作者: 史迅, 研究员. E-mail: xshi@mail.sic.ac.cn
作者简介:杨青雨(1995-), 男, 博士研究生. E-mail: yangqingyu@student.sic.ac.cn
基金资助:
国家杰出青年科学基金(51625205)

Application of Entropy Engineering in Thermoelectrics

YANG Qingyu¹^,²(), QIU Pengfei¹^,², SHI Xun¹^,²(), CHEN Lidong¹^,²

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-07-27 Revised:2020-09-14 Published:2021-04-20 Online:2020-09-20
Contact: SHI Xun, professor. E-mail: xshi@mail.sic.ac.cn
About author:YANG Qingyu(1995-), male, PhD candidate. E-mail: yangqingyu@student.sic.ac.cn
Supported by:
National Science Foundation for Distinguished Young Scholars(51625205)

摘要/Abstract

摘要：

作为高熵合金设计思想的延伸, 熵工程可从电子和声子输运两方面引导热电材料的性能优化, 在多种热电材料体系已经获得了成功应用。特别是, 熵具有内禀的类似基因特性, 可以作为热电材料的指征因子, 对多元热电材料实现快速筛选。本文首先揭示熵作为热电材料基因特性的内禀原因, 阐述构型熵增加导致材料晶体结构对称性增强、泽贝克系数提升、晶格热导率下降的物理机制; 然后着重介绍熵工程在类液态材料和IV-VI族半导体等典型热电材料体系中的应用, 总结熵工程提高材料热电性能的研究进展; 并介绍多元单相高熵热电材料的热力学稳定性预测方法; 最后指出了熵工程将来的研究重点。

关键词: 熵工程, 热电材料, 材料基因工程, 电声输运, 综述

Abstract:

As the extension of high-entropy alloy, entropy engineering has been already extensively used in thermoelectrics because it can guide the optimization of thermoelectric (TE) performance from the aspects of both electrical and thermal transports. Due to the inherent material gene-like feature, entropy can be used as a performance indicator to rapidly screen new multicomponent TE materials. In this review, we first reveal the reason why entropy can be used as the performance indicator of TE materials. The physical mechanisms of enhanced structure symmetry, improved Seebeck coefficient, and suppressed lattice thermal conductivity as a result of the increased configurational entropy are discussed. Then, the applications of entropy engineering in typical TE materials, such as liquid-like materials and IV-VI semiconductors, are outlined, and the approach to screen and identify candidate multicomponent TE materials with high configurational entropy is introduced. Finally, the future directions for entropy engineering are highlighted.

Key words: entropy engineering, thermoelectric material, materials genome engineering, electrical and thermal transports, review

中图分类号:

TB34

杨青雨, 仇鹏飞, 史迅, 陈立东. 熵工程在热电材料中的应用[J]. 无机材料学报, 2021, 36(4): 347-354.

YANG Qingyu, QIU Pengfei, SHI Xun, CHEN Lidong. Application of Entropy Engineering in Thermoelectrics[J]. Journal of Inorganic Materials, 2021, 36(4): 347-354.

图/表 8

图1 熵工程在热电材料中的应用示意图

Fig. 1 Schematic of entropy engineering in thermoelectrics

图2 Cu2(S/Se/Te)体系泽贝克系数与构型熵的关系[10]

Fig. 2 Room-temperature Seebeck coefficient as a function of configurational entropy in Cu2(S/Se/Te)-based multicomponent materials[10]

图3 代表性热电材料晶格热导率与构型熵的关系[10,39-40]

Fig. 3 Lattice thermal conductivity as a function of configurational entropy for typical TE materials[10,39-40] The red zone presents the minimum lattice thermal conductivity

图4 代表性热电材料体系中ZT值与构型熵的关系

Fig. 4 TE figure of merit as a function of configurational entropy for typical TE materials

图5 Cu2X (X=S, Te, Se)体系泽贝克系数与载流子浓度的关系[10]

Fig. 5 Carrier concentration dependence of room-temperature Seebeck coefficient in Cu2(S/Se/Te)-based TE materials with different crystal symmetry[10]

图6 (Sn, Ge, Pb, Mn)Te体系(a)泽贝克系数和(b)晶格热导率与构型熵的关系[39]

Fig. 6 (a) Seebeck coefficient and (b) lattice thermal conductivity as a function of configurational entropy in (Sn, Ge, Pb, Mn)Te-based materials[39]

图7 固溶吉布斯自由能与平均溶解度参数$\bar{\delta }$和材料组元数n的关系[10] (1 ? = 0.1 nm)

