Heterogeneous Interface Microstructure and Thermoelectromagnetic Conversion Performance of BiSbTe/MnCoGe Multifunctional Materials

doi:10.1007/s40195-025-01854-w

Abstract

Abstract:

The synergistic cooling of thermoelectromagnetic materials promises a breakthrough in the efficiency of single refrigeration and has attracted extensive research. The study of heterogeneous interface is crucial for achieving the synergistic performance of both materials. In this work, a composite material comprising Bi₂Te₃-based thermoelectric material and MnCoGe-based magnetocaloric material is synthesized, which is a material exhibiting both thermoelectric and magnetocaloric properties. During the plasma-activated sintering process of the composite material, elemental interdiffusion of Mn, Co, Sb, and Te occurs, forming a diffusion layer of MnTe and CoSbTe. Reaction of heterogeneous interface leads to point defects within the material, significantly increasing the carrier concentration. Optimization of the sintering temperature results in a thermoelectric figure of merit (ZT) of 0.69 at 300 K and −ΔS_max of 0.97 J kg⁻¹ K⁻¹ at room temperature under a 5 T magnetic field for the Bi_0.5Sb_1.5Te₃/10 wt% Mn_0.9Cu_0.1CoGe composite sintered at 623 K and under 50 MPa. This study demonstrates that Bi_0.5Sb_1.5Te₃/Mn_0.9Cu_0.1CoGe is a potential candidate for efficient thermoelectromagnetic cooling applications.

Key words: Thermoelectromagnetic cooling, Elemental diffusion, Thermoelectric, Magnetocaloric, Composite

Longli Wang, Rongcheng Li, Peilin Miao, Jiushun Zhu, Gangjian Tan, Xinfeng Tang. Heterogeneous Interface Microstructure and Thermoelectromagnetic Conversion Performance of BiSbTe/MnCoGe Multifunctional Materials[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(5): 839-848.

Figures/Tables 9

Fig. 1 a XRD patterns of Mn1-xCuxCoGe (x = 0, 0.09-0.13), b DSC curves of Mn1-xCuxCoGe (x = 0, 0.09-0.13), c temperature dependence of magnetization curves under an applied magnetic field of 0.1 T upon cooling of Mn1-xCuxCoGe (x = 0.10, 0.11), d ΔS as a function of temperature of Mn1-xCuxCoGe (x = 0.10, 0.11) under different magnetic fields

Fig. 2 Flowchart of the preparation process for thermoelectromagnetic coupling materials

Fig. 3 a XRD patterns of BST/MCCG composites sintered at different temperatures and b magnification of diffraction peaks at 2θ = 27° to 30°

Fig. 4 a-d Backscattered electron images of the composites at different sintering temperatures, e elemental mapping overlay of the sample sintered at 723 K, f-l elemental mapping images of Bi, Sb, Te, Mn, Co, Ge, and Cu

Fig. 5 Diffusion mechanism diagram of BST/MCCG

Fig. 6 Temperature-dependent electrical properties of BST/MCCG composites sintered at different temperatures: a electrical conductivity, b Seebeck coefficient, and c power factor

Table 1 Room temperature charge transport properties and mass densities of BST/MCCG composites sintered at different temperatures

Samples	p (10¹⁹ cm⁻³)	μ (cm² V⁻¹ s⁻¹)	ρ (g/cm³)	σ (10⁴ S m⁻¹)	S (μV K⁻¹)
573 K PAS	9.9	48.7	6.56	7.7	161.9
623 K PAS	22	34.6	6.77	12.2	146.9
673 K PAS	31.1	30.7	6.81	15.3	110.5
723 K PAS	68.5	16.8	6.85	18.4	76.2

Fig. 7 a Total and b latice thermal conductivities as a function of temperature for BST/MCCG sintered at different temperatures, c ZT values as a function of temperature for BST/MCCG sintered at different temperatures

Fig. 8 a Temperature dependence of magnetization curves under a magnetic field of 0.1 T upon cooling of Mn0.9Cu0.1CoGe and BST/MCCG and b ΔS as a function of temperature of BST/MCCG under different magnetic fields

