Cu ions migration modulation advances thermoelectric performance in copper selenides

doi:10.1016/j.jmst.2025.05.046

Abstract

Abstract: Ion-blocking barriers play a key role in improving the electrical stability of superionic conductors. However, simultaneous enhancement of the thermoelectric performance and stability of superionic conductors requires a compromise among carrier, phonon, and ion propagation. In this study, a strategy of Cu ions migration modulation by compositing macroscopic and insulating phlogopite into Cu-based superionic conductors is proposed, which is effective in improving the thermoelectric properties and stability of copper selenide. The adverse effect of Cu ions migration on carrier transport was weakened at high temperatures for the composites by the phlogopite sheets. Multiscale lattice defects, including point defects, dislocations, nanopores, and nanoprecipitates, in copper selenide will help strengthen all-scale phonon scattering, reducing the lattice thermal conductivity of composites. A peak ZT value of 2.5 is yielded at 973 K in the composite due to the maintained electrical transport properties and significantly reduced thermal conductivity. The stability of the bulk composite and thermoelectric module was improved owing to the suppressed Cu-ion migration and the constructed voltage division circuit by the insulating phlogopite sheets. These findings help gain a deep understanding of the role played by macroscopic insulating phlogopite in manipulating Cu ions migration for enhancing the thermoelectric performance and stability of other Cu-based superionic conductors.

Key words: Copper slenide, Phlogopite, Cu ions migration, Thermoelectric performance, Stability

Yi-Xin Zhang, Xi Yan, Xing Yang, Lan Yu, Yue-Xing Chen, Ding-Yi Yu, Zulai Li, Zhen-Hua Ge, Jiushuai Deng, Jing Feng. Cu ions migration modulation advances thermoelectric performance in copper selenides[J]. J. Mater. Sci. Technol., 2026, 248: 189-198.

