高活性FeCoNiCuMn高熵合金纳米粒子/碳布复合材料的合成及其在热电化学电池中的性能

doi:10.15541/jim20260030

无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1387-1395.DOI: 10.15541/jim20260030

高活性FeCoNiCuMn高熵合金纳米粒子/碳布复合材料的合成及其在热电化学电池中的性能

朱梦婷(), 张瑞峰, 乔紫涵, 马汝广(), 吴正颖()

苏州科技大学材料科学与工程学院, 江苏省环境功能材料重点实验室, 苏州 215009

收稿日期:2026-01-19 修回日期:2026-03-19 出版日期:2026-10-20 网络出版日期:2026-04-20
通讯作者: 马汝广, 教授. E-mail: ruguangma@usts.edu.cn;
吴正颖, 教授. E-mail: zywu@mail.usts.edu.cn
作者简介:朱梦婷(1999-), 女, 硕士研究生. E-mail: zmt1501322726@163.com
基金资助:
国家自然科学基金(22579119);江苏省自然科学基金(BK20241946)

Highly Active FeCoNiCuMn High-entropy Alloys/Carbon Cloth Composite: Synthesis and Its Performance in Thermo-electrochemical Cells

ZHU Mengting(), ZHANG Ruifeng, QIAO Zihan, MA Ruguang(), WU Zhengying()

Jiangsu Key Laboratory for Environment Functional Materials, School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, China

Received:2026-01-19 Revised:2026-03-19 Published:2026-10-20 Online:2026-04-20
Contact: MA Ruguang, professor. E-mail: ruguangma@usts.edu.cn;
WU Zhengying, professor. E-mail: zywu@mail.usts.edu.cn
About author:ZHU Mengting (1999-), female, Master candidate. E-mail: zmt1501322726@163.com
Supported by:
National Natural Science Foundation of China(22579119);Natural Science Foundation of Jiangsu Province(BK20241946)

摘要/Abstract

摘要：

热电化学电池(Thermo-electrochemical cells, TECs)是一种新型低品位热富集系统, 对其开发利用将有利于提高整体能源效率并缓解城市热岛效应。金属铂(Pt)是TECs研究中常用的电极材料, 但Pt高昂的价格限制了TECs的推广应用。因此, 开发低成本且性能优异的替代电极成为TECs领域的研究热点。本研究以商用碳布(Carbon cloth, CC)为基底和结构导向剂, 将具有高催化活性的FeCoNiCuMn高熵合金(High-entropy alloys, HEAs)纳米粒子均匀生长在碳布上, 得到FeCoNiCuMn HEAs/CC复合材料, 并将其用作TECs电极。HEAs的高熵效应不仅赋予复合材料稳定的化学结构, 其多主元互相作用也提升了材料的催化活性和反应动力学。因此, FeCoNiCuMn HEAs/CC具有比CC、三元FeCoNi/CC和四元FeCoNiCu/CC更大的电化学活性表面积(2.52 cm²)以及更小的电荷转移电阻(2 Ω)。将HEAs/CC用作TECs电极, 在22.0 K温差下, 该电池具有0.35 mA·cm^-2的电流密度和30.40 mW·m^-2的输出功率密度, 远高于相同条件下以CC (0.17 mA·cm^-2/14.55 mW·m^-2)、FeCoNi/CC (0.27 mA·cm^-2/19.00 mW·m^-2)和FeCoNiCu/CC (0.30 mA·cm^-2/24.44 mW·m^-2)为电极的TECs体系。并且, 该电池体系循环7 d依然保持了91.5%的短路电流, 且电池可逆性良好。本研究所构建的高活性FeCoNiCuMn HEAs/CC复合材料为低成本、高性能TECs电极材料的开发应用提供了新的思路。

关键词: 低品位热富集, 热电化学电池, 电极材料, 高熵合金

Abstract:

Thermo-electrochemical cells (TECs) are a new type of system for harvesting low-grade waste heat. Their development and utilization can contribute to improving overall energy efficiency and mitigating the urban heat island effect. Metallic platinum (Pt), a commonly used electrode material in TEC research, is costly, which significantly limits the widespread application of TECs. Therefore, developing low-cost, high-performance alternative electrodes has become a research hotspot in the field of TECs. In this study, commercial carbon cloth (CC) was used as both the substrate and structural directing agent. Then, catalytically active FeCoNiCuMn high-entropy alloys (HEAs) nanoparticles were uniformly grown onto CC, forming a FeCoNiCuMn HEAs/CC composite used as an electrode material for TECs. The high-entropy effect of HEAs endows the composite with the stable chemical structure, while the interaction among its multiple principal elements enhances its catalytic activity and reaction kinetics. Thus, the FeCoNiCuMn HEAs/CC electrode possesses a higher electrochemical active surface area (2.52 cm²) and a lower charge transfer resistance (2 Ω) compared to CC, the ternary FeCoNi/CC, and the quaternary FeCoNiCu/CC. Furthermore, the HEAs/CC-based TECs achieve a current density of 0.35 mA·cm^-2 and an output power density of 30.40 mW·m^-2 under a temperature difference of 22.0 K, significantly higher than those achieved by TECs using CC (0.17 mA·cm^-2/14.55 mW·m^-2), FeCoNi/CC (0.27 mA·cm^-2/19.00 mW·m^-2), and FeCoNiCu/CC (0.30 mA·cm^-2/24.44 mW·m^-2) as electrodes under the same conditions. Additionally, the cell system maintains 91.5% of its initial short-circuit current after 7 d of cycling and also exhibits good reversibility. The highly active FeCoNiCuMn HEAs/CC composite constructed in this study provides a promising pathway for the development and application of low-cost, high-performance TECs electrode materials.