References 69

[1]	X. She, L. Cong, B. Nie, G. Leng, H. Peng, Y. Chen, X. Zhang, T. Wen, H. Yang, Y. Luo, Appl. Energy 232, 157 (2018)
[2]	R. Khosla, R. Renaldi, A. Mazzone, C. Mcelroy, G. Palafox-Alcantar, Annu. Rev. Environ. Resour. 47, 449 (2022)
[3]	Y. Wang, Z. Zhang, T. Usui, M. Benedict, S. Hirose, J. Lee, J. Kalb, D. Schwartz, Science 370, 129 (2020)
[4]	K. Harby, Renew. Sust. Energ. Rev. 73, 1247 (2017)
[5]	N. Kumma, S.S.H. Kruthiventi, Renew. Sust. Energ. Rev. 189, 114073 (2024)
[6]	M.O. Mclinden, J.S. Brown, R. Brignoli, A.F. Kazakov, P.A. Domanski, Nat. Commun. 8, 14476 (2017)
[7]	G. Restrepo, M. Weckert, R. Brüggemann, S. Gerstmann, H. Frank, Environ. Sci. Technol. 42, 2925 (2008)
[8]	J. Shi, D. Han, Z. Li, L. Yang, S.G. Lu, Z. Zhong, J. Chen, Q.M. Zhang, X. Qian, Joule 3, 1200 (2019)
[9]	G. Tan, L.D. Zhao, M.G. Kanatzidis, Chem. Rev. 116, 12123 (2016)
[10]	X. Tang, Z. Li, W. Liu, Q. Zhang, C. Uher, Interdisc. Mater. 1, 88 (2022)
[11]	J. Mao, G. Chen, Z. Ren, Nat. Mater. 20, 454 (2021)
[12]	G. Tan, W. Liu, H. Chi, X. Su, S. Wang, Y. Yan, X. Tang, W. Wong-Ng, C. Uher, Acta Mater. 61, 7693 (2013)
[13]	G. Tan, F. Shi, S. Hao, H. Chi, T.P. Bailey, L.D. Zhao, C. Uher, C. Wolverton, V.P. Dravid, M.G. Kanatzidis, J. Am. Chem. Soc. 137, 11507 (2015)
[14]	G. Tan, L.D. Zhao, F. Shi, J.W. Doak, S.H. Lo, H. Sun, C. Wolverton, V.P. Dravid, C. Uher, M.G. Kanatzidis, J. Am. Chem. Soc. 136, 7006 (2014)
[15]	G. Tan, S. Hao, S. Cai, T.P. Bailey, Z. Luo, I. Hadar, C. Uher, V.P. Dravid, C. Wolverton, M.G. Kanatzidis, J. Am. Chem. Soc. 141, 4480 (2019)
[16]	R. Li, C. Xie, Y. Wang, B. Jin, J. Zhu, X. Tang, G. Tan, Mater. Today Phys. 48, 101573 (2024)
[17]	V. Franco, J.S. Blázquez, J.J. Ipus, J.Y. Law, L.M. Moreno-Ramírez, A. Conde, Prog. Mater. Sci. 93, 112 (2018)
[18]	K. Klinar, J.Y. Law, V. Franco, X. Moya, A. Kitanovski, Adv. Energy Mater. 14, 2401739 (2024)
[19]	Z. Zhao, W. Guo, Z. Zhang, Adv. Funct. Mater. 32, 2203866 (2022)
[20]	S. Wang, Y. Shi, Y. Li, H. Lin, K. Fan, X. Teng, Renew. Sust. Energ. Rev. 187, 113762 (2023)
[21]	G. Zhou, Y. Zhu, S. Yao, Q. Sun, Joule 7, 2003 (2023)
[22]	N.A. Zolpakar, N. Mohd-Ghazali, M.H. El-Fawal, Renew. Sustain. Energy Rev. 54, 626 (2016)
[23]	F.W. Jordan, Nature 86, 380 (1911)
[24]	J. Flipse, F.L. Bakker, A. Slachter, F.K. Dejene, B.J. Van Wees, Nat. Nanotechnol. 7, 166 (2012) DOI PMID
[25]	G. Tan, F. Shi, S. Hao, L.D. Zhao, H. Chi, X. Zhang, C. Uher, C. Wolverton, V.P. Dravid, M.G. Kanatzidis, Nat. Commun. 7, 12167 (2016)
