1. School of Materials Science and Engineering, Beihang University, Beijing 100191, China 2. AVIC SAC Commercial Aircraft Co. Ltd., Shenyang 110034, China 3. Liaoning Tieling Sales Branch, Petro China Co. Ltd., Tieling 112000, China 4. Shenyang Liming Areo-Engine Co. Ltd., Shenyang 110043, China 5. College of Physics and Materials Science, Henan Normal University, Xinxiang 453007, China
Recently, bismuth sulfide (Bi2S3) has attracted much attention in the thermoelectric community owing to its abundance, low cost, and advanced properties. However, its poor electrical transport properties have prevented Bi2S3 devices from realizing high thermoelectric performance. In this work, our motivation is to decrease the large electrical resistivity, which is recognized as the origin of the low ZT value in undoped Bi2S3. We combined melting and spark plasma sintering (SPS) in a continuous fabrication process to produce Bi2S3–xSex (x = 0, 0.09, 0.15, 0.21) and Bi2S2.85–ySe0.15Cly (y = 0.0015, 0.0045, 0.0075, 0.015, 0.03) samples. Our results show that Se alloying at S sites can narrow the band gap and activate intrinsic electron conduction, leading to a high power factor of ~2.0 μW·cm–1·K–2 at room temperature in Bi2S2.85S0.15, about 100 times higher than that of undoped Bi2S3. Moreover, our further introduction of Cl atoms into the S sites resulted in a second-stage optimization of carrier concentration and simultaneously reduced the lattice thermal conductivity, which contributed to a high ZT value of ~0.6 at 723 K for Bi2S2.835Se0.15Cl0.015. Our results indicate that high thermoelectric performance could be realized in Bi2S3 with earth-abundant and low-cost elements.
C. Chang, M. Wu, D. He, Y. Pei, C. F. Wu, X. Wu, H. Yu, F. Zhu, K. Wang, Y. Chen, L. Huang, J. F. Li, J. He, and L. D. Zhao, 3D charge and 2D phonon transports leading to high out-of-plane ZTin n-type SnSe crystals, Science 360(6390), 778 (2018) https://doi.org/10.1126/science.aaq1479
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G. Tan, L. D. Zhao, and M. G. Kanatzidis, Rationally designing high-performance bulk thermoelectric materials, Chem. Rev. 116(19), 12123 (2016) https://doi.org/10.1021/acs.chemrev.6b00255
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Z. H. Ge, B. P. Zhang, P. P. Shang, Y. Q. Yu, C. Chen, and J. F. Li, Enhancing thermoelectric properties of polycrystalline Bi2S3 by optimizing a ball-milling process, J. Electron. Mater. 40(5), 1087 (2011) https://doi.org/10.1007/s11664-011-1548-6
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L.-D. Zhao, S.-H. Lo, Y. Zhang, H. Sun, G. Tan, C. Uher, C. Wolverton, V. P. Dravid, and M. G. Kanatzidis, Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals, Nature 508(7496), 373 (2014) https://doi.org/10.1038/nature13184
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X. Zhang, D. Wang, H. Wu, M. Yin, Y. Pei, S. Gong, L. Huang, S. J. Pennycook, J. He, and L. D. Zhao, Simultaneously enhancing the power factor and reducing the thermal conductivity of SnTe via introducing its analogues, Energy Environ. Sci. 10(11), 2420 (2017) https://doi.org/10.1039/C7EE02530K
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Y. M. Zhou, H. J. Wu, Y. L. Pei, C. Chang, Y. Xiao, X. Zhang, S. K. Gong, J. Q. He, and L. D. Zhao, Strategy to optimize the overall thermoelectric properties of SnTe via compositing with its property-counter CuInTe2, Acta Mater. 125, 542 (2017) https://doi.org/10.1016/j.actamat.2016.11.049
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W. He, D. Wang, J. F. Dong, Y. Qiu, L. Fu, Y. Feng, Y. Hao, G. Wang, J. Wang, C. Liu, J. F. Li, J. He, and L. D. Zhao, Remarkable electron and phonon band structures lead to a high thermoelectric performance ZT>1 in earth-abundant and eco-friendly SnS crystals, J. Mater. Chem. A 6(21), 10048 (2018) https://doi.org/10.1039/C8TA03150A
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Z. H. Ge, L. D. Zhao, D. Wu, X. Liu, B. P. Zhang, J. F. Li, and J. He, Low-cost, abundant binary sulfides as promising thermoelectric materials, Mater. Today 19(4), 227 (2016) https://doi.org/10.1016/j.mattod.2015.10.004
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Z. Liu, Y. Pei, H. Geng, J. Zhou, X. Meng, W. Cai, W. Liu, and J. Sui, Enhanced thermoelectric performance of Bi2S3 by synergistical action of bromine substitution and copper nanoparticles, Nano Energy 13, 554 (2015) https://doi.org/10.1016/j.nanoen.2015.03.036
