Enhanced Thermoelectric and Mechanical Properties of ZrNiSn Half-Heusler Compounds by Excess Ag Doping at Ni Sites

doi:10.1007/s40195-025-01853-x

Abstract

Abstract:

Different from full-Heusler compounds, four vacancies in the face-centered cubic crystal structure provide extra sites for enhancing the thermoelectric properties of half-Heusler compounds (HHs). Herein, excess Ag is introduced to the Ni-site vacancies of ZrNiSn to optimize thermoelectric properties. The ZrNiAg_xSn (x = 0, 0.01, 0.02, and 0.03) samples were synthesized by levitation melting and spark plasma sintering. Remarkably, the introduction of excess Ag significantly improves the Seebeck coefficient of ZrNiAg_0.01Sn, and a peak power factor of ~ 4.52 mW/(m K²) is achieved in ZrNiAg_0.01Sn at 923 K, which is enhanced by 22.8% than that of pristine ZrNiSn. As a result, the figure of merit zT of pristine ZrNiSn is enhanced from ~ 0.60 to ~ 0.72 of ZrNiAg_0.01Sn at 923 K. Additionally, grain refinement effectively increases the Vickers hardness of ZrNiAg_0.01Sn, which is enhanced by 32.8% than that of pristine ZrNiSn. These results demonstrate a viable doping strategy for designing ZrNiSn-based HHs with excellent thermoelectric and mechanical properties.

Key words: ZrNiSn, Thermoelectric properties, Ag doping, Vickers hardness

Xinghui Wang, Yu Yan, Wen Zhang, Huijun Kang, Enyu Guo, Zongning Chen, Rongchun Chen, Tongmin Wang. Enhanced Thermoelectric and Mechanical Properties of ZrNiSn Half-Heusler Compounds by Excess Ag Doping at Ni Sites[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(5): 763-771.

Figures/Tables 7

Fig. 1 Crystal structures of ZrNiSn (HH) and ZrNi2Sn (FH) (Schematic diagram depicting the two defects present in ZrNiSn and the structural link between the FH/HH phases)

Fig. 2 a XRD patterns of the ZrNiAgxSn (x = 0.00, 0.01, 0.02, and 0.03) HHs, b lattice parameters with Ag content (x) in ZrNiAgxSn

Fig. 3 Microstructure a, and elemental mappings b-e of ZrNiAg0.01Sn

Fig. 4 SEM micrographs of the fracture section of ZrNiAgxSn: a x = 0, b x = 0.01, c x = 0.02, and d x = 0.03. Grain size distributions of ZrNiAgxSn: a1 x = 0, b1 x = 0.01, c1 x = 0.02, and d1 x = 0.03. Histogram of grain size distributions of ZrNiAgxSn: a2 x = 0, b2 x = 0.01, c2 x = 0.02, and d2 x = 0.03. e-h Elements maps of the fracture section of ZrNiAg0.02Sn

Fig. 5 a Temperature-dependent σ. b nH and μH at room temperature. c Temperature-dependent S. d Room temperature Pisarenko plot with m* = 3.56 me, where me is the electron effective mass. e Temperature-dependent PF for ZrNiAgxSn

Fig. 6 Temperature-dependent a κ, b κe, c L, d κl for ZrNiAgxSn

Fig. 7 Figure of merit zT for ZrNiAgxSn samples: a zT and b average zT. c Comparison of zT values of several typical Hf-free ZrNiSn TE materials. d Vickers hardness of ZrNiAgxSn samples at room temperature

