摘要
热电材料利用Seebeck与Pelitier效应可以实现热能和电能的相互转化, 是颇具潜力的新型功能材料. 本文聚焦四元硫属化合物 Cu2BIICIVSe4 (其中, B位为Zn, Cd, Mn, Hg, C位为Si, Ge, Sn)的热电性能. 此类材料具有复杂的晶格结构, 导致其具有较低的晶格热导率, 是一类具有本征低热导的热电材料. 本文系统地总结了各类优化四元硫属化合物电学及热学的方法. 首先, 非化学计量法、 元素掺杂和η=1定理用于改善其电学性能. 然后, 纳米结构工程可用于进一步降低其热导率. 最后, 基于文中的论述, 我们提出通过多种实验方法的结合使用, 协同调控四元硫属化合物的电、 热性能, 以期进一步提高其热电性能.
Article PDF
References
Bell LE. Cooling, heating, generating power, and recovering waste heat with thermoelectric systems. Science, 2008, 321: 1457–1461
Zebarjadi M, Esfarjani K, Dresselhaus MS, et al. Perspectives on thermoelectrics: from fundamentals to device applications. Energy Environ Sci, 2012, 5: 5147–5162
Gayner C, Kar KK. Recent advances in thermoelectric materials. Prog Mater Sci, 2016, 83: 330–382
Chasmar RP, Stratton R. The thermoelectric figure of merit and its relation to thermoelectric generators. J Electron Control, 1959, 7: 52–72
Zhu T, Liu Y, Fu C, et al. Compromise and synergy in highefficiency thermoelectric materials. Adv Mater, 2017, 29: 1605884
Pei Y, LaLonde A, Iwanaga S, et al. High thermoelectric figure of merit in heavy hole dominated PbTe. Energy Environ Sci, 2011, 4: 2085–2089
Wang H, Hwang J, Zhang C, et al. Enhancement of the thermoelectric performance of bulk SnTe alloys via the synergistic effect of band structure modification and chemical bond softening. J Mater Chem A, 2017, 5: 14165–14173
Zhang Q, Liao B, Lan Y, et al. High thermoelectric performance by resonant dopant indium in nanostructured SnTe. Proc Natl Acad Sci USA, 2013, 110: 13261–13266
Heremans JP, Jovovic V, Toberer ES, et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008, 321: 554–557
Faleev SV, Leonard F. Theory of enhancement of thermoelectric properties of materials with nanoinclusions. Phys Rev B, 2008, 77: 214304
Lim KH, Wong KW, Liu Y, et al. Critical role of nanoinclusions in silver selenide nanocomposites as a promising room temperature thermoelectric material. J Mater Chem C, 2019, 7: 2646–2652
Wang H, Bahk JH, Kang C, et al. Right sizes of nano- and microstructures for high-performance and rigid bulk thermoelectrics. Proc Natl Acad Sci USA, 2014, 111: 10949–10954
Brown SR, Kauzlarich SM, Gascoin F, et al. Yb14MnSb11: new high efficiency thermoelectric material for power generation. Chem Mater, 2006, 18: 1873–1877
Zhao LD, Lo SH, Zhang Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508: 373–377
Dong Y, Eckert B, Wang H, et al. Synthesis, crystal structure, and transport properties of Cu2.2Zn0.8SnSe4−xTex (0.1 ≤ x ≤ 0.4). Dalton Trans, 2015, 44: 9014–9019
Dong Y, Wang H, Nolas GS. Synthesis and thermoelectric properties of Cu excess Cu2ZnSnSe4. Phys Status Solidi RRL, 2014, 8: 61–64
Shi XY, Huang FQ, Liu ML, et al. Thermoelectric properties of tetrahedrally bonded wide-gap stannite compounds Cu2ZnSn1−xInxSe4. Appl Phys Lett, 2009, 94: 122103
Kumta PN, Risbud SH. Rare-earth chalcogenides—an emerging class of optical materials. J Mater Sci, 1994, 29: 1135–1158
Zhang J, Liu R, Cheng N, et al. High-performance pseudocubic thermoelectric materials from non-cubic chalcopyrite compounds. Adv Mater, 2014, 26: 3848–3853
Wei TR, Qin Y, Deng T, et al. Copper chalcogenide thermoelectric materials. Sci China Mater, 2019, 62: 8–24
Song Q, Qiu P, Hao F, et al. Quaternary pseudocubic Cu2TMSnSe4 (TM = Mn, Fe, Co) chalcopyrite thermoelectric materials. Adv Electron Mater, 2016, 2: 1600312
Bathula S, Jayasimhadri M, Gahtori B, et al. Enhancement in thermoelectric performance of SiGe nanoalloys dispersed with SiC nanoparticles. Phys Chem Chem Phys, 2017, 19: 25180–25185
Zhu Y, Liu Y, Ren G, et al. Lattice dynamics and thermal conductivity in Cu2Zn1–xCoxSnSe4. Inorg Chem, 2018, 57: 6051–6056
Chetty R, Bali A, Mallik RC. Thermoelectric properties of indium doped Cu2CdSnSe4. Intermetallics, 2016, 72: 17–24
Xiao Y, Wu H, Li W, et al. Remarkable roles of Cu to synergistically optimize phonon and carrier transport in n-type PbTe-Cu2Te. J Am Chem Soc, 2017, 139: 18732–18738
Liu ML, Chen IW, Huang FQ, et al. Improved thermoelectric properties of Cu-doped quaternary chalcogenides of Cu2CdSnSe4. Adv Mater, 2009, 21: 3808–3812
Raju C, Falmbigl M, Rogl P, et al. Thermoelectric properties of chalcogenide based Cu2+xZnSn1−xSe4. AIP Adv, 2013, 3: 032106
Song Q, Qiu P, Chen H, et al. Improved thermoelectric performance in nonstoichiometric Cu2+δMn1−δSnSe4 quaternary diamondlike compounds. ACS Appl Mater Interfaces, 2018, 10: 10123–10131
Dong Y, Wang H, Nolas GS. Synthesis, crystal structure, and high temperature transport properties of p-type Cu2Zn1–xFexSnSe4. Inorg Chem, 2013, 52: 14364–14367