References

[1] Y. Xiao, L.-D. Zhao, Science 367 (2020) 1196-1197.
[2] X.-L. Shi, J.Zou, Z.-G. Chen, Chem. Rev. 120(2020) 7399-7515.
[3] R. Pathak, L. Xie, S. Das, T. Ghosh, A. Bhui, K. Dolui, D. Sanyal, J. He, K. Biswas, Energy Environ. Sci. 16(2023) 3110.
[4] K. Zhao, P. Qiu, X. Shi, L. Chen, Adv. Funct. Mater. 30(2020) 1903867.
[5] S.Y. Back, S. Meikle, T. Mori, J. Mater. Sci.Technol. 227(2025) 57-66.
[6] L.D. Zhao, V.P. Dravidb, M.G. Kanatzidis, Energy Environ. Sci. 7(2014) 251.
[7] D. Yang, X. Su, J. Li, H. Bai, S. Wang, H.T.Zhi Li, K.Tang, T. Luo, Y. Yan, J. Wu, J. Yang, Q. Zhang, C. Uher, M.G. Kanatzidis, X. Tang, Adv. Mater. 32(2020) 2003730.
[8] H. Liang, J. Guo, Y.-X. Zhou, Z.-Y. Wang, J. Feng, Z.-H. Ge, J. Materiomics 8 (2022) 174-183.
[9] Z. Long, Y. Wang, X. Sun, Y. Li, Z. Zeng, L. Zhang, H. Chen, Adv. Mater. 35(2023) 2210345.
[10] Y.-X. Zhang, X.Yang, X. Yan, T.-E. Shi, J. Feng, Z.-H. Ge, J. Alloys Compd. 1002(2024) 175222.
[11] X. Yan, H. Pan, Y. Zhang, T. Yang, Y. Wang, K. Huang, C. Wang, J. Feng, Z. Ge, J. Adv. Ceram. 13(2024) 641-651.
[12] H. Hu, Y. Ju, J. Yu, Z. Wanh, J. Pei, H.-C. Thong, J.-W. Li, B. Cai, F. Liu, Z. Han, B. Su, H.-L. Zhuang, Y. Jiang, H. Li, Q. Li, H. Zhao, B.-P. Zhang, J. Zhu, J.-F. Li, Nat. Mater. 23(2024) 527-534.
[13] Y. Li, S. Bai, Y. Wen, Z. Zhao, L. Wang, S. Liu, J. Zheng, S. Wang, S. Liu, D. Gao, D. Liu, Y. Zhu, Q. Cao, X. Gao, H. Xie, L.-D. Zhao, Sci.Bull. 69(2024) 1728-1737.
[14] L. Miao, X. Lu, Q. Zhang, X. Tan, L. Chen, K. Pang, R. Li, Q. Sun, M. Wang, P. Sun, J. Wu, G. Liu, Z. Song, J. Jiang, J. Mater. Sci.Technol. 223(2025) 114-122.
[15] Y. Qin, B. Qin, T. Hong, X. Zhang, D. Wang, D. Liu, Z.-Y. Wang, L. Su, S. Wang, X. Gao, Z.-H. Ge, L.-D. Zhao, Science 383 (2024) 1204-1209.
[16] L. Wang, Y. Wen, S. Bai, C. Chang, Y. Li, S. Liu, D. Liu, S. Wang, Z. Zhao, S. Zhan, Q. Cao, X. Gao, H. Xie, L.-D. Zhao, Nat.Commun. 15(2024) 3782.
[17] Q. Zhang, P. Ying, A. Farrukh, Y. Gong, J. Liu, X. Huang, D. Li, M. Wang, G. Chen, G. Tang, Acta Mater. 276(2024) 120132.
[18] Q. Chen, C. Yang, T. Xing, J. Xi, W. Zhang, J. Yang, L. Xi, J. Materiomics 11 (2025) 100832.
[19] C. Zhou, Y.K. Lee, Y. Yu, S. Byun, Z.-Z. Luo, H.Lee, B. Ge, Y.-L. Lee, X. Chen, J.Y. Lee, O. Cojocaru-Mirédin, H. Chang, J. Im, S.-P. Cho, M. Wuttig, V.P. Dravid, M.G. Kanatzidis, I. Chung, Nat. Mater. 20(2021) 1378-1384.
[20] D. Liu, D. Wang, T. Hong, Z. Wang, Y. Wang, Y. Qin, L. Su, T. Yang, X. Gao, Z. Ge, B. Qin, L.-D. Zhao, Science 380 (2023) 841-846.
[21] S. Byun, B. Ge, H. Song, S.-P. Cho, M.S. Hong, J. Im, I. Chung, Joule 8 (2024) 1520-1538.
[22] H. Liu, X. Shi, F. Xu, L. Zhang, W. Zhang, L. Chen, Q. Li, C. Uher, T. Day, G.J. Snyder, Nat. Mater. 11(2012) 422-425.
[23] J. Yu, X. Liu, H. Hu, Y. Jiang, H.-L. Zhuang, H. Li, B. Su, J.-W. Li, Z. Han, Z. Wang, L. Chen, K. Hayashi, Y. Miyazaki, B.L. Mehdi, J.-F. Li, Joule 8 (2024) 1-15.
[24] P. Ying, Q. Jian, Y. Gong, T. Song, Y. Yang, Y. Geng, J. Huang, R. Sun, C. Chen, T. Shen, Y. Li, W. Dou, C. Liang, Y. Liu, D. Xiang, T. Feng, X. Fei, Y. Zhang, K. Song, Y. Zhang, H. Wu, G. Tang, Nat. Commun. 16(2025) 3305-3316.
[25] D.J. Voneshen, H.C. Walker, K. Refson, J.P. Goff, Phys. Rev. Lett. 118(2017) 145901.
[26] Z.W. Chen, X.Y. Zhang, Y.Z. Pei, Adv. Mater. 30(2018) 1705617.
[27] Y.-X. Sun, L.-L. Xi, J. Yang, L.-H. Wu, X. Shi, L.-D. Chen, J. Snyder, J.-H. Yang, W.-Q. Zhang, J. Mater. Chem. A 5 (2017) 5098-5105.
[28] P. Qiu, M.T. Agne, Y. Liu, Y. Zhu, H. Chen, T. Mao, J. Yang, W. Zhang, S.M. Haile, W.G. Zeier, J. Janek, C. Uher, X. Shi, L. Chen, G.J. Snyder, Nat. Commun. 9(2018) 2910.