References 64

[1]	D. Liu, Q. Cao, B. Qin, L. Zhao, Mater. Lab. 2, 230032 (2024)
[2]	Y. Fan, C. Xie, J. Li, X. Meng, J. Sun, J. Wu, X. Tang, G. Tan, Energy Environ. Mater. 7, e12535 (2024)
[3]	H. Su, H. Zhang, M. Zhou, Mater. Lab. 2, 230015 (2023)
[4]	J.P. Heremans, V. Jovovic, E.S. Toberer, A. Saramat, K. Kurosaki, A. Charoenphankdee, S. Yamanaka, G.J. Snyder, Science 321, 554 (2008) DOI PMID
[5]	P. Chen, H. Xie, L. Zhao, Acta Metall. Sin.-Engl. Lett. (2024). https://doi.org/10.1007/s40195-024-01798-7
[6]	J. Mao, H.S. Kim, J. Shuai, Z. Liu, R. He, U. Saparamadu, F. Tian, W. Liu, Z. Ren, Acta Mater. 633, 103 (2016)
[7]	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
[8]	Z. Hu, H. Yu, J. He, Y. Ran, H. Zeng, Y. Zhao, Z. Yu, K. Tai, Acta Metall. Sin.-Engl. Lett. 36, 1699 (2023)
[9]	Q. Zhang, H. Wang, W. Liu, H. Wang, B. YU, Q. Zhang, Z. Tian, G. Ni, S. Lee, K. Esfarjani, G. Chen, Z. Ren, Energy Environ. Sci. 5, 5246 (2012)
[10]	W. Liu, J. Zhou, Q. Jie, Y. Li, H.S. Kim, J. Bao, G. Chen, Z. Ren, Energy Environ. Sci. 9, 530 (2016)
[11]	H. Yang, J.H. Bahk, T. Day, A.M.S. Mohammed, G.J. Snyder, A. Shakouri, Y. Wu, Nano Lett. 15, 1349 (2015)
[12]	J.R. Sootsman, D.Y. Chung, M.G. Kanatzidis, Angew. Chem. Int. Ed. 48, 8616 (2009) DOI PMID
[13]	S. Bhattacharya, A. Bohra, R. Basu, R. Bhatt, S. Ahmad, K.N. Meshram, A.K. Debnath, A. Singh, S.K. Sarkar, M. Navneethan, Y. Hayakawa, D.K. Aswal, S.K. Gupta, J. Mater. Chem. A 2, 17122 (2014)
[14]	P. Jood, M. Ohta, Materials 8, 1124 (2015)
[15]	Y. Zhu, Z. Han, F. Jiang, E. Dong, B. Zhang, W. Zhang, W. Liu, Mater. Today Phys. 16, 100327 (2021)
[16]	P. Qiu, J. Yang, X. Huang, X. Chen, L. Chen, Appl. Phys. Lett. 96, 152105 (2010)
[17]	M. Hong, Z. Chen, L. Yang, T.C. Chasapis, S.D. Kang, Y. Zou, G.J. Auchterlonie, M.G. Kanatzidis, G.J. Snyder, J. Zou, J. Mater. Chem. A 5, 10713 (2017)
[18]	G. Joshi, X. Yan, H. Wang, W. Liu, G. Chen, Z. Ren, Adv. Energy Mater. 1, 643 (2011)
[19]	Y. Pan, B. He, C. Felser, Mater. Lab. 2, 230016 (2023)
[20]	R. Chen, Y. Yan, W. Zhang, F. Liu, H. Kang, E. Guo, Z. Chen, T. Wang, Chem. Mater. 35, 2202 (2023)
[21]	Q. Zhang, P. Xie, C. Liu, S. Li, X. Lei, L. Huang, G. Yuan, F. Cai, Mater. Today Phys. 24, 100648 (2022)
[22]	R. Akram, Y. Yan, D. Yang, X. She, G. Zheng, X. Su, X. Tang, Intermetallics 74, 1 (2016)
[23]	C. Jia, B. Zhu, C. Pang, C. Yuan, P. Xu, B. Xu, J. Bai, L. Tao, F. Xue, G. Tang, Mater. Today Phys. 33, 101039 (2023)
