粉末热压法制备高性能n型PVDF/Ag2Se自支撑柔性复合热电薄膜

doi:10.15541/jim20250158

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 462-468.DOI: 10.15541/jim20250158 CSTR: 32189.14.10.15541/jim20250158

粉末热压法制备高性能n型PVDF/Ag₂Se自支撑柔性复合热电薄膜

徐子硕¹^,²(), 胡悦娟¹^,², 胡宇晨¹^,³, 陈立东¹^,², 姚琴¹^,²()

¹ 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050
² 中国科学院大学材料科学与光电工程中心, 北京 100049
³ 上海科技大学物质科学与技术学院, 上海 201210

收稿日期:2025-04-15 修回日期:2025-06-04 出版日期:2025-06-10 网络出版日期:2025-06-10
通讯作者: 姚琴, 正高级工程师. E-mail: yaoqin@mail.sic.ac.cn
作者简介:徐子硕(1999-), 男, 硕士研究生. E-mail: xuzishuo22@mails.ucas.ac.cn
基金资助:
国家自然科学基金(U23A20685);国家重点研发计划(2024YFF0505900)

High-performance n-type PVDF/Ag₂Se Free-standing Flexible Composite Thermoelectric Films Fabricated by Powder Hot-pressing

XU Zishuo¹^,²(), HU Yuejuan¹^,², HU Yuchen¹^,³, CHEN Lidong¹^,², YAO Qin¹^,²()

¹ State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
³ School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China

Received:2025-04-15 Revised:2025-06-04 Published:2025-06-10 Online:2025-06-10
Contact: YAO Qin, professor. E-mail: yaoqin@mail.sic.ac.cn
About author:XU Zishuo (1999-), male, Master candidate. E-mail: xuzishuo22@mails.ucas.ac.cn
Supported by:
National Natural Science Foundation of China(U23A20685);National Key Research and Development Program of China(2024YFF0505900)

摘要/Abstract

摘要：

可穿戴设备、微电子器件和物联网等领域应用的快速发展, 对自支撑柔性薄膜热电材料提出了迫切需求。当前, n型自支撑有机/无机复合柔性薄膜热电材料的研究进展滞后, 亟需通过优化制备工艺来提升薄膜性能。本研究采用简便高效的粉末热压工艺, 开发出高性能n型聚偏氟乙烯/硒化银(PVDF/Ag₂Se)自支撑柔性复合热电薄膜。热压过程的高温高压环境诱导Ag₂Se晶粒再结晶和长大, 有效减少了晶界数量, 显著降低了载流子散射和界面电阻, 从而使载流子迁移率、电导率和塞贝克系数同步提升。并且, 热压过程中熔融态PVDF能填充Ag₂Se导电网络的间隙, 在提高材料致密度的同时显著增强了柔韧性。实验结果表明, Ag₂Se质量分数为80%的热压复合薄膜展现出优异的室温热电性能: 电导率达277.0 S·cm^-1, 塞贝克系数为-135 μV·K^-1, 功率因子(PF)和热电优值(ZT)分别达到509 μW·m^-1·K^-1和0.26。这些性能不仅显著优于已报道的同类型PVDF/Ag₂Se自支撑薄膜, 在Ag₂Se基有机/无机复合自支撑柔性热电薄膜中也处于领先水平。力学性能测试显示, 该薄膜在5 mm半径下经过500次弯曲循环后, 电导率保持率仍超过92%, 最大拉伸应变是纯Ag₂Se薄膜的4倍。本研究为有机/无机复合热电材料中热电性能与力学柔性的协同优化提供了新思路。

关键词: 硒化银, 复合热电薄膜, 自支撑, 柔性, 热压

Abstract:

Rapid development of applications in wearable devices, microelectronics, and internet of things has created an urgent demand for free-standing flexible thermoelectric films. Currently, research on n-type free-standing flexible thermoelectric films significantly lags behind, and there is an urgent need to enhance film performance through the optimization of preparation processes. In this study, high-performance n-type poly(vinylidene fluoride)/silver selenide (PVDF/Ag₂Se) free-standing flexible thermoelectric composite films were developed using a simple and efficient powder hot-pressing method. The high-temperature and high-pressure conditions during hot pressing induced recrystallization and grain growth of Ag₂Se, effectively reducing grain boundary density, significantly decreasing carrier scattering and interfacial resistance, thereby simultaneously enhancing carrier mobility, electrical conductivity and Seebeck coefficient. Meanwhile, the melted PVDF filled interstices of the Ag₂Se conductive network during hot pressing, substantially improving material flexibility while increasing density. Experimental results demonstrate that the hot-pressed sample with 80% (in mass) Ag₂Se exhibits outstanding room-temperature thermoelectric performance with an electrical conductivity of 277.0 S·cm^-1 and a Seebeck coefficient of -135 μV·K^-1, and thermoelectric power factor (PF) and estimated figure of merit (ZT) reach 509 μW·m^-1·K^-2 and 0.26, respectively. This performance not only significantly surpasses that of previously reported PVDF/Ag₂Se free-standing films but also ranks among the highest for all reported Ag₂Se-based organic/inorganic free-standing flexible thermoelectric films. Furthermore, mechanical tests reveal that the film maintains over 92% of its original conductivity after 500 bending cycles at a 5 mm radius, while exhibiting a maximum tensile strain four times greater than pure Ag₂Se films. This study provides a novel strategy for synergistic optimization of thermoelectric performance and mechanical flexibility in organic/inorganic composite thermoelectric materials.