[29] K. Zhao, A.B. Blichfeld, H. Chen, Q. Song, T. Zhang, C. Zhu, D. Ren, R. Hanus, P. Qiu, B.B. Iversen, F. Xu, G.J. Snyder, X. Shi, L. Chen, Chem. Mater. 29(2017) 6367-6377.
[30] T. Mao, P. Qiu, X. Du, P. Hu, K. Zhao, J. Xiao, X. Shi, L. Chen, Adv. Funct. Mater. 30(2019) 1908315.
[31] W.-D. Liu, L.Yang, Z.-G. Chen, J. Zou, Adv. Mater. 32(2020) 1905703.
[32] T. Mao, P. Qiu, P. Hu, X. Du, K. Zhao, T.-R. Wei, J.Xiao, X. Shi, L. Chen, Adv. Sci. 7(2019) 1901598.
[33] H. Hu, B. Su, X. Liu, H.-C. Thong, Y. Jiang, H. Li, J.-W. Li, H.-L. Zhuang, Z. Han, J. Yu, B.L. Mehdi, J.-F. Li, Joule 8 (2024) 1-14.
[34] J. Yu, H. Hu, Y. Jiang, H.-L. Zhuang, H.-C. Thong, B. Su, J.-W. Li, Z. Han, H. Li, J. Pei, J.-F. Li, Adv. Energy Mater. 14(2024) 2303942.
[35] Y.-X. Zhang, Q.-Y. Huang, X. Yan, C.-Y. Wang, T.-Y. Yang, Z.-Y. Wang, Y.-C. Shi, Q. Shan, J. Feng, Z.-H. Ge, Nat. Commun. 15(2024) 2736.
[36] H. Tang, F.-H. Sun, J.-F. Dong, H. Asfandiyar, L. Zhuang, Y. Pan, J.-F. Li, Nano Energy 49 (2018) 267-273.
[37] Z.-H. Ge, Y.-X. Zhang, T.-Y. Yang, D. He, Y. Xiao, H. Lai, Y. Wang, J. Deng, J.-F. Li, J. Feng, J. He, L.-D. Zhao, Joule 8 (2024) 1-12.
[38] K. Zhao, A.B. Blichfeld, E. Eikeland, P. Qiu, D. Ren, B.B. Iversen, X. Shi, L. Chen, J. Mater. Chem. A 5 (2017) 18148.
[39] K. Zhao, P. Qiu, Q. Song, A.B. Blichfeld, E. Eikeland, D. Ren, B. Ge, B.B. Iversen, X. Shi, L. Chen, Mater. Today Phys. 1(2017) 14-23.
[40] M.F. Brigatti, L. Medici, E. Saccani, C. Vaccaro, Am. Mineral. 81(1996) 913-927.
[41] M. Zema, G. Ventruti, M. Lacalamita, F. Scordari, Am. Mineral. 95(2010) 1458-1466.
[42] F. Najafkhani, S. Kheiri, B. Pourbahari, H. Mirzadeh, Arch. Civ. Mech. Eng. 21(2021) 1-20.
[43] M. Li, Z. Ding, Q. Meng, J. Zhou, Y. Zhu, H. Liu, M.S. Dresselhaus, G. Chen, Nano Lett. 17(2017) 1587-1594.
[44] H.-S. Kim, S.D. Kang, Y. Tang, R. Hanus, G.J. Snyder, Mater. Horiz. 3(2016) 234.
[45] Z. Chen, B. Ge, W. Li, S. Lin, J. Shen, Y. Chang, R. Hanus, G.J. Snyder, Y. Pei, Nat. Commun. 8(2017) 13828.
[46] L. Wang, X. Zhang, L.-D. Zhao, Acc.Mater. Res. 4(2023) 448-456.
[47] J. Zhu, X. Zhang, M. Guo, J. Li, J. Hu, S. Cai, W. Cai, Y. Zhang, J. Sui, NPG Asia Mater. 7(2021) 116.
[48] G. Xu, P. Ren, T. Lin, X. Wu, Y. Zhang, S. Niu, T.P. Bailey, J. Appl. Phys. 123(2018) 015101.
[49] L. Su, H. Shi, S. Wang, D. Wang, B. Qin, Y. Wang, C. Chang, L.-D. Zhao, Adv.Energy Mater. 13(2023) 2300312.
[50] T.D. Chheda, M. Mookherjee, D. Mainprice, A.M.d. Santos, J.J. Molaison, J. Chantel, G. Manthilake, W.A. Bassett, Phys. Earth Planet. Inter. 233(2014) 1-12.
[51] R. Nunna, P. Qiu, M. Yin, H. Chen, R. Hanus, Q. Song, T. Zhang, M.-Y. Chou, M.T. Agne, J. He, G.J. Snyder, X. Shi, L. Chen, Energy Environ. Sci. 10(2017) 1928.
[52] A .A . Olvera, N.A . Moroz, P. Sahoo, P. Ren, T.P. Bailey, A .A . Page, C. Uher, P.F.P. Poudeu, Energy Environ. Sci. 10(2017) 1668.
[53] F. Kong, J. Bai, Y. Zhao, Y. Liu, J. Shi, Z. Wang, R. Xiong, Appl. Phys. Lett. 115(2019) 203901.
[54] M. Li, S.M.K.N. Islam, M. Yahyaoglu, D. Pan, X. Shi, L. Chen, U. Aydemir, X. Wang, InfoMat 1 (2019) 108-115.
[55] D. Yang, H. Bai, X. Su, Z. Li, T. Luo, J. Li, H. Tang, H. Luo, Q. Zhang, C. Uher, J. Wu, X. Tang, Cell Rep. Phys. Sci. 2(2021) 100345.
[56] T. Mao, P. Qiu, J. Liu, X. Du, P. Hu, K. Zhao, D. Ren, X. Shi, L. Chen, Phys. Chem. Chem. Phys. 22(2020) 7374-7380.
[57] S. Xiang, Y. Liang, X. Han, P. Yan, X. Zhang, Inorg. Chem. 61(2022) 14973-14986.
[58] P. Qiu, T. Mao, Z. Huang, X. Xia, J. Liao, M.T. Agne, M. Gu, Q. Zhang, D. Ren, S. Bai, X. Shi, G.J. Snyder, L. Chen, Joule 3 (2019) 1-11.
[59] S. Zhao, H. Chen, X. Zhao, J. Luo, Z. Tang, G. Zeng, K. Yang, Z. Wei, W. Wen, X. Chen, Y. Sun, Mater. Today Phys. 15(2020) 100271 .