[24]	R. Chen, Q. Jiang, L. Jiang, R. Min, H. Kang, Z. Chen, E. Guo, X. Yang, T. Wang, Chem. Eng. J. 455, 140676 (2023)
[25]	S. Li, X. Bao, L. Yin, X. Ye, J. Mao, Q. Zhang, Acta Mater. 271, 119896 (2024)
[26]	R. Chen, Y. Yan, G. Li, R. Min, H. Kang, E. Guo, Z. Chen, X. Yang, T. Wang, J. Materiomics 10, 45 (2024)
[27]	M.A.A. Mohamed, E.M.M. Ibrahim, N.P. Rodriguez, S. Hampel, B. Büchner, G. Schierning, K. Nielsch, R. He, Acta Mater. 196, 669 (2020) DOI
[28]	R.B. Villoro, D. Zavanelli, C. June, D.A. Mattlat, R.H. Naderloo, N. Pérez, K. Nielsch, C.J. Snyder, C. Scheu, R. He, S. Zhang, Adv. Energy Mater. 13, 2204321 (2023)
[29]	S. Li, H. Zhu, J. Mao, Z. Feng, X. Li, C. Chen, F. Cao, X. Liu, D.J. Singh, Z. Ren, Q. Zhang, ACS Appl. Mater. Interfaces 11, 41321 (2019)
[30]	E. Haque, M.A. Hossain, Results Phys. 10, 458 (2018)
[31]	P.R. Raghuvanshi, S. Mondal, A. Bhattacharya, J. Mater. Chem. A 8, 25187 (2020)
[32]	V.V. Romaka, G. Rogl, A. Grytsiv, P. Rogl, Comput. Mater. Sci. 172, 109307 (2020)
[33]	X. Yang, Z. Jiang, J. Li, H. Kang, D. Liu, F. Yang, Z. Chen, E. Guo, X. Jiang, T. Wang, Nano Energy 78, 105372 (2020)
[34]	P. Larson, S.D. Mahanti, Phys. Rev. B 62, 12754 (2000)
[35]	K. Miyamoto, A. Kimura, K. Sakamoto, M. Ye, Y. Cui, K. Shimada, H. Namatame, M. Taniguchi, S. Fujimori, Y. Saitoh, E. Ikenaga, K. Kobayashi, J. Tadano, T. Kanometa, Appl. Phys. Express 1, 081901 (2008)
[36]	N.S. Chauhan, S. Bathula, B. Gahtori, S.D. Mahanti, A. Bhattacharya, A. Vishwakarma, R. Bhardwaj, V.N. Singh, A. Dhar, ACS Appl. Mater. Interfaces 11, 47830 (2019)
[37]	S.A. Barczak, J.E. Halpin, J. Buckman, R. Decourt, M. Pollet, R.I. Smith, D.A. MacLaren, J.G. Bos, ACS Appl. Mater. Interfaces 10, 4786 (2018)
[38]	R. Yan, C. Shen, M. Widenmeyer, T. Luo, R. Winkler, E. Adabifiroozjaei, R. Xie, S. Yoon, E. Suard, L. Molina-Luna, H. Zhang, W. Xie, A. Weidenkaff, Mater. Today Phys. 33, 101049 (2023)
[39]	S. Jain, A.K. Verma, K.K. Johari, C. Candolfi, B. Lenoir, B. Gahtori, J. Mater. Res. 39, 3249 (2024)
[40]	B. Ge, M. Yang, Q. Zu, J. Guo, Y. Tian, Q. Peng, Acta Mater. 201, 477 (2020)
[41]	R.B. Villoro, M. Wood, T. Luo, H. Bishara, L. Abdellaoui, D. Zavanelli, B. Gault, G.J. Snyder, C. Scheu, S. Zhang, Acta Mater. 249, 118816 (2023)
[42]	X. Chen, H. Wu, J. Cui, Y. Xiao, Y. Zhang, J. He, Y. Chen, J. Cao, W. Cai, S.J. Pennycook, Z. Liu, L. Zhao, J. Sui, Nano Energy 52, 246 (2018)
[43]	N. Qu, Y. Zhu, J. Zhu, K. Yu, F. Guo, Z. Liu, Q. Zhang, W. Cai, J. Sui, J. Magnes. Alloy. 12, 4538 (2024)
