Ag2Se热电纤维的硒化反应制备及其性能研究

doi:10.15541/jim20260013

无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1238-1246.DOI: 10.15541/jim20260013

Ag₂Se热电纤维的硒化反应制备及其性能研究

尚勃屹¹(), 孙婷婷²(), 王连军¹^,³(), 江莞¹^,³

¹ 东华大学材料科学与工程学院, 先进纤维材料全国重点实验室, 上海 201620
² 东华大学生物与医学工程学院, 上海 201620
³ 东华大学先进玻璃制造技术教育部工程研究中心, 上海 201620

收稿日期:2026-01-10 修回日期:2026-03-19 出版日期:2026-09-20 网络出版日期:2026-05-19
通讯作者: 孙婷婷, 讲师. E-mail: tingtingsun@dhu.edu.cn;
王连军, 教授. E-mail: wanglj@dhu.edu.cn
作者简介:尚勃屹(2001-), 男, 硕士研究生. E-mail: 2230368@mail.dhu.edu.cn
基金资助:
国家自然科学基金(U23A2068);国家自然科学基金(U24A2061);国家自然科学基金(52403349)

Fabrication and Properties of Ag₂Se Thermoelectric Fibers via Selenization

SHANG Boyi¹(), SUN Tingting²(), WANG Lianjun¹^,³(), JIANG Wan¹^,³

¹ State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
² College of Biological Science and Medical Engineering, Donghua University, Shanghai 201620, China
³ Engineering Research Center of Advanced Glass Manufacturing Technology, Ministry of Education, Donghua University, Shanghai 201620, China

Received:2026-01-10 Revised:2026-03-19 Published:2026-09-20 Online:2026-05-19
Contact: SUN Tingting, lecturer. E-mail: tingtingsun@dhu.edu.cn;WANG Lianjun, professor. E-mail: wanglj@dhu.edu.cn
About author:SHANG Boyi (2001-), male, Master candidate. E-mail: 2230368@mail.dhu.edu.cn
Supported by:
National Natural Science Foundation of China(U23A2068);National Natural Science Foundation of China(U24A2061);National Natural Science Foundation of China(52403349)

摘要/Abstract

摘要：

纤维基热电材料及器件因其优异的可编织性和与人体皮肤的高贴合度, 在可穿戴设备供能领域展现出巨大潜力。传统的无机热电纤维制备方法成本高, 对温度要求严格。本研究报道了一种使用多巴胺表面改性结合原位化学沉积制备Ag₂Se热电纤维的方法。利用多巴胺在聚酰亚胺纤维表面自聚合形成聚多巴胺黏附层, 随后通过银镜反应在黏附层表面生成致密银层, 最后进行硒化反应将银转化为Ag₂Se, 探究了多巴胺功能化和Ag前驱体浓度对纤维微观形貌及热电性能的影响。结果表明, 聚多巴胺显著促进了无机层的成核与沉积, 经多巴胺功能化的热电纤维实现了更为致密且连续的Ag₂Se沉积, 功率因子从16.74 μW·m^-1·K^-2(未处理纤维)提升至40.14 μW·m^-1·K^-2。进一步探究银前驱体浓度对纤维性能的影响, 发现在硝酸银质量浓度为0.015 g·mL^-1条件下, Ag₂Se热电纤维表现出最佳性能, 室温功率因子达42.9 μW·m^-1·K^-2; 此外, 经500次弯曲测试后纤维最大相对电阻变化为11.5%, 10次重复水洗后纤维塞贝克系数保持稳定。搭建的双臂器件在38.0 K温差下开路电压可达7.84 mV, 展现出良好的服役稳定性。本研究为制备柔性Ag₂Se热电纤维材料与器件提供了新的思路。

关键词: 硒化反应, 热电纤维, Ag₂Se, 多巴胺

Abstract:

Fiber-based thermoelectric materials and devices have garnered significant attention in the field of self-powered wearable electronics due to their excellent weavability and superior conformability to human skin. However, conventional fabrication strategies for inorganic thermoelectric fibers are often limited by high manufacturing costs and stringent temperature requirements. Herein, a facile approach to fabricate Ag₂Se thermoelectric fibers via dopamine surface modification combined with in-situ chemical deposition is reported. Specifically, a polydopamine adhesive layer was formed on the surface of polyimide fibers through self-polymerization. Subsequently, a dense silver layer was deposited onto the adhesive layer via a silver mirror reaction, followed by a selenization process to convert the silver into Ag₂Se. The effects of dopamine functionalization and Ag precursor concentration on the fiber microstructure and thermoelectric performance were systematically investigated. The results indicated that the dopamine-functionalized fibers facilitated a more compact and continuous Ag₂Se deposition, increasing the power factor from 16.74 μW·m^-1·K^-2 to 40.14 μW·m^-1·K^-2 compared to untreated fibers. Further investigating the effect of Ag precursor concentration, it was found that the thermoelectric Ag₂Se fibers with an AgNO₃ concentration of 0.015 g·mL^-1 exhibited optimal performance, achieving a power factor of 42.9 μW·m^-1·K^-2 at room temperature. Furthermore, the fibers demonstrated excellent service stability, with a maximum relative resistance change of only 11.5% after 500 bending cycles and a stable Seebeck coefficient after 10 repeated washing cycles. Notably, an assembled two-leg device delivered an open-circuit voltage of 7.84 mV at a temperature difference of 38.0 K. This study provides a novel strategy for the low-cost fabrication of flexible Ag₂Se thermoelectric materials and devices.

