一种耐高温的柔性压电/热释电双功能传感器

李银辉; 殷荣艳; 梁建国; 李玮栋; 范凯; 周赟磊

doi:10.7498/aps.73.20241006

摘要

提高压电聚合物的耐温性, 且构建压电特异结构提高电学输出特性, 成为柔性耐高温压电/热释电双功能传感器制造的关键. 本文采用静电纺丝法制备了聚丙烯腈(PAN)纳米纤维薄膜, 通过程序控温对PAN纳米纤维膜进行热处理得到了耐高温的柔性纤维薄膜. 研究结果表明, PAN耐高温柔性纤维薄膜纳米传感器可以在高温环境(> 500 ℃)中使用, 其输出性能随热处理温度的升高先增大(< 260 ℃)后基本保持不变(260—450 ℃), 最后输出性能减小(> 450 ℃), 当热处理温度达到260 ℃时, 输出电压可达10.08 V, 输出电流达到2.89 μA, 与未进行热处理的PAN膜相比, 其输出电压和电流分别提高了3.54倍和2.83倍. 同时, 该传感器在高温环境下的输出不发生变化. 发现热处理的PAN具有热释电效应, 且热释电输出随着温度梯度的增大而变大. 在5000次的敲击循环测试中, 经过热处理的PAN纳米纤维薄膜传感器具有稳定的输出, 这表明该传感器有望应用在消防安全、航空航天等高温环境中.

关键词:

Abstract

Most of existing piezoelectric polymers have low glass transition temperatures, so they can only operate at lower temperatures (<150 ℃). Once the operating temperature is exceeded, the piezoelectric performance of the device rapidly decreases. At higher temperatures, dense chain motion can interfere with the orientation of dipoles, thus limiting the development of polymer based high-temperature piezoelectric sensors. High-temperature piezoelectric sensor devices are entirely made of inorganic materials, however, inorganic materials are rigid and can only work under small strains. Therefore, enhancing the temperature resistance of piezoelectric polmers and constructing piezoelectric asymmetric structure are the key to fabricating flexible high-temperature resistant piezoelectric/pyroelectric dual functional sensors. In this study, polyacrylonitrile (PAN) nanofiber film is prepared by electrospinning, and then subjected to heat treatment through programmed temperature control. The effects of the different heat-treatment temperatures on the mechanical and electrical performance of PAN nanofiber film are studied systematically, and the results show that PAN high temperature resistant flexible nanofiber film sensors can be used in high temperature environments (>500 ℃). Its output performance is improved with the increase of heat treatment temperature (<260 ℃) and then basically remains unchanged in a temperature range of 260–450 ℃. Finally, the output performance decreases at temperatures higher than 450 ℃. When the heat treatment temperature reaches 260 ℃, the output voltage increases to 10.08 V, and current reaches 2.89 μA. Compared with those of the untreated PAN membranes , its output voltage and current are increase by 3.54 times and 2.83 times, respectively. At the same time, the output of the PAN high temperature resistant flexible nanofiber film sensors is almost unchanged in the high-temperature environments. This is the first time that the pyroelectric effect has been observed in heat-treated PAN nanofiber films and both the open-circuit voltage and short-circuit current have been shown to increase with temperature gradient increasing. Besides, the PAN nanofiber film sensors have durability of more than 5000 cycles at room temperature(25 ℃) even at high temperature (400 ℃). Overall, good flexible, high-temperature resistance, and bifunctional sensing ability make PAN flexible nanofiber film sensors expected to be widely used in high temperature environments such as fire safety, aerospace and other harsh environment.

Keywords:

polyacrylonitrile /
cyclization /
high-temperature flexible nanofiber films /
piezoelectric/pyroelectric bifunctional sensor

作者及机构信息

1.
太原理工大学电子信息与光学工程学院, 微纳系统研究中心, 太原　030024

2.
西安电子科技大学杭州研究院, 杭州　311231

通信作者: 李银辉, liyinhui@tyut.edu.cn ; 周赟磊, zhouyunlei@xidian.edu.cn

基金项目: 国家自然科学基金(批准号: 52075361, 52205593)、山西省科技重大专项(批准号: 20201102003)、山西省青年科学基金(批准号: 20210302124046)、山西省面上科学基金(批准号: 20210302123156)和吕梁市校地合作重点研发专项(批准号: 2022XDHZ08)资助的课题.