Fig. 7 Gibbs free energy as a function of the average solubility parameter$(\bar{\delta })$for given multicomponent TE materials with different number of components[10] (1 ? = 0.1 nm)

图8 不同材料体系多元固溶焓变与组元数n的关系[10]

Fig. 8 Enthalpy as a function of the number of components for typical TE materials[10]

参考文献 71

[1]	陈立东, 刘睿恒, 史迅. 热电材料与器件, 北京: 科学出版社. 2018: 1-6.
[2]	ZHU T J, LIU Y T, FU C G, et al. Compromise and synergy in high-efficiency thermoelectric materials. Advanced Materials, 2017,29(14):26.
[3]	SLACK G A, ROWE D. CRC Handbook of Thermoelectrics. Boca Raton, FL: CRC press, 1995: 407-440.
[4]	HICKS L, DRESSELHAUS. Thermoelectric figure of merit of a one-dimensional conductor. Physical Review B, 1993,47(24):16631.
[5]	SHI X, ZHANG W, CHEN L D, et al. Filling fraction limit for intrinsic voids in crystals: doping in skutterudites. Physical Review Letters, 2005,95(18):185503. URL PMID
[6]	SHI X, KONG H, LI C P, et al. Low thermal conductivity and high thermoelectric figure of merit in n-type Ba_xYb_yCo₄Sb₁₂ double-filled skutterudites. Applied Physics Letters, 2008,92(18):182101.
[7]	SHI X, YANG J, SALVADOR J R, et al. Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports. Journal of the American Chemical Society, 2011,133(20):7837-7846. URL PMID
[8]	PEI Y, SHI X, LALONDE A, et al. Convergence of electronic bands for high performance bulk thermoelectrics. Nature, 2011,473(7345):66-69. DOI URL PMID
[9]	LIU H, SHI X, XU F, et al. Copper ion liquid-like thermoelectrics. Nature Materials, 2012,11(5):422-425. DOI URL PMID
[10]	LIU R, CHEN H, ZHAO K, et al. Entropy as a gene-like performance indicator promoting thermoelectric materials. Advanced Materials, 2017,29(38):1702712.
[11]	YEH J W, CHEN S K, LIN S J, et al. Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes. Advanced Engineering Materials, 2004,6(5):299-303.
[12]	SENKOV O N, MILLER J D, MIRACLE D B, et al. Accelerated exploration of multi-principal element alloys with solid solution phases. Nature Communications, 2015,6(1):1-10.
[13]	ZHANG Y, ZUO T T, TANG Z, et al. Microstructures and properties of high-entropy alloys. Progress in Materials Science, 2014,61:1-93.
[14]	WEI P C, LIAO C N, WU H J, et al. Thermodynamic routes to ultralow thermal conductivity and high thermoelectric performance. Advanced Materials, 2020,32(12):1906457.
[15]	MIRACLE D B, MILLER J D, SENKOV O N, et al. Exploration and development of high entropy alloys for structural applications. Entropy, 2014,16(1):494-525.
[16]	ZHANG Y, ZUO T T, CHENG Y Q, et al. High-entropy alloys with high saturation magnetization, electrical resistivity, and malleability. Scientific Reports, 2013,3:1455. URL PMID
[17]	LUCAS M S, BELYEA D, BAUER C, et al. Thermomagnetic analysis of FeCoCr_xNi alloys: magnetic entropy of high-entropy alloys. Journal of Applied Physics, 2013,113(17):17A923.
[18]	KOZELJ P, VRTNIK S, JELEN A, et al. Discovery of a superconducting high-entropy alloy. Physical Review Letters, 2014,113(10):5.
[19]	KAO Y F, CHEN S K, SHEU J H, et al. Hydrogen storage properties of multi-principal-component CoFeMnTi_xV_yZr_z alloys. International Journal of Hydrogen Energy, 2010,35(17):9046-9059.
[20]	BERARDAN D, FRANGER S, DRAGOE D, et al. Colossal dielectric constant in high entropy oxides. Physica Status Solidi-Rapid Research Letters, 2016,10(4):328-333.
[21]	BERARDAN D, FRANGER S, MEENA A K, et al. Room temperature lithium superionic conductivity in high entropy oxides. Journal of Materials Chemistry A, 2016,4(24):9536-9541.
[22]	SHAFEIE S, GUO S, HU Q, et al. High-entropy alloys as high-temperature thermoelectric materials. Journal of Applied Physics, 2015,118(18):184905.
[23]	RA S. Thermodynamics of Solids. New York: John Wiley and Sons, 1972: 178.
[24]	SONOMURA H. Internal strain energy in quaternary III-V compound alloys. Journal of Applied Physics, 1986,59(3):739-742.
[25]	SLAUGHTER W, PETROLITO J. The linearized theory of elasticity. Applied Mechanics Reviews, 2002,55(5):B90.
