V取代Al位提升全赫斯勒合金Fe2VAl的热电性能

doi:10.15541/jim20250041

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1425-1432.DOI: 10.15541/jim20250041

V取代Al位提升全赫斯勒合金Fe₂VAl的热电性能

郑元顺¹(), 余健²(), 叶先峰¹, 梁栋¹, 朱婉婷¹, 聂晓蕾¹, 魏平¹, 赵文俞¹(), 张清杰¹

1.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
2.九江学院材料科学与工程学院, 九江 332005

收稿日期:2025-02-02 修回日期:2025-04-13 出版日期:2025-12-20 网络出版日期:2025-04-27
通讯作者: 余健, 副教授. E-mail: yujian@jju.edu;
赵文俞, 教授. E-mail: wyzhao@whut.edu.cn
作者简介:郑元顺(1999-), 男, 硕士研究生. E-mail: yszheng@whut.edu.cn

Boosting the Thermoelectric Performance of Full-Heusler Fe₂VAl Alloy via Substituting Al Site with V

ZHENG Yuanshun¹(), YU Jian²(), YE Xianfeng¹, LIANG Dong¹, ZHU Wanting¹, NIE Xiaolei¹, WEI Ping¹, ZHAO Wenyu¹(), ZHANG Qingjie¹

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. School of Materials Science and Engineering, Jiujiang University, Jiujiang 332005, China

Received:2025-02-02 Revised:2025-04-13 Published:2025-12-20 Online:2025-04-27
Contact: YU Jian, associate professor. E-mail: yujian@jju.edu;
ZHAO Wenyu, professor. E-mail: wyzhao@whut.edu.cn
About author:ZHENG Yuanshun (1999-), male, Master candidate. E-mail: yszheng@whut.edu.cn
Supported by:
National Natural Science Foundation of China(52130203);National Natural Science Foundation of China(92463310);National Natural Science Foundation of China(52201256);Guangdong Basic and Applied Basic Research Foundation(2022B1515120005)

摘要/Abstract

摘要： 全赫斯勒合金Fe₂VAl具有机械强度较高、电输运性能好和组成元素地球丰度高的优势, 在热电领域受到广泛关注。然而, 该合金的高晶格热导率极大限制了热电优值(zT)的提升。本研究采用电弧熔炼法制备了一系列名义化学成分为Fe₂V₁₊_xAl_1-_x(x=0~0.21)的块体材料, 系统研究了V取代Al位对物相组成、显微结构、能带结构和热电输运性能的影响。结果表明, 所有材料均为部分无序的B2单相结构。V掺杂可将费米能级上移至导带, 大幅度增大载流子浓度, 并将功率因子提升至4.5 mW·K^-2·m^-1。同时, 由于质量与应力波动引起的声子散射作用增强, 晶格热导率显著降低。最终, x=0.15的材料的最大zT达到0.14, 与未掺杂Fe₂VAl材料相比提升近280倍。该研究表明V取代Al位可以有效提升Fe₂VAl合金的热电性能。

关键词: Fe₂VAl基全赫斯勒合金, 反位缺陷, 显微结构, 热电性能

Abstract:

Full-Heusler Fe₂VAl alloy has received significant attention for thermoelectric (TE) applications due to its high mechanical strength, favorable electrical transport behavior, and earth-abundant constituent elements. However, its intrinsically high lattice thermal conductivity hinders the enhancement of the figure of merit (zT). In this study, a series of bulk materials with the nominal composition of Fe₂V₁₊_xAl_1-_x (x=0-0.21) were prepared by the arc-melting method. Effects of substituting Al site with V on the phase composition, microstructure, band structure, and TE transport properties were systematically investigated. All materials exhibit a single phase with a partially disordered B2 structure. V-doping shifts the Fermi level into the conduction band, significantly enhancing the carrier concentration, and resulting in a high power factor of 4.5 mW·K^-2·m^-1. Additionally, the lattice thermal conductivity is substantially reduced due to enhanced phonon scattering induced by the mass and stress fluctuations. Ultimately, a maximum zT of 0.14 is achieved for the material with x=0.15, which is nearly 280 times larger than that of undoped Fe₂VAl. This work demonstrates that substituting Al site with V can effectively improve the TE performance of Fe₂VAl alloy.

Key words: Fe₂VAl-based full-Heusler alloy, antisite defect, microstructure, thermoelectric performance

中图分类号:

TB34

郑元顺, 余健, 叶先峰, 梁栋, 朱婉婷, 聂晓蕾, 魏平, 赵文俞, 张清杰. V取代Al位提升全赫斯勒合金Fe₂VAl的热电性能[J]. 无机材料学报, 2025, 40(12): 1425-1432.

ZHENG Yuanshun, YU Jian, YE Xianfeng, LIANG Dong, ZHU Wanting, NIE Xiaolei, WEI Ping, ZHAO Wenyu, ZHANG Qingjie. Boosting the Thermoelectric Performance of Full-Heusler Fe₂VAl Alloy via Substituting Al Site with V[J]. Journal of Inorganic Materials, 2025, 40(12): 1425-1432.