Key words: selenization, thermoelectric fiber, Ag₂Se, dopamine

中图分类号:

TQ174

尚勃屹, 孙婷婷, 王连军, 江莞. Ag₂Se热电纤维的硒化反应制备及其性能研究[J]. 无机材料学报, 2026, 41(9): 1238-1246.

SHANG Boyi, SUN Tingting, WANG Lianjun, JIANG Wan. Fabrication and Properties of Ag₂Se Thermoelectric Fibers via Selenization[J]. Journal of Inorganic Materials, 2026, 41(9): 1238-1246.

图/表 9

图1 热电纤维的制备流程及表面改性表征

Fig. 1 Fabrication process and surface modification characterization of thermoelectric fibers (a) Fabrication process of Ag2Se fibers; (b) FT-IR spectra of PDA, PI and PDA-PI; (c-f) SEM images of (c) PI, (d) PDA-PI, (e) PI/Ag and (f) PDA-PI/Ag

图2 热电纤维的微观结构表征

Fig. 2 Microstructural characterizations of thermoelectric fibers (a, b) SEM images of (a) PDA-PI/Ag2Se and (b) PI/Ag2Se; (c) XRD patterns of PDA-PI/Ag2Se and PDA-PI/Ag; (d-f) XPS spectra of (d) PDA-PI/Ag and (e, f) PDA-PI/Ag2Se

图3 预处理Ag2Se纤维和未预处理Ag2Se纤维的热电性能

Fig. 3 Thermoelectric performance of Ag2Se fibers with and without pretreatment Colorful figure is available on website

图4 基于不同硝酸银浓度PDA-PI/Ag纤维的SEM照片

Fig. 4 SEM images of PDA-PI/Ag fibers prepared with different AgNO3 concentrations (a, b) 0.005 g·mL-1; (c, d) 0.010 g·mL-1; (e, f) 0.015 g·mL-1; (g, h) 0.020 g·mL-1

图5 基于不同硝酸银浓度制备的Ag2Se热电纤维的XRD图谱

Fig. 5 XRD patterns of Ag2Se thermoelectric fibers prepared with different AgNO3 concentrations

图6 基于不同硝酸银浓度PDA-PI/Ag2Se纤维的SEM照片

Fig. 6 SEM images of PDA-PI/Ag2Se fibers prepared with different AgNO3 concentrations (a, b) 0.005 g·mL-1; (c, d) 0.010 g·mL-1; (e, f) 0.015 g·mL-1; (g, h) 0.020 g·mL-1

图7 基于不同硝酸银浓度Ag2Se纤维的热电性能

Fig. 7 Thermoelectric performance of Ag2Se fibers prepared with different AgNO3 concentrations Colorful figure is available on website

图8 柔性热电纤维器件的输出性能与稳定性

Fig. 8 Output performance and stability of the flexible thermoelectric fiber device (a) Schematic illustration of the flexible thermoelectric (TE) device assembly; (b) Open-circuit voltage of the fiber device; (c) Bending and (d) washing stability of the thermoelectric fiber

表1 本工作与已报道涂层热电纤维的性能对比[8,12,34-35]

Table 1 Performance comparison of coated thermoelectric fibers in this work and the literature[8,12,34-35]

Material	S/(μV·K^-1)	σ/(S·cm^-1)	PF/(μW·m^-1·K^-2)	Ref.
Ag₂Se/cotton	-26.98	134.45	9.8	[8]
Bi₂Te₃/cotton	-83.79	36.7	25.77	[34]
CuI/SP	203.6	2.96	12.29	[35]
PEDOT-CNT-Bi₂Te₃/PET	47.1	55.26	12.26	[12]
PDA-PI/Ag₂Se	-117.7	30.9	42.9	This work

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Ag₂Se热电纤维的硒化反应制备及其性能研究

Fabrication and Properties of Ag₂Se Thermoelectric Fibers via Selenization

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