Wei K, Beauchemin L, Wang H, et al. Enhanced thermoelectric properties of Cu2ZnSnSe4 with Ga-doping. J Alloys Compd, 2015, 650: 844–847
Zeier WG, Pei Y, Pomrehn G, et al. Phonon scattering through a local anisotropic structural disorder in the thermoelectric solid solution Cu2Zn1–xFexGeSe4. J Am Chem Soc, 2013, 135: 726–732
Liu ML, Huang FQ, Chen LD, et al. A wide-band-gap p-type thermoelectric material based on quaternary chalcogenides of Cu2ZnSnQ4 (Q=S,Se). Appl Phys Lett, 2009, 94: 202103
Liu FS, Wang B, Ao WQ, et al. Crystal structure and thermoelectric properties of Cu2Cd1−xZnxSnSe4 solid solutions. Intermetallics, 2014, 55: 15–21
Kanatzidis MG. Nanostructured thermoelectrics: the new paradigm? Chem Mater, 2010, 22: 648–659
Zhao LD, Wu HJ, Hao SQ, 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: 3346–3355
Li Z, Chen Y, Li JF, et al. Systhesizing SnTe nanocrystals leading to thermoelectric performance enhancement via an ultra-fast microwave hydrothermal method. Nano Energy, 2016, 28: 78–86
Li ZY, Li JF, Zhao WY, et al. PbTe-based thermoelectric nanocomposites with reduced thermal conductivity by SiC nanodispersion. Appl Phys Lett, 2014, 104: 113905
Tiwari KJ, Prem Kumar DS, Mallik RC, et al. Ball mill synthesis of bulk quaternary Cu2ZnSnSe4 and thermoelectric studies. J Elec Materi, 2017, 46: 30–39
Zeier WG, LaLonde A, Gibbs ZM, et al. Influence of a nano phase segregation on the thermoelectric properties of the p-type doped stannite compound Cu2+ xZn1–xGeSe4. J Am Chem Soc, 2012, 134: 7147–7154
Ibanez M, Cadavid D, Zamani R, et al. Composition control and thermoelectric properties of quaternary chalcogenide nanocrystals: the case of stannite Cu2CdSnSe4. Chem Mater, 2012, 24: 562–570
Ibanez M, Zamani R, LaLonde A, et al. Cu2ZnGeSe4 nanocrystals: synthesis and thermoelectric properties. J Am Chem Soc, 2012, 134: 4060–4063
Chen D, Zhao Y, Chen Y, et al. Hot-injection synthesis of Cudoped Cu2ZnSnSe4 nanocrystals to reach thermoelectric zT of 0.70 at 450°C. ACS Appl Mater Interfaces, 2015, 7: 24403–24408
Biswas K, He J, Blum ID, et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature, 2012, 489: 414–418
Acknowledgements
The work was financially supported by the National Basic Research Program of China (2013CB632506), the National Natural Science Foundation of China (51871134, 51672159, 51501105 and 51611540342), Shandong Provincial Natural Science Foundation, China (ZR2019MEM007), the Young Scholars Program of Shandong University (2015WLJH21), China Postdoctoral Science Foundation (2015M580588 and 2016T90631), the Postdoctoral Innovation Foundation of Shandong Province (201603027), and the Foundation of the State Key Laboratory of Metastable Materials Science and Technology (201703).
Author information
Authors and Affiliations
Contributions
Wang T and Huo T wrote the paper; Wang H and Wang C guided the writing of this paper. All authors contributed to the general discussion.
Corresponding authors
Additional information
Teng Wang received his Bachelor degree in 2014 from Shandong Normal University. He is now a PhD candidate at Shandong University. His research interest is the thermoelectric properties of n-type CaMnO3 and p-type SnTe alloys.
Taichang Huo received his Bachelor degree in 2018 from Ludong University. He is now a Master degree candidate at Shandong University. His research interest is the thermoelectric properties of the quaternary chalcogenide alloys.
Hongchao Wang is currently an associate professor at Shandong University, China. He received his Bachelor degree in physics from Ludong University in 2006 and his PhD degree in material physics and chemistry from Shandong University in 2011. He was the BK post-doctoral researcher fellow at Yonsei University from 2012 to 2015. His current major research interest is thermoelectric materials and their physical properties.
Chunlei Wang, born in China in 1963, studied physics at Shandong University where he gained his BSc degree in 1983 and MSc degree in 1986. He received his PhD in 1996 at Essex University, UK. He became a staff member at the Department of Physics of Shandong University in 1986, and Professor of physics in 1997.
Rights and permissions
About this article
Cite this article
Wang, T., Huo, T., Wang, H. et al. Quaternary chalcogenides: Promising thermoelectric material and recent progress. Sci. China Mater. 63, 8–15 (2020). https://doi.org/10.1007/s40843-019-9467-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-019-9467-2