图/表 6

Fig. 1 Crystal structure and phase composition obtained from XRD analysis (a) L21, B2, and A2 type crystal structures of Fe2VAl; (b) Powder XRD patterns of all Fe2V1+xAl1-x materials; (c) Changes of the diffraction peak of (220) plane with the doping amount increasing; (d) XRD Rietveld refinement result of V15; (e) Lattice parameter of all Fe2V1+xAl1-x materials obtained through Rietveld refinement

Fig. 2 Backscattered electron images and EDS mappings of selected Fe2V1+xAl1-x alloys (a-c) Backscattered electron images of (a) V00, (b) V12, and (c) V18; (d-f) EDS elemental mappings of V18

Table 1 Nominal compositions, EDS-measured compositions, carrier concentrations, and carrier mobilities of Fe2V1+xAl1-x alloys at 300 K

Nom. Comp.	EDS Comp.	n/(×10²⁰, cm^-3)	μ/(cm²·V^-1·s^-1)	Nom. Comp.	EDS Comp.	n/(×10²⁰, cm^-3)	μ/(cm²·V^-1·s^-1)
Fe₂VAl	Fe₂V_1.02Al	3.5	11.5	Fe₂V_1.12Al_0.88	Fe₂V_1.14Al_0.87	-29.6	5.9
Fe₂V_1.03Al_0.97	Fe₂V_1.05Al_0.95	-10.0	10.1	Fe₂V_1.15Al_0.85	Fe₂V_1.16Al_0.82	-57.8	4.7
Fe₂V_1.06Al_0.94	Fe₂V_1.07Al_0.91	-13.7	13.4	Fe₂V_1.18Al_0.82	Fe₂V_1.19Al_0.81	-59.5	4.2
Fe₂V_1.09Al_0.91	Fe₂V_1.11Al_0.90	-35.5	3.8	Fe₂V_1.21Al_0.79	Fe₂V_1.24Al_0.77	-86.0	2.7

Fig. 3 Band structure and total density of states (TDOS) diagrams of the Fe2V1+xAl1-x alloys (a-c) Energy band structure diagrams for (a) V00, (b) V06 and (c) V15; (d) Corresponding TDOS diagram showing the rigid band shift of the Fermi level caused by doping

Fig. 4 Temperature dependence of (a) electrical conductivity, (b) Seebeck coefficient, and (c) power factor for all Fe2V1+xAl1-x materials in the temperature range of 300-800 K

Fig. 5 Temperature dependence of (a) thermal conductivity, (b) electronic thermal conductivity, (c) lattice thermal conductivity, and (d) zT for all Fe2V1+xAl1-x alloys in the temperature range of 300-800 K