[26]	GREAVES G N, GREER A, LAKES R S, et al. Poisson's ratio and modern materials. Nature Materials, 2011,10(11):823-837. URL PMID
[27]	YANG J, MEISNER G P, CHEN L. Strain field fluctuation effects on lattice thermal conductivity of ZrNiSn-based thermoelectric compounds. Applied Physics Letters, 2004,85(7):1140-1142.
[28]	MEISNER G P, MORELLI D T, HU S, et al. Structure and lattice thermal conductivity of fractionally filled skutterudites: solid solutions of fully filled and unfilled end members. Physical Review Letters, 1998,80(16):3551-3554.
[29]	PLIRDPRING T, KUROSAKI K, KOSUGA A, et al. Chalcopyrite CuGaTe₂: a high-efficiency bulk thermoelectric material. Advanced Materials, 2012,24(27):3622-3626. URL PMID
[30]	CHENG N, LIU R, BAI S, et al. Enhanced thermoelectric performance in Cd doped CuInTe₂ compounds. Journal of Applied Physics, 2014,115(16):163705.
[31]	QIN Y, QIU P, LIU R, et al. Optimized thermoelectric properties in pseudocubic diamond-like CuGaTe₂ compounds. Journal of Materials Chemistry A, 2016,4(4):1277-1289.
[32]	GASCOIN F, OTTENSMANN S, STARK D, et al. Zintl phases as thermoelectric materials: tuned transport properties of the compounds Ca_xYb_1-xZn₂Sb₂. Advanced Functional Materials, 2005,15(11):1860-1864. DOI URL
[33]	MAO J, KIM H S, SHUAI J, et al. Thermoelectric properties of materials near the band crossing line in Mg₂Sn-Mg₂Ge-Mg₂Si system. Acta Materialia, 2016,103:633-642.
[34]	LIU W, TAN X, YIN K, et al. Convergence of conduction bands as a means of enhancing thermoelectric performance of n-type Mg₂Si_1-xSn_x solid solutions. Physical Review Letters, 2012,108(16):166601. URL PMID
[35]	BANERJEE S, RAMAKRISHNAN T V, DASGUPTA C. Phenomenological Ginzburg-Landau-like theory for superconductivity in the cuprates. Physical Review B, 2011,83(2):024510.
[36]	LIU W, LUKAS K C, MCENANEY K, et al. Studies on the Bi₂Te₃-Bi₂Se₃-Bi₂S₃ system for mid-temperature thermoelectric energy conversion. Energy & Environmental Science, 2013,6(2):552-560.
[37]	YAMINI S A, WANG H, GIBBS Z M, et al. Chemical composition tuning in quaternary p-type Pb-chalcogenides—a promising strategy for enhanced thermoelectric performance. Physical Chemistry Chemical Physics, 2014,16(5):1835-1840. DOI URL PMID
[38]	KORKOSZ R J, CHASAPIS T C, LO S H, et al. High ZT in p-type (PbTe)_1-2x(PbSe)_x(PbS)_x thermoelectric materials. Journal of the American Chemical Society, 2014,136(8):3225-3237. URL PMID
[39]	HU L, ZHANG Y, WU H, et al. Entropy engineering of SnTe: multi-principal-element alloying leading to ultralow lattice thermal conductivity and state-of-the-art thermoelectric performance. Advanced Energy Materials, 2018,8(29):1802116.
[40]	ZHAO S Y, CHEN R, LI J Q, et al. Synergistic effects on thermoelectric properties of Sn_0.5Ge_0.4875Te with Pb alloying. Journal of Alloys and Compounds, 2019,777:1334-1339.
[41]	POSFAI M, BUSECK P R. Djurleite, digenite, and chalcocite: intergrowths and transformations. American Mineralogist, 1994,79(3/4):308-315.
[42]	GULAY L, DASZKIEWICZ M, STROK O, et al. Crystal structure of Cu₂Se. Chemistry of Metals and Alloys, 2011,4(3/4):200-205.
[43]	PASHINKIN A, FEDOROV V. Phase equilibria in the Cu-Te system. Inorganic Materials, 2003,39(6):539-554.
[44]	HE Y, LU P, SHI X, et al. Ultrahigh thermoelectric performance in mosaic crystals. Advanced Materials, 2015,27(24):3639-3644. URL PMID
[45]	ZHAO K, QIU P, SONG Q, et al. Ultrahigh thermoelectric performance in Cu_2-ySe_0.5S_0.5 liquid-like materials. Materials Today Physics, 2017,1:14-23.
[46]	ZHAO K, ZHU C, QIU P, et al. High thermoelectric performance and low thermal conductivity in Cu_2-yS_1/3Se_1/3Te_1/3 liquid-like materials with nanoscale mosaic structures. Nano Energy, 2017,42:43-50.
[47]	WELDERT K S, ZEIER W G, DAY T W, et al. Thermoelectric transport in Cu₇PSe₆ with high copper ionic mobility. Journal of the American Chemical Society, 2014,136(34):12035-12040. DOI URL PMID
[48]	CHEN R, QIU P, JIANG B, et al. Significantly optimized thermoelectric properties in high-symmetry cubic Cu₇PSe₆ compounds via entropy engineering. Journal of Materials Chemistry A, 2018,6(15):6493-6502.