[44]	S.V. Faleev, F. Léonard, Phys. Rev. B 77, 214304 (2008)
[45]	J.P.A. Makongo, D.K. Misra, X. Zhou, A. Pant, M.R. Shabetai, X. Su, C. Uher, K.L. Stokes, P.F.P. Poudeu, J. Am. Chem. Soc. 133, 18843 (2011) DOI PMID
[46]	W.J. Xie, J. He, S. Zhu, X.L. Su, S.Y. Wang, T. Holgate, J.W. Graff, V. Ponnambalam, S.J. Poon, X.F. Tang, Q.J. Zhang, T.M. Tritt, Acta Mater. 58, 4705 (2010)
[47]	N.S. Chauhan, A. Bhardwaj, T.D. Senguttuvan, R.P. Pant, R.C. Mallik, D.K. Misra, J. Mater. Chem. C 4, 5766 (2016)
[48]	K.K. Johari, R. Bhardwaj, N.S. Chauhan, B. Gahtori, S. Bathula, S. Auluck, S.R. Dhakate, ACS Appl. Energy Mater. 3, 1349 (2019)
[49]	N.S. Chauhan, S. Bathula, A. Vishwakarma, R. Bhardwaj, B. Gahtori, A. Kumar, A. Dhar, ACS Appl. Energy Mater. 1, 757 (2018)
[50]	L. Zhao, S. Lo, J. He, H. Li, K. Biswas, J. Androulakis, C. Wu, T.P. Hogan, D. Chung, V.P. Dravid, M.G. Kanatzidis, J. Am. Chem. Soc. 133, 20476 (2011) DOI PMID
[51]	X. Guan, Z. Liu, N. Ma, Z. Li, J. Liu, H. Zhang, H. Li, Q. Ba, J. Ma, C. Jin, A. Xia, Acta Metall. Sin.-Engl. Lett. (2024). https://doi.org/10.1007/s40195-024-01794-x
[52]	R. Min, Y. Wang, X. Jiang, R. Chen, H. Kang, E. Guo, Z. Chen, X. Yang, T. Wang, Chem. Eng. J. 449, 137898 (2022)
[53]	J. Shen, C. Fu, Y. Liu, X. Zhao, T. Zhu, Energy Storage Mater. 10, 69 (2018)
[54]	H. Kim, Z.M. Gibbs, Y. Tang, H. Wang, G.J. Snyder, APL Mater. 3, 041506 (2015)
[55]	J.P.A. Makongo, D.K. Misra, J.R. Salvador, N.J. Takas, G. Wang, M.R. Shabetai, A. Pant, P. Paudel, C. Uher, K.L. Stokes, P.F.P. Poudeu, J. Solid State Chem. 184, 2948 (2011)
[56]	C. Zhang, G. Yan, Y. Wang, L. Hu, F. Liu, W. Ao, O. Cojocaru-Mirédin, M. Wutting, G.J. Snyder, Y. Yu, Adv. Energy Mater. 13, 2203361 (2022)
[57]	P.G. Klemens, Phys. Rev. 119, 507 (1960)
[58]	X. Yang, Z. Jiang, H. Kang, Z. Chen, E. Guo, D. Liu, F. Yang, R. Li, X. Jiang, T. Wang, ACS Appl. Mater. Interfaces 12, 3773 (2019)
[59]	T. Dahal, S. Gahlawat, Q. Jie, K. Dahal, Y. Lan, K. White, Z. Ren, J. Appl. Phys. 117, 055101 (2015)
[60]	Z. Liu, W. Gao, X. Meng, X. Li, J. Mao, Y. Wang, J. Shuai, W. Cai, Z. Ren, J. Sui, Scr. Mater. 127, 72 (2017)
[61]	G. Li, K.R. Gadelrab, T. Souier, P.L. Potapov, G. Chen, M. Chiesa, Nanotechnology 23, 065703 (2012)
[62]	R.D. Schmidt, E.D. Case, L. Zhao, M.G. Kanatzidis, J. Mater. Sci. 50, 1770 (2014)
[63]	R.D. Schmidt, E.D. Case, J.E. Ni, R.M. Trejo, E. Lara-Curzio, R.J. Korkosz, M.G. Kanatzidis, J. Mater. Sci. 48, 8244 (2013)
[64]	B. Li, P. Xie, S. Zhang, D. Liu, J. Mater. Sci. 46, 4000 (2011)