Key words: low-grade waste heat harvesting, thermo-electrochemical cell, electrode material, high-entropy alloy

中图分类号:

TQ174

朱梦婷, 张瑞峰, 乔紫涵, 马汝广, 吴正颖. 高活性FeCoNiCuMn高熵合金纳米粒子/碳布复合材料的合成及其在热电化学电池中的性能[J]. 无机材料学报, 2026, 41(10): 1387-1395.

ZHU Mengting, ZHANG Ruifeng, QIAO Zihan, MA Ruguang, WU Zhengying. Highly Active FeCoNiCuMn High-entropy Alloys/Carbon Cloth Composite: Synthesis and Its Performance in Thermo-electrochemical Cells[J]. Journal of Inorganic Materials, 2026, 41(10): 1387-1395.

图/表 11

图1 HEAs/CC的合成示意图和SEM和TEM表征

Fig. 1 Schematic illustration, SEM and TEM characterizations of HEAs/CC (a) Schematic illustration for the formation of HEAs/CC; SEM images of (b, c) HEAs/CC As and (d) HEAs/CC; (e) TEM image with inset showing the particle size distribution; (f, g) HRTEM images with insets in (f) showing fast Fourier transform (FFT) images of HEAs/CC; (h) EDS elemental mappings of Fe, Co, Ni, Cu, and Mn elements

图2 HEAs/CC的XRD和XPS谱图

Fig. 2 XRD and XPS results of HEAs/CC (a) XRD patterns of HEAs/CC As and HEAs/CC; (b) Magnified XRD pattern of HEAs/CC; (c) Survey, (d) C1s, (e) Fe2p, (f) Co2p, (g) Ni2p, (h) Cu2p, and (i) Mn2p XPS spectra of HEAs/CC. Colorful figures are available on website

图3 CC、FeCoNi/CC、FeCoNiCu/CC和HEAs/CC的电化学性能

Fig. 3 Electrochemical performance of CC, FeCoNi/CC, FeCoNiCu/CC and HEAs/CC CV curves of (a) FeCoNi/CC, (b) FeCoNiCu/CC, and (c) HEAs/CC under different scan rates; (d) Fitting lines of peak current vs. v1/2; (e) CV curves at a scan rate of 10 mV·s-1; (f) ESA histogram; (g) LSV curves; (h) EIS spectra and (i) magnified area

图4 TECs的示意图

Fig. 4 Schematic diagram of TECs

图5 CC、FeCoNi/CC、FeCoNiCu/CC和HEAs/CC的热电化学性能

Fig. 5 Thermo-electrochemical performance of CC, FeCoNi/CC, FeCoNiCu/CC and HEAs/CC (a) VOC-ΔT curves and histogram of Se; (b) ISC-ΔT fitting lines; (c) Pmax-ΔT curves; (d-g) JSC-V and P-V curves; (h) Cycling performance; (i) Reversibility in the ΔT range from 4.0 K to 20.8 K. Colorful figures are available on website

图6 HEAs/CC-TECs在ΔT=13.0 K运行7 d的稳定性

Fig. 6 Stability of HEAs/CC-TECs for over 7 d at ΔT=13.0 K Colorful figure is available on website

图S1 TECs装置的(a)示意图和(b)实物照片[S2]

Fig. S1 (a) Schematic diagram and (b) physical photo of the TECs device[S2]

图S2 以HEAs/CC、Pt为电极的TECs体系的热电化学性能对比

Fig. S2 Comparison of thermo-electrochemical performance of TEC systems with HEAs/CC and Pt as electrodes (a) ISC-ΔT fitting lines; (b) Pmax-ΔT curves; (c, d) JSC-V and P-V curves

图S3 循环7 d后HEAs/CC的SEM表征

Fig. S3 SEM characterizations of HEAs/CC after the 7-day cycles (a, b) SEM images of HEAs/CC; (c) Magnified SEM image in the yellow line frame of (a); (d) EDS elemental mappings of Fe, Co, Ni, Cu, and Mn elements

图S4 循环7 d前后HEAs/CC的XPS全谱图

Fig. S4 XPS survey spectra of HEAs/CC before and after the 7-day cycles

图S5 循环7 d前后HEAs/CC的XPS精细谱图

Fig. S5 High-resolution XPS spectra of HEAs/CC before and after the 7-day cycles (a) C1s; (b) Fe2p; (c) Co2p; (d) Ni2p; (e) Cu2p; (f) Mn2p

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高活性FeCoNiCuMn高熵合金纳米粒子/碳布复合材料的合成及其在热电化学电池中的性能

Highly Active FeCoNiCuMn High-entropy Alloys/Carbon Cloth Composite: Synthesis and Its Performance in Thermo-electrochemical Cells

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