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Z. H. Ge, B. P. Zhang, Y. Liu, and J. F. Li, Nanostructured Bi2–xCuxS3 bulk materials with enhanced thermoelectric performance, Phys. Chem. Chem. Phys. 14(13), 4475 (2012) https://doi.org/10.1039/c2cp23955h
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Y. Q. Yu, B. P. Zhang, Z. H. Ge, P. P. Shang, and Y. X. Chen, Thermoelectric properties of Ag-doped bismuth sulfide polycrystals prepared by mechanical alloying and spark plasma sintering, Mater. Chem. Phys. 131(1–2), 216 (2011) https://doi.org/10.1016/j.matchemphys.2011.09.010
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J. Yang, G. Liu, J. Yan, X. Zhang, Z. Shi, and G. Qiao, Enhanced the thermoelectric properties of n-type Bi2S3 polycrystalline by iodine doping, J. Alloys Compd. 728, 351 (2017) https://doi.org/10.1016/j.jallcom.2017.08.148
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X. Du, F. Cai, and X. Wang, Enhanced thermoelectric performance of chloride doped bismuth sulfide prepared by mechanical alloying and spark plasma sintering, J. Alloys Compd. 587, 6 (2014) https://doi.org/10.1016/j.jallcom.2013.10.185
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K. Biswas, L. D. Zhao, and M. G. Kanatzidis, Telluriumfree thermoelectric: The anisotropic n-type semiconductor Bi2S3, Adv. Energy Mater. 2(6), 634 (2012) https://doi.org/10.1002/aenm.201100775
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L. J. Zhang, B. P. Zhang, Z. H. Ge, and C. G. Han, Fabrication and properties of Bi2S3–xSex thermoelectric polycrystals, Solid State Commun. 162, 48 (2013) https://doi.org/10.1016/j.ssc.2013.03.013
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W. Liu, K. C. Lukas, K. McEnaney, S. Lee, Q. Zhang, C. P. Opeil, G. Chen, and Z. Ren, Studies on the Bi2Te3- Bi2Se3-Bi2S3 system for mid-temperature thermoelectric energy conversion, Energy Environ. Sci. 6(2), 552 (2013) https://doi.org/10.1039/C2EE23549H
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L. D. Zhao, B. P. Zhang, W. S. Liu, H. L. Zhang, and J. F. Li, Enhanced thermoelectric properties of bismuth sulfide polycrystals prepared by mechanical alloying and spark plasma sintering, J. Solid State Chem. 181(12), 3278 (2008) https://doi.org/10.1016/j.jssc.2008.08.022
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Y. Xiao, C. Chang, Y. L. Pei, D. Wu, K. L. Peng, X. Y. Zhou, S. K. Gong, J. Q. He, Y. S. Zhang, Z. Zeng, and L. D. Zhao, Origin of low thermal conductivity in SnSe, Phys. Rev. B 94(12), 125203 (2016) https://doi.org/10.1103/PhysRevB.94.125203
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L. D. Zhao, G. Tan, S. Hao, J. He, Y. Pei, H. Chi, H. Wang, S. Gong, H. Xu, V. P. Dravid, C. Uher, G. J. Snyder, C. Wolverton, and M. G. Kanatzidis, Ultrahigh power factor and thermoelectric performance in holedoped single-crystal SnSe, Science 351(6269), 141 (2016) https://doi.org/10.1126/science.aad3749
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R. Chmielowski, D. Péré, C. Bera, I. Opahle, W. Xie, S. Jacob, F. Capet, P. Roussel, A. Weidenkaff, G. K. H. Madsen, and G. Dennler, Theoretical and experimental investigations of the thermoelectric properties of Bi2S3, J. Appl. Phys. 117(12), 125103 (2015) https://doi.org/10.1063/1.4916528
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K. Peng, X. Lu, H. Zhan, S. Hui, X. Tang, G. Wang, J. Dai, C. Uher, G. Wang, and X. Zhou, Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals, Energy Environ. Sci. 9(2), 454 (2016) https://doi.org/10.1039/C5EE03366G
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L. D. Zhao, S. H. Lo, J. He, H. Li, K. Biswas, J. Androulakis, C. I. Wu, T. P. Hogan, D. Y. Chung, V. P. Dravid, and M. G. Kanatzidis, High performance thermoelectrics from earth-abundant materials: Enhanced figure of merit in PbS by second phase nanostructures, J. Am. Chem. Soc. 133(50), 20476 (2011) https://doi.org/10.1021/ja208658w
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H. Wu, C. Chang, D. Feng, Y. Xiao, X. Zhang, Y. Pei, L. Zheng, D. Wu, S. Gong, Y. Chen, J. He, M. G. Kanatzidis, and L. D. Zhao, Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe, Energy Environ. Sci. 8(11), 3298 (2015) https://doi.org/10.1039/C5EE02423D
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Y. Xiao, H. Wu, W. Li, M. Yin, Y. Pei, Y. Zhang, L. Fu, Y. Chen, S. J. Pennycook, L. Huang, J. He, and L. D. Zhao, Remarkable roles of Cu to synergistically optimize phonon and carrier Transport in n-Type PbTe-Cu2Te, J. Am. Chem. Soc. 139(51), 18732 (2017) https://doi.org/10.1021/jacs.7b11662
