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

• 研究论文 •

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
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 Zishuo^1,2, HU Yuejuan^1,2, HU Yuchen^1,3, CHEN Lidong^1,2, YAO Qin^1,2

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, 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
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,亟需通过制备工艺优化提升薄膜性能。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 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,其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弯曲半径下经过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 using a simple and efficient powder hot-pressing method were developed. 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 S·cm^-1 and a Seebeck coefficient of -135 μV·K^-1, and thermoelectric power factor (PF) and estimated figure of merit (ZT value) reaches 509 μW·m^-1·K^-2 and 0.26, respectively. This performance not only significantly surpasses 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 maintained 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 the 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, DOI: 10.15541/jim20250158.

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, DOI: 10.15541/jim20250158.

参考文献

[1] BASKARAN P, RAJASEKAR M.Recent progress in thermoelectric devices and applications. Chemical Engineering Journal, 2025, 506: 159929.
[2] MAO J, CHEN G, REN Z F. Thermoelectric cooling materials. Nature Materials, 2021, 20(4): 454.
[3] BERETTA D, NEOPHYTOU N, HODGES J M, et al. Thermoelectrics: from history, a window to the future. Materials Science and Engineering: R: Reports, 2019, 138: 100501.
[4] SHI X L, WANG L J, LYU W Y, et al. Advancing flexible thermoelectrics for integrated electronics. Chemical Society Reviews, 2024, 53(18): 9254.
[5] PEI J, CAI B W, ZHUANG H L, et al. Bi2Te3-based applied thermoelectric materials: research advances and new challenges. National Science Review, 2020, 7(12): 1856.
[6] SHARMA P K, SENGUTTUVAN T D, SHARMA V K, et al. Revisiting the thermoelectric properties of lead telluride. Materials Today Energy, 2021, 21: 100713.
[7] ABBASI M S, SULTANA R, AHMED I, et al. Contemporary advances in organic thermoelectric materials: fundamentals, properties, optimization strategies, and applications. Renewable and Sustainable Energy Reviews, 2024, 200: 114579.
[8] JIN P H, LI D J, IOCOZZIA J, et al. Hybrid organic-inorganic thermoelectric materials and devices. Angewandte Chemie International Edition, 2019, 58(43): 15206.
[9] ZHANG B T, SUN T T, WANG L J, et al. Inkjet printing preparation of AgCuTe thermoelectric thin films. Journal of Inorganic Materials, 2024, 39(12): 1325.
[10] DENG L H, LIU Y R, ZHANG Y Y,et al. Organic thermoelectric materials: niche harvester of thermal energy. Advanced Functional Materials, 2023, 33(3): 2210770.
[11] NANDIHALLI N, LIU C J, MORI T. Polymer based thermoelectric nanocomposite materials and devices: fabrication and characteristics. Nano Energy, 2020, 78: 105186.
[12] TRIPATHI A, LEE Y, LEE S, et al. Recent advances in n-type organic thermoelectric materials, dopants, and doping strategies. Journal of Materials Chemistry C, 2022, 10(16): 6114.
[13] LIU M, ZHANG X Y, ZHANG S X, et al. Ag₂Se as a tougher alternative to n-type Bi₂Te₃ thermoelectrics. Nature Communications, 2024, 15: 6580.
[14] ZHANG Z, SUN T T, WANG L J,et al. Flexible thermoelectric films with different Ag₂Se dimensions: performance optimization and device integration. Journal of Inorganic Materials, 2024, 39(11): 1221.
[15] LIU Y, ZHANG Q H, HUANG A B, et al. Fully inkjet-printed Ag₂Se flexible thermoelectric devices for sustainable power generation. Nature Communications, 2024, 15: 2141.
[16] LIU Y, LI J J, WANG Z X, et al. High thermoelectric performance of flexible Ag/Ag₂Se composite film on Nylon for low-grade energy harvesting. Journal of Materials Science & Technology, 2024, 179: 79.
[17] YANG D, SHI X L, LI M, et al. Flexible power generators by Ag₂Se thin films with record-high thermoelectric performance. Nature Communications, 2024, 15: 923.
[18] PEREZ-TABORDA J A, CABALLERO-CALERO O, VERA-LONDONO L, et al. High thermoelectric zT in n-type silver selenide films at room temperature. Advanced Energy Materials, 2018, 8(8): 1702024.
[19] DU J J, ZHANG B T, JIANG M, et al. Inkjet printing flexible thermoelectric devices using metal chalcogenide nanowires. Advanced Functional Materials, 2023, 33(26): 2213564.
[20] ZHANG L, SHI X L, YANG Y L, et al. Flexible thermoelectric materials and devices: from materials to applications. Materials Today, 2021, 46: 62.
[21] AGHAYARI S.PVDF composite nanofibers applications.Heliyon, 2022, 8(11): e11620.
[22] PARK D, JU H, KIM J. Enhanced thermoelectric properties of flexible N-type Ag₂Se nanowire/polyvinylidene fluoride composite films synthesized via solution mixing. Journal of Industrial and Engineering Chemistry, 2021, 93: 333.
[23] PARK D, KIM M, KIM J. High-performance PANI-coated Ag₂Se nanowire and PVDF thermoelectric composite film for flexible energy harvesting. Journal of Alloys and Compounds, 2021, 884: 161098.
[24] ZHOU H J, ZHANG Z J, SUN C X, et al. Biomimetic approach to facilitate the high filler content in free-standing and flexible thermoelectric polymer composite films based on PVDF and Ag₂Se nanowires. ACS Applied Materials & Interfaces, 2020, 12(46): 51506.
[25] DING Y F, QIU Y, CAI K F, et al. High performance n-type Ag₂Se film on nylon membrane for flexible thermoelectric power generator. Nature Communications, 2019, 10: 841.
[26] ZHANG M C, LI J J, LIU Y, et al. Screen printing high-performance free-standing Ag₂Se/carbon composite film for flexible thermoelectric converters. Nano Energy, 2025, 138: 110836.
[27] YUE Y C, LYU W Y, LIU W D, et al. Solvothermal synthesis of micro-pillar shaped Ag₂Se and its thermoelectric potential. Materials Today Chemistry, 2024, 39: 102183.
[28] LU Y, QIU Y, CAI K, et al. Ultrahigh performance PEDOT/Ag₂Se/CuAgSe composite film for wearable thermoelectric power generators. Materials Today Physics, 2020, 14: 100223.
[29] JIN Q, JIANG S, ZHAO Y, et al. Flexible layer-structured Bi₂Te₃ thermoelectric on a carbon nanotube scaffold. Nature Materials, 2019, 18: 62.
[30] LIU D, ZHAO Y X, YAN Z Q, et al. Screen-printed flexible thermoelectric device based on hybrid silver selenide/PVP composite films. Nanomaterials, 2021, 11(8): 2042.
[31] PALAPORN D, MONGKOLTHANARUK W, FAUNGNAWAKIJ K, et al. Flexible thermoelectric paper and its thermoelectric generator from bacterial cellulose/Ag₂Se nanocomposites. ACS Applied Energy Materials, 2022, 5(3): 3489.
[32] PARK D, KIM M, KIM J. Conductive PEDOT:PSS-based organic/inorganic flexible thermoelectric films and power generators. Polymers, 2021, 13(2): 210.