[49]	JIANG B, QIU P, CHEN H, et al. Entropy optimized phase transitions and improved thermoelectric performance in n-type liquid-like Ag₉GaSe₆ materials. Materials Today Physics, 2018,5:20-28.
[50]	JIANG B, QIU P, CHEN H, et al. An argyrodite-type Ag₉GaSe₆ liquid-like material with ultralow thermal conductivity and high thermoelectric performance. Chemical Communications, 2017,53(85):11658-11661. URL PMID
[51]	PEI Y, LALONDE A, IWANAGA S, et al. High thermoelectric figure of merit in heavy hole dominated PbTe. Energy & Environmental Science, 2011,4(6):2085-2089.
[52]	LI J, ZHANG X, CHEN Z, et al. Low-symmetry rhombohedral GeTe thermoelectrics. Joule, 2018,2(5):976-987.
[53]	ZHAO L D, LO S H, ZHANG Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014,508(7496):373-377. URL PMID
[54]	FAN Z, WANG H, WU Y, et al. Thermoelectric performance of PbSnTeSe high-entropy alloys. Materials Research Letters, 2017,5(3):187-194.
[55]	WU Y, NAN P, CHEN Z, et al. Manipulation of band degeneracy and lattice strain for extraordinary PbTe thermoelectrics. Research, 2020,2020:8151059. DOI URL PMID
[56]	RAOUX S, MUñOZ B, CHENG H Y, et al. Phase transitions in Ge-Te phase change materials studied by time-resolved X-ray diffraction. Applied Physics Letters, 2009,95(14):143118.
[57]	ALPTEKIN S. Structural phase transition of SnSe under uniaxial stress and hydrostatic pressure: an ab initio study. Journal of Molecular Modeling, 2011,17(11):2989-2994. DOI URL PMID
[58]	MUIR J A, BEATO V. Phase transformations in the system GeSe- GeTe. Journal of the Less Common Metals, 1973,33(3):333-340.
[59]	WIEDEMEIER H, SIEMERS P. The thermal expansion and high temperature transformation of GeSe. Zeitschrift für Anorganische und Allgemeine Chemie, 1975,411(1):90-96.
[60]	SIST M, GATTI C, NØRBY P, et al. High-temperature crystal structure and chemical bonding in thermoelectric germanium selenide (GeSe). Chemistry-A European Journal, 2017,23(28):6888-6895.
[61]	HUANG Z, MILLER S A, GE B, et al. High thermoelectric performance of new rhombohedral phase of GeSe stabilized through alloying with AgSbSe₂. Angewandte Chemie International Edition, 2017,129(45):14301-14306.
[62]	QIU Y, JIN Y, WANG D, et al. Realizing high thermoelectric performance in GeTe through decreasing the phase transition temperature via entropy engineering. Journal of Materials Chemistry A, 2019,7(46):26393-26401. DOI URL
[63]	ZHANG R Z, GUCCI F, ZHU H, et al. Data-driven design of ecofriendly thermoelectric high-entropy sulfides. Inorganic Chemistry, 2018,57(20):13027-13033. DOI URL PMID
[64]	FAN Z, WANG H, WU Y, et al. Thermoelectric high-entropy alloys with low lattice thermal conductivity. RSC Advances, 2016,6(57):52164-52170.
[65]	RAPHEL A, VIVEKANANDHAN P, KUMARAN S. High entropy phenomena induced low thermal conductivity in BiSbTe_1.5Se_1.5 thermoelectric alloy through mechanical alloying and spark plasma sintering. Materials Letters, 2020,269:127672. DOI URL
[66]	YAN J, LIU F, MA G, et al. Suppression of the lattice thermal conductivity in NbFeSb-based half-Heusler thermoelectric materials through high entropy effects. Scripta Materialia, 2018,157:129-134.
[67]	SAKURADA S, SHUTOH N. Effect of Ti substitution on the thermoelectric properties of (Zr,Hf)NiSn half-Heusler compounds. Applied Physics Letters, 2005,86(8):082105.
[68]	VOLYKHOV A, YASHINA L, TAMM M, et al. Phase equilibria in ternary reciprocal systems based on IV-VI compounds. Inorganic Materials 2009,45(9):968-974.
[69]	WANG Y Y, ROGADO N S, CAVA R J, et al. Spin entropy as the likely source of enhanced thermopower in Na_xCo₂O₄. Nature, 2003,423(6938):425-428. DOI URL PMID
[70]	EMIN D. Enhanced Seebeck coefficient from carrier-induced vibrational softening. Physical Review B, 1999,59(9):6205-6210.
[71]	HAN C G, QIAN X, LI Q K, et al. Giant thermopower of ionic gelatin near room temperature. Science, 2020,368(6495):1091-1098. URL PMID