Key words: silver selenide, composite thermoelectric film, free-standing, flexible, hot-pressing

中图分类号:

TB34

徐子硕, 胡悦娟, 胡宇晨, 陈立东, 姚琴. 粉末热压法制备高性能n型PVDF/Ag₂Se自支撑柔性复合热电薄膜[J]. 无机材料学报, 2026, 41(4): 462-468.

XU Zishuo, HU Yuejuan, HU Yuchen, CHEN Lidong, YAO Qin. High-performance n-type PVDF/Ag₂Se Free-standing Flexible Composite Thermoelectric Films Fabricated by Powder Hot-pressing[J]. Journal of Inorganic Materials, 2026, 41(4): 462-468.

图/表 10

图1 (a) Ag2Se纳米线和(b) PVDF/Ag2Se复合薄膜的制备流程图

Fig. 1 Schematic diagrams of preparation process for (a) Ag2Se nanowires and (b) PVDF/Ag2Se composite film

图2 Ag2Se纳米线的(a)XRD图谱和(b)SEM照片

Fig. 2 (a) XRD pattern and (b) SEM image of Ag2Se nanowires

图3 CP/HP-40%、80%复合薄膜的XRD图谱

Fig. 3 XRD patterns of CP/HP-40% and 80% composite films

图4 PVDF/Ag2Se冷压和热压样品的(a) S、(b) σ和(c) PF

Fig. 4 (a) S, (b) σ and (c) PF of PVDF/Ag2Se cold/hot-pressed samples Colorful figures are available on website

表1 典型的Ag2Se基自支撑柔性复合薄膜的室温热电性能(300 K)

Table 1 Typical thermoelectric performance of Ag2Se-based free-standing flexible composite films at room temperature (300 K)

Sample	Method	PF/(μW·m^-1·K^-2)	κ/(W·m^-1·K^-1)	ZT	Ref.
PVDF/Ag₂Se	Drip coating	281	-	-	[22]
PVDF/Ag₂Se	Suction filtration	189	7	0.0079	[24]
PVP/Ag₂Se	Silk screen	3.4	-	-	[29]
PVDF/PANI-coated Ag₂Se	Drip coating	196	-	-	[23]
BC/Ag₂Se	Suction filtration	386	0.41	0.22	[30]
Carbon/Ag₂Se	Silk screen	1761	0.66	0.81	[26]
PEDOT:PSS/Ag₂Se	Drip coating	327	-	-	[31]
PVDF/Ag₂Se	Hot pressing	509	0.59	0.26	This work

图5 PVDF/Ag2Se复合薄膜及纯Ag2Se薄膜的(a~f)表面和(g~i)断面SEM照片

Fig. 5 (a-f) Surface and (g-i) cross-sectional SEM images of PVDF/Ag2Se composite and pure Ag2Se films (a) CP-60%; (b) CP-80%; (c) CP-Ag2Se; (d, g) HP-60%; (e, h) HP-80%; (f, i) HP-Ag2Se

表2 CP/HP-70%、80%复合薄膜的载流子浓度及迁移率

Table 2 Carrier concentrations and mobilities of CP/HP-70% and 80% composite films

Sample	Carrier concentration/ (×10¹⁸, cm^-3)	Carrier mobility/ (cm²·V^-1·s^-1)
CP-70%	5.15	18
CP-80%	7.29	15
HP-70%	3.94	288
HP-80%	4.81	321

图6 HP-Ag2Se薄膜和HP-80%复合薄膜的力学性能

Fig. 6 Mechanical properties of HP-Ag2Se film and HP-80% composite film (a, b) Photographs of (a) HP-Ag2Se film and (b) HP-80% composite film before and after bending tests (around a 5 mm-radius cylinder); (c) Relative electrical conductivity (σ/σ0) of HP-80% composite film as a function of bending cycle; (d) Tensile stress-strain curves of HP-Ag2Se film and HP-80% composite film

图S1 HP-80%复合薄膜的SEM照片及对应的EDS结果

Fig. S1 SEM image and corresponding EDS results of HP-80% composite film

图S2 Ag2Se、Se的DSC曲线

Fig. S2 DSC curves of Ag2Se and Se

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粉末热压法制备高性能n型PVDF/Ag₂Se自支撑柔性复合热电薄膜

High-performance n-type PVDF/Ag₂Se Free-standing Flexible Composite Thermoelectric Films Fabricated by Powder Hot-pressing

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