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

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	魏相霞, 张晓飞, 徐凯龙, 陈张伟. 增材制造柔性压电材料的现状与展望[J]. 无机材料学报, 2024, 39(9): 965-978.
[2]	荀道祥, 罗序维, 周明冉, 何佳乐, 冉茂进, 胡执一, 李昱. 锂硒电池ZIF-L衍生氮掺杂碳纳米片/碳布自支撑电极的电化学性能研究[J]. 无机材料学报, 2024, 39(9): 1013-1021.
[3]	施桐, 甘乔炜, 刘东, 张莹, 冯浩, 李强. 自支撑Bi@Cu纳米树电极高效电化学还原CO₂制甲酸[J]. 无机材料学报, 2024, 39(7): 810-818.
[4]	陈甜, 罗媛, 朱刘, 郭学益, 杨英. 有机-无机共添加增强柔性钙钛矿太阳能电池机械弯曲及环境稳定性能[J]. 无机材料学报, 2024, 39(5): 477-484.
[5]	李腊, 沈国震. 二维MXenes材料在柔性光电探测器中的应用展望[J]. 无机材料学报, 2024, 39(2): 186-194.
[6]	张波涛, 孙婷婷, 王连军, 江莞. 喷墨打印制备AgCuTe热电薄膜[J]. 无机材料学报, 2024, 39(12): 1325-1330.
[7]	张哲, 孙婷婷, 王连军, 江莞. 不同维度Ag₂Se构筑柔性热电薄膜的性能优化与器件集成研究[J]. 无机材料学报, 2024, 39(11): 1221-1227.
[8]	王博, 蔡德龙, 朱启帅, 李达鑫, 杨治华, 段小明, 李雅楠, 王轩, 贾德昌, 周玉. SrAl₂Si₂O₈增强BN陶瓷的力学性能及抗热震性能[J]. 无机材料学报, 2024, 39(10): 1182-1188.
[9]	赵雅文, 屈发进, 汪岩屹, 王智文, 陈初升. 基于硅酸铝纤维的柔性氧敏感元件的制备和性能[J]. 无机材料学报, 2024, 39(10): 1084-1090.
[10]	冒爱琴, 陆文宇, 贾洋刚, 王冉冉, 孙静. 柔性压电器件及其可穿戴应用[J]. 无机材料学报, 2023, 38(7): 717-730.
[11]	杨洋, 崔航源, 祝影, 万昌锦, 万青. 柔性神经形态晶体管研究进展[J]. 无机材料学报, 2023, 38(4): 367-377.
[12]	刘丹, 赵亚欣, 郭锐, 刘艳涛, 张志东, 张增星, 薛晨阳. 退火条件对磁控溅射MgO-Ag₃Sb-Sb₂O₄柔性薄膜热电性能的影响[J]. 无机材料学报, 2022, 37(12): 1302-1310.
[13]	罗艺, 夏书海, 牛波, 张亚运, 龙东辉. 柔性有机硅气凝胶的制备及其高温无机化转变研究[J]. 无机材料学报, 2022, 37(12): 1281-1288.
[14]	梁汉琴, 尹金伟, 左开慧, 夏咏锋, 姚冬旭, 曾宇平. 添加BaTiO₃的热压烧结Si₃N₄陶瓷的力学和介电性能[J]. 无机材料学报, 2021, 36(5): 535-540.
[15]	方华靖, 赵泽天, 武文婷, 汪宏. 柔性电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 140-151.