Authors and contacts

1.
Micro-Nano System Research Center, School of Electronic Information and Optical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

2.
Hangzhou Institute of Technology, Xidian University, Hangzhou 311231, China

Corresponding author: Li Yin-Hui, liyinhui@tyut.edu.cn ; Zhou Yun-Lei, zhouyunlei@xidian.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 52075361, 52205593), the Major Science and Technology Project of Shanxi Province, China (Grant No. 20201102003), the Science Foundation for Youths of Shanxi Province, China (Grant No. 20210302124046), the National Science Foundation of Shanxi Province, China (Grant No. 20210302123156), the Key Research and Development Special Projects of Luliang City and University Cooperation, China (Grant No. 2022XDHZ08).

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参考文献

[1]	Wang Y, Zhang J S, Jia X X, Chen M M, Wang H R, Ji G N, Zhou H Y, Fang Z Z, Gao Z X 2024 Nano Energy 119 109080 Google Scholar
[2]	李凤超, 孔振, 吴锦华, 纪欣宜, 梁嘉杰 2021 物理学报 70 100703 Google Scholar Li F C, K Z, W J H, Ji X Y, Liang J J 2021 Acta Phys. Sin. 70 100703 Google Scholar
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施引文献

图 1 热处理程序温控图

Fig. 1. Temperature control chart of the heat treatment program.

下载: 全尺寸图片幻灯片

图 2 耐高温柔性PAN压电/热释电双功能传感器示意图

Fig. 2. Schematic diagram of the high temperature resistant flexible PAN piezo/pyrooelectric dual function sensor.

下载: 全尺寸图片幻灯片

图 3 不同温度热处理PAN纤维的SEM图　(a)未处理; (b) 150 ℃; (c) 260 ℃; (d) 350 ℃; (e) 450 ℃; (f) 550 ℃

Fig. 3. SEM of PAN fibers at different heat treatment temperatures: (a) Untreated; (b) 150 ℃; (c) 260 ℃; (d) 350 ℃; (e) 450 ℃; (f) 550 ℃.

下载: 全尺寸图片幻灯片

图 4 (a) 不同温度热处理PAN纤维薄膜的XRD图谱; (b) PAN-untreated, (c) PAN-150 ℃, (d) PAN-260 ℃的XRD谱图的拟合曲线　　　

Fig. 4. (a) XRD profiles of PAN fiber films at different heat treatment temperatures; the peak-fitting curves of XRD spectrum of (b) PAN-untreated, (c) PAN-150 ℃, (d) PAN-260 ℃.

下载: 全尺寸图片幻灯片

图 5 PAN-untreated, PAN-260 ℃, PAN-550 ℃纳米纤维膜DSC曲线

Fig. 5. DSC curve of PAN-untreated, PAN-260 ℃ and PAN-550 ℃ nanofiber films.

下载: 全尺寸图片幻灯片

图 6 不同温度热处理PAN纤维薄膜的压电输出　(a) 开路电压; (b) 短路电流; (c) 正反接测试; (d) 输出功率(PAN-450 ℃)

Fig. 6. Piezoelectric output of PAN fiber films at different heat treatment temperatures: (a) Open circuit voltage; (b) short-circuit current; (c) positive and negative test; (d) output power (PAN-450 ℃).

下载: 全尺寸图片幻灯片

图 7 PAN-450 ℃纤维薄膜的高温压电测试　(a) 不同高温环境下的电压输出; (b) 正反接测试(400 ℃)

Fig. 7. High-temperature piezoelectric test of PAN-450 ℃ fiber film: (a) Voltage output at different high-temperature environments; (b) positive and negative test (400 ℃).

下载: 全尺寸图片幻灯片

图 8 PAN-450 ℃纤维薄膜的热释电性能测试　(a) 电压输出; (b) 电流输出

Fig. 8. Pyroelectric performance test of PAN-450 ℃ fiber film: (a) Voltage output; (b) current output.

下载: 全尺寸图片幻灯片

图 9 (a) 电偶极子取向示意图; (b) 压电效应原理图; (c) 热释电效应原理图

Fig. 9. (a) Schematic illustration of the orientation of the electric dipoles; (b) schematic diagram of the piezoelectric effect; (c) schematic diagram of the pyroelectric effect.

下载: 全尺寸图片幻灯片

图 10 PAN-450 ℃纤维薄膜的稳定性测试　(a) 室温(25 ℃); (b) 高温(400 ℃)

Fig. 10. Stability testing of the PAN-450 ℃ fiber film: (a) Room temperature (25 ℃); (b) high temperature (400 ℃).