熵工程在热电材料中的应用

Application of Entropy Engineering in Thermoelectrics

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 71

相关文章 15

编辑推荐

Metrics

本文评价

[1]	丁玲, 蒋瑞, 唐子龙, 杨运琼. MXene材料的纳米工程及其作为超级电容器电极材料的研究进展[J]. 无机材料学报, 2023, 38(6): 619-633.
[2]	杨卓, 卢勇, 赵庆, 陈军. X射线衍射Rietveld精修及其在锂离子电池正极材料中的应用[J]. 无机材料学报, 2023, 38(6): 589-605.
[3]	陈强, 白书欣, 叶益聪. 热管理用高导热碳化硅陶瓷基复合材料研究进展[J]. 无机材料学报, 2023, 38(6): 634-646.
[4]	林俊良, 王占杰. 铁电超晶格的研究进展[J]. 无机材料学报, 2023, 38(6): 606-618.
[5]	牛嘉雪, 孙思, 柳鹏飞, 张晓东, 穆晓宇. 铜基纳米酶的特性及其生物医学应用[J]. 无机材料学报, 2023, 38(5): 489-502.
[6]	贺丹琪, 魏明旭, 刘蕤之, 汤志鑫, 翟鹏程, 赵文俞. 一步法制备重费米子YbAl₃热电材料及其性能提升[J]. 无机材料学报, 2023, 38(5): 577-582.
[7]	苑景坤, 熊书锋, 陈张伟. 聚合物前驱体转化陶瓷增材制造技术研究趋势与挑战[J]. 无机材料学报, 2023, 38(5): 477-488.
[8]	杜剑宇, 葛琛. 光电人工突触研究进展[J]. 无机材料学报, 2023, 38(4): 378-386.
[9]	杨洋, 崔航源, 祝影, 万昌锦, 万青. 柔性神经形态晶体管研究进展[J]. 无机材料学报, 2023, 38(4): 367-377.
[10]	游钧淇, 李策, 杨栋梁, 孙林锋. 氧化物双介质层忆阻器的设计及应用[J]. 无机材料学报, 2023, 38(4): 387-398.
[11]	陈昆峰, 胡乾宇, 刘锋, 薛冬峰. 多尺度晶体材料的原位表征技术与计算模拟研究进展[J]. 无机材料学报, 2023, 38(3): 256-269.
[12]	张超逸, 唐慧丽, 李宪珂, 王庆国, 罗平, 吴锋, 张晨波, 薛艳艳, 徐军, 韩建峰, 逯占文. 新型GaN与ZnO衬底ScAlMgO₄晶体的研究进展[J]. 无机材料学报, 2023, 38(3): 228-242.
[13]	齐占国, 刘磊, 王守志, 王国栋, 俞娇仙, 王忠新, 段秀兰, 徐现刚, 张雷. GaN单晶的HVPE生长与掺杂进展[J]. 无机材料学报, 2023, 38(3): 243-255.
[14]	林思琪, 李艾燃, 付晨光, 李荣斌, 金敏. Zintl相Mg₃X₂(X=Sb, Bi)基晶体生长及热电性能研究进展[J]. 无机材料学报, 2023, 38(3): 270-279.
[15]	刘岩, 张珂颖, 李天宇, 周菠, 刘学建, 黄政仁. 陶瓷材料电场辅助连接技术研究现状及发展趋势[J]. 无机材料学报, 2023, 38(2): 113-124.