[26]	G. Tan, F. Shi, H. Sun, L.D. Zhao, C. Uher, V.P. Dravid, M.G. Kanatzidis, J. Mater. Chem. A 2, 20849 (2014)
[27]	G. Tan, W.G. Zeier, F. Shi, P. Wang, G.J. Snyder, V.P. Dravid, M.G. Kanatzidis, Chem. Mater. 27, 7801 (2015)
[28]	Y. Qin, B. Qin, D. Wang, C. Chang, L.D. Zhao, Energy Environ. Sci. 15, 4527 (2022)
[29]	G. Tan, C.C. Stoumpos, S. Wang, T.P. Bailey, L.D. Zhao, C. Uher, M.G. Kanatzidis, Adv. Energy Mater. 7, 1700099 (2017)
[30]	S. Lin, S. Wang, Y. Li, Z. Lai, X. Yang, X. Lu, M. Jin, Acta Metall. Sin.-Engl. Lett. (2024). https://doi.org/10.1007/s40195-024-01790-1
[31]	Z.G. Chen, W.D. Liu, J. Mater. Sci. Technol. 121, 256 (2022)
[32]	J. Ding, W. Zhao, W. Jin, C.A. Di, D. Zhu, Adv. Funct. Mater. 31, 2010695 (2021)
[33]	W. Sun, W.D. Liu, Q. Liu, Z.G. Chen, Chem. Eng. J. 450, 138389 (2022)
[34]	T. Cao, X.L. Shi, Z.G. Chen, Prog. Mater. Sci. 131, 101003 (2023)
[35]	R. Zhan, J. Lyu, D. Yang, Y. Liu, S. Hua, Z. Xu, C. Wang, X. Peng, Y. Yan, X. Tang, Mater. Today Phys. 24, 100670 (2022)
[36]	G. Tan, M. Ohta, M.G. Kanatzidis, Philos. Trans. Royal Soc. A 377, 20180450 (2019)
[37]	J. Dong, J. Jiang, Y. Wang, M. Huang, J. Cui, T. Song, Acta Metall. Sin.-Engl. Lett. (2024). https://doi.org/10.1007/s40195-024-01796-9
[38]	S. Li, X. Fang, T. Lyu, J. Cheng, W. Ao, C. Zhang, F. Liu, J. Li, L. Hu, Mater. Today Phys. 27, 100764 (2022)
[39]	G. Zheng, X. Su, X. Li, T. Liang, H. Xie, X. She, Y. Yan, C. Uher, M.G. Kanatzidis, X. Tang, Adv. Energy Mater. 6, 1600595 (2016)
[40]	B. Nan, X. Song, C. Chang, K. Xiao, Y. Zhang, L. Yang, S. Horta, J. Li, K.H. Lim, M. Ibáñez, A.C.S. Appl. Mater. Interf. 15, 23380 (2023)
[41]	J. Qiu, Y. Yan, T. Luo, K. Tang, L. Yao, J. Zhang, M. Zhang, X. Su, G. Tan, H. Xie, Energy Environ. Sci. 12, 3106 (2019)
[42]	X. Guan, Z. Liu, N. Ma, Z. Li, J. Liu, H. Zhang, H. Li, Q. Ba, J. Ma, C. Jin, Acta Metall. Sin.-Engl. Lett. (2024). https://doi.org/10.1007/s40195-024-01794-x
[43]	R. Deng, X. Su, S. Hao, Z. Zheng, M. Zhang, H. Xie, W. Liu, Y. Yan, C. Wolverton, C. Uher, Energy Environ. Sci. 11, 1520 (2018)
[44]	Z. Han, J.W. Li, F. Jiang, J. Xia, B.P. Zhang, J.F. Li, W. Liu, J. Materiomics 8, 427 (2022)
[45]	N. Terada, H. Mamiya, Nat. Commun. 12, 1212 (2021)
[46]	Y. Taguchi, H. Sakai, D. Choudhury, Adv. Mater. 29, 1606144 (2017)
[47]	J. RomeroGómez, R. Ferreiro Garcia, A. De MiguelCatoira, M. RomeroGómez, Renew. Sust. Energ. Rev. 17, 74 (2013)