参考文献 34

[1]	YANG G S, SANG L A, ZHANG C, et al. The role of spin in thermoelectricity. Nature Reviews Physics, 2023, 5(8): 466. DOI
[2]	KIM H S, LIU W S, REN Z F. The bridge between the materials and devices of thermoelectric power generators. Energy & Environmental Science, 2017, 10(1): 69.
[3]	PEI Y, SHI X, LALONDE A, et al. Convergence of electronic bands for high performance bulk thermoelectrics. Nature, 2011, 473(7345): 66. DOI
[4]	HEREMANS J P, JOVOVIC V, TOBERER E S, et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science, 2008, 321(5888): 554. DOI PMID
[5]	LABORATORY M, LIMITED D I, MIYUKIGAOKA. Improvement of the efficiency of thermoelectric energy conversion by utilizing potential barriers. Japanese Journal of Applied Physics, 1997, 36(1): 170. DOI
[6]	ZHAO L D, LO S H, ZHANG Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508(7496): 373. DOI
[7]	LAN Y C, MINNICH A J, CHEN G, et al. Enhancement of thermoelectric figure-of-merit by a bulk nanostructuring approach. Advanced Functional Materials, 2010, 20(3): 357. DOI URL
[8]	MAHAN G D, SOFO J O. The best thermoelectric. Proceedings of the National Academy of Sciences of the United States of America, 1996, 93(15): 7436. PMID
[9]	TAVARES S S, YANG K S, MEYERS M A. Heusler alloys: past, properties, new alloys, and prospects. Progress in Materials Science, 2023, 137: 101017.
[10]	GRAF T, FELSER C, PARKIN S S P. Simple rules for the understanding of Heusler compounds. Progress in Solid State Chemistry, 2011, 39(1): 1. DOI URL
[11]	VAN DER REST C, DUPONT V, ERAUW J P, et al. On the reactive sintering of Heusler Fe₂VAl-based thermoelectric compounds. Intermetallics, 2020, 125: 106890. DOI URL
[12]	HARI S R, SRINIVAS V, LI C R, et al. Thermoelectric properties of rare-earth doped Fe₂VAl Heusler alloys. Journal of Physics- Condensed Matter, 2020, 32(35): 355706. DOI URL
[13]	KAWAHARADA Y, KUROSAKI K. Thermophysical properties of Fe₂VAl. Journal of Alloys and Compounds, 2003, 352(1/2): 48. DOI URL
[14]	SHAMIM S K, DEVI P, SINGH S, et al. Thermoelectric properties of Fe₂VAl in the temperature range 300-800 K: a combined experimental and theoretical study. Physica B-Condensed Matter, 2024, 673: 415496. DOI URL
[15]	HINTERLEITNER B, KNAPP I, PONEDER M, et al. Thermoelectric performance of a metastable thin-film Heusler alloy. Nature, 2019, 576(7785): 85. DOI
[16]	GARMROUDI F, PARZER M, RISS A, et al. Solubility limit and annealing effects on the microstructure & thermoelectric properties of Fe₂V_1-_xTa_xAl_1-_ySi_y Heusler compounds. Acta Materialia, 2021, 212: 116867. DOI URL
[17]	FUKUTA K, TSUCHIYA K, MIYAZAKI H, et al. Improving thermoelectric performance of Fe₂VAl-based Heusler compounds via high-pressure torsion. Applied Physics A: Materials Science & Processing, 2022, 128(3): 184.
[18]	ALLENO E. Review of the thermoelectric properties in nanostructured Fe₂VAl. Metals, 2018, 8(11): 864. DOI URL
[19]	ALLENO E, DIACK-RASSELIO A, NOUTACK M S T. Optimization of the thermoelectric properties in self-substituted Fe₂VAl. Physical Review Materials, 2023, 7(7): 075403. DOI URL
[20]	MIYAZAKI H, TANAKA S, IDE N, et al. Thermoelectric properties of Heusler-type off-stoichiometric Fe₂V₁₊_xAl_1-_x alloys. Materials Research Express, 2014, 1(1): 015901. DOI URL
[21]	DIACK-RASSELIO A, ROULEAU O, COULOMB L, et al. Influence of self-substitution on the thermoelectric Fe₂VAl Heusler alloy. Journal of Alloys and Compounds, 2022, 920: 166037. DOI URL
[22]	GARMROUDI F, PARZER M, RISS A, et al. Anderson transition in stoichiometric Fe₂VAl: high thermoelectric performance from impurity bands. Nature Communications, 2022, 13: 3599. DOI
[23]	CUI X, FENG Z, JIN Y. AutoFP: a GUI for highly automated Rietveld refinement using an expert system algorithm based on FullProf. Journal of Applied Crystallography, 2015, 48(5): 1581. DOI URL
[24]	PERDEW J P, RUZSINSZKY A, CSONKA G I, et al. Exchange and correlation in open systems of fluctuating electron number. Physical Review A, 2007, 76(4): 040501. DOI URL
[25]	SHAM L J, KOHN W. One-particle properties of an inhomogeneous interacting electron gas. Physical Review B, 1966, 145(2): 561.
[26]	MAIER S, DENIS S, ADAM S, et al. Order-disorder transitions in the Fe₂VAl Heusler alloy. Acta Materialia, 2016, 121: 126. DOI URL
[27]	HINTERLEITNER B, GARMROUDI F, REUMANN N, et al. The electronic pseudo band gap states and electronic transport of the full-Heusler compound Fe₂VAl. Journal of Materials Chemistry C, 2021, 9(6): 2073. DOI URL
[28]	OKAMURA H, KAWAHARA J, NANBA T, et al. Pseudogap formation in the intermetallic compounds (Fe_1-_xV_x)₃Al. Physical Review Letters, 2000, 84(16): 3674. PMID
[29]	NISHINO Y, KATO M, ASANO S, et al. Semiconductor-like behavior of electrical resistivity in Heusler-type Fe₂VAl compound. Physical Review Letters, 1997, 79(10): 1909. DOI URL
[30]	KNAPP I, BUDINSKA B, MILOSAVLJEVIC D, et al. Impurity band effects on transport and thermoelectric properties of Fe_2-_xNi_xVAl. Physical Review B, 2017, 96(4): 045204. DOI URL
[31]	GARMROUDI F, RUSS A, PARZER M, et al. Boosting the thermoelectric performance of Fe₂VAl-type Heusler compounds by band engineering. Physical Review B, 2021, 103(8): 085202. DOI URL
[32]	SHIN W H, ROH J W, RYU B, et al. Enhancing thermoelectric performances of bismuth antimony telluride via synergistic combination of multiscale structuring and band alignment by FeTe₂ Incorporation. ACS Applied Materials & Interfaces, 2018, 10(4): 3689.
[33]	KIM H S, GIBBS Z M, TANG Y L. Characterization of Lorenz number with Seebeck coefficient measurement. APL Materials, 2015, 3(4): 041506. DOI URL
[34]	YE X F, YU J, KE S Q, et al. Excellent thermoelectric performance of Fe₂NbAl alloy induced by strong crystal anharmonicity and high band degeneracy. npj Quantum Materials, 2024, 9(1): 60. DOI

V取代Al位提升全赫斯勒合金Fe₂VAl的热电性能

Boosting the Thermoelectric Performance of Full-Heusler Fe₂VAl Alloy via Substituting Al Site with V

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