下载: 全尺寸图片幻灯片

下载: 全尺寸图片幻灯片

[1]	Wang Y, Zhang J S, Jia X X, Chen M M, Wang H R, Ji G N, Zhou H Y, Fang Z Z, Gao Z X 2024 Nano Energy 119 109080 Google Scholar
[2]	李凤超, 孔振, 吴锦华, 纪欣宜, 梁嘉杰 2021 物理学报 70 100703 Google Scholar Li F C, K Z, W J H, Ji X Y, Liang J J 2021 Acta Phys. Sin. 70 100703 Google Scholar
[3]	Hyeon D Y, Nam C, Ham S S, Hwang G T, Yi S, Kim K T, Park K 2020 Adv. Electron. Mat. 7 1
[4]	Hyeon D Y, Lee G J, Lee S H, Park J J, Kim S, Lee M K, Park K I 2022 Compos Part B-eng 234 109671 Google Scholar
[5]	Li Y H, Sun J J, Li P W, Li X R, Tan J Q, Zhang H L, Li T Y, Liang J G, Zhou Y L, Hai Z Y, Zhang J 2023 J. Mater. Chem. A 11 13708 Google Scholar
[6]	Hosseini E S, Manjakkal L, Shakthivel D, Dahiya R 2020 ACS Appl. Mater. Interfaces 12 9008 Google Scholar
[7]	Maity K, Mondal A, Saha M C 2023 ACS Appl. Mater. Interfaces 15 13956
[8]	Dong L, Lou J, Shenoy V B 2017 ACS Nano 11 8242 Google Scholar
[9]	Su Y J, Chen C X, Pan H, Yang Y, Chen G R, Zhao X, Li W X, Gong Q C, Xie G Z, Zhou Y H, Zhang S L, Tai H L, Jiang Y D, Chen J 2021 Adv. Funct. Mater. 31 2010962 Google Scholar
[10]	Jackson N, Mathewson A 2017 Smart Mater. Struct. 26 045005 Google Scholar
[11]	Tu Y L, Zheng Y, Guo S Y, Shen J B 2022 ACS Appl. Mater. Interfaces 14 40331 Google Scholar
[12]	Ding W J, Xu W W, Dong Z J, Liu Y Q, Wang Q 2021 Ceram. Int. 47 29681 Google Scholar
[13]	Khanbareh H, Hegde M, Bijleveld J C 2017 Royal Society of Chemistry 5 9389
[14]	Bahl O, Manocha L 1974 Carbon 12 417 Google Scholar
[15]	Zhang W X, Liu J, Wu G 2003 Carbon 41 2805 Google Scholar
[16]	Xue Y, Liu J, Liang J Y 2013 Polym. Degrad. Stabil. 98 219 Google Scholar
[17]	Li Y, Tan J, Liang K, Li Y, Sun J, Zhang H, Luo C, Li P, Xu J, Jiang H, Wang K 2022 J. Mater. Sci. Mater. Electron. 33 4291 Google Scholar
[18]	Moon S C, Farris R J 2009 Carbon 47 2829 Google Scholar
[19]	Lian F, Liu J, Ma Z, Liang J Y 2012 Carbon 50 488 Google Scholar
[20]	Liu Y, Liu Y, Shang L, Ao Y 2022 J. Appl. Polym. Sci. 139 18
[21]	Ge Y, Fu Z Y, Zhang M Y, Zhang H X 2021 J. Appl. Polym. Sci. 138 49603 Google Scholar
[22]	Sun L H, Shang L, Xiao L H, Zhang M J, Ao Y H , Li M 2020 J. Mater. Sci. 55 3408
[23]	Wang W Y, Zheng Y D, Sun Y, Jin X, Niu J R, Cheng M Y, Wang H X, Shao H, Lin T 2021 J. Mater. Chem. A 9 20395 Google Scholar
[24]	Bai S, Xu Q, Gu L, Ma F, Qin Y, Wang Z L 2012 Nano Energy 1 789 Google Scholar
[25]	Chen C J, Zhao S L, Pan C F, Zi Y L, Wang F C, Yang C, Wang Z L 2022 Nat. Commun. 13 1391 Google Scholar
[26]	Fu R M, Tu L J, Zhou Y H, Fan L, Zhang F M, Wang Z G, Xing J, Chen D F, Deng C L, Tan G X, Yu P, Zhou L, Ning C Y 2019 Chem. Mater. 31 9850 Google Scholar
[27]	Korkmaz S, Kariper I A 2021 Nano Energy 84 105888 Google Scholar

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一种耐高温的柔性压电/热释电双功能传感器