[48]	D.J. Silva, B.D. Bordalo, A.M. Pereira, J. Ventura, J.P. Araújo, Appl. Energy 93, 570 (2012)
[49]	C. Li, W. Zhao, Q. Zhang, Sci. Bull. 67, 891 (2022)
[50]	Y. Gong, J. Sun, W. Hu, S. Li, W. Xu, G. Tan, X. Tang, Appl. Phys. Lett. 120, 023905 (2022)
[51]	W. Yan, X. Nie, S. Ke, Y. Hu, X. Ai, W. Zhu, W. Zhao, Q. Zhang, Adv. Funct. Mater. 32, 2209739 (2022)
[52]	X. Li, C. Sun, K. Yang, D. Liang, X. Ye, W. Song, W. Xu, W. Zhao, Q. Zhang, Small 20, 2311478 (2024)
[53]	X. Mo, J. Liao, G. Yuan, S. Zhu, X. Lei, L. Huang, Q. Zhang, C. Wang, Z. Ren, J. Magnes, Alloys 10, 1024 (2022)
[54]	J. Feng, R. Geutjens, N.V. Thang, J. Li, X. Guo, A. Kéri, S. Basak, G. Galbács, G. Biskos, H. Nirschl, H.W. Zandbergen, E. Brück, A. Schmidt-Ott, A.C.S. Appl. Mater. Interf. 10, 6073 (2018)
[55]	G. Cao, Q. Wang, J. Liu, Y. Zhang, X. Wang, M. Huang, H. Shen, L. Zheng, J. Alloys Compd. 800, 363 (2019)
[56]	Z. Xu, F. Wang, G. Lin, J. Supercond. Nov. Magn. 34, 243 (2021)
[57]	L. Pfeuffer, A. Gràcia-Condal, T. Gottschall, D. Koch, T. Faske, E. Bruder, J. Lemke, A. Taubel, S. Ener, F. Scheibel, Acta Mater. 217, 117157 (2021)
[58]	J.H. Chen, N.M. Bruno, I. Karaman, Y. Huang, J. Li, J.H. Ross, Acta Mater. 105, 176 (2016)
[59]	C. Liu, W. Xu, P. Wei, S. Ke, W. Cui, L. Li, D. Liang, X. Ye, T. Chen, X. Nie, Energy Environ. Mater. 7, e12710 (2024)
[60]	L. Xing, W. Cui, X. Sang, F. Hu, P. Wei, W. Zhu, X. Nie, Q. Zhang, W. Zhao, J. Materiomics 7, 998 (2021) DOI
[61]	R. Li, L. Wang, P. Miao, C. Xie, X. Tang, G. Tan, J. Magn. Magn. Mater. 603, 172224 (2024)
[62]	H. Imam, H.G. Zhang, W.J. Pan, B.T. Song, J.H. Shi, M. Yue, Intermetallics 107, 53 (2019) DOI
[63]	N. Ul Hassan, I. A. Shah, J. Liu, G. Xu, Y. Gong, X. Miao, F. Xu, J. Supercond. Nov. Magn. 31, 3809 (2018)
[64]	J.H. Chen, T. PoudelChhetri, C.K. Chang, Y.C. Huang, D.P. Young, I. Dubenko, S. Talapatra, N. Ali, S. Stadler, J. Appl. Phys. 129, 215108 (2021)
[65]	P. Gębara, Z. Śniadecki, J. Alloys Compd. 796, 153 (2019)
[66]	Y. Luo, J. Wang, J. Yang, D. Mao, J. Cui, B. Jia, X. Liu, K. Nielsch, X. Xu, J. He, Energy Environ. Sci. 16, 3743 (2023)
[67]	X. She, X. Su, H. Xie, J. Fu, Y. Yan, W. Liu, P.F. PoudeuPoudeu, X. Tang, A.C.S. Appl. Mater. Interf. 10, 25519 (2018)
[68]	H.S. Kousar, D. Srivastava, M. Karppinen, G.C. Tewari, J. Phys. Condens. Matter 31, 405704 (2019)
[69]	A. Quintana-Nedelcos, J. L. Sánchez Llamazares, C. F. Sánchez-Valdés, P. Álvarez Alonso, P. Gorria, P. Shamba, N. A. Morley, J. Alloys Compd. 694, 1189 (2017)