Piezoelectric sensing properties of PAN/MoS<sub>2</sub> flexible composite nanofiber film

ZHANG Hengbo; LI Yinhui; LI Weidong; GAO Fei; YIN Rongyan; LIANG Jianguo; ZHAO Peng; ZHOU Yunlei; LI Pengwei; BIAN Guibin

doi:10.7498/aps.74.20241676

Abstract

Flexible piezoelectric materials can convert mechanical energy into electrical energy to power micro/nano electronic devices. In recent years, research into piezoelectric technologies has revealed that molybdenum disulfide (MoS₂) can improve the piezoelectric properties of composite materials. In this research the fabrication of a PAN/MoS₂ flexible composite nanofiber film piezoelectric sensor via electrospinning is presented. The influence of MoS₂ nanosheet content on the piezoelectric performance of the PAN/MoS₂ composite nanofiber films is systematically investigated, and the morphology and structure of the composite nanofiber films are characterized. The results show that MoS₂ is uniformly distributed in the composite nanofiber films, and the zigzag conformation of the PAN molecular is enhanced by adding MoS₂. As the MoS₂ doping content increases, the performance of the PAN/MoS₂ composite nanofiber film sensor shows a first-increasing-and-then-decreasing trend, and ultimately reaching a maximum value when the MoS₂ weight content is 3.0%. When the MoS₂ doping content increases from 0% to 3.0%, the open-circuit output voltage of the PAN/MoS₂ composite nanofiber film sensor increases from 1.92 V to 4.64 V, and the short-circuit output current increases from 1.03 μA to 2.69 μA. At 3.0% MoS₂ doping, the maximum output power of the PAN/MoS₂ composite nanofiber film sensor reaches 3.46 μW, with an internal resistance of approximately 10 MΩ. The output voltage of the composite nanofiber film sensor increases with the applied external force increasing. At a frequency of 10 Hz, when external forces of 2 N, 3 N, 4 N, 5 N, and 6 N are applied, the sensor output voltages are 2 V, 3.4 V, 5.9 V, 8.7 V, and 10.3 V, respectively. Compared with pure PAN film, the PAN/MoS₂ composite nanofiber film has a piezoelectric constant d₃₃ increases by 4.86 times. The PAN/MoS₂ composite nanofiber film sensor can efficiently charge commercial capacitors, and the discharging of capacitors can successfully power a green LED. Additionally, it can monitor in real-time, under passive conditions, the bending state of the knee and the forward movement of the bicycle wheel during cycling. After 10000 impact cycles, the PAN/MoS₂ composite nanofiber film sensor shows stable voltage output with no obvious fluctuations, demonstrating excellent stability. All in all, the PAN/MoS₂ flexible composite nanofiber film sensor exhibits outstanding flexibility, low cost, and self-powered capabilities, showing promising potential for applications in wearable/portable electronics, smart devices, and intelligent robotics.

Keywords:

Authors and contacts

1.
College of Electronic Information and Optical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2.
College of Integrated Circuits, Taiyuan University of Technology, Taiyuan 030024, China
3.
Hangzhou Institute of Technology, Xidian University, Hangzhou 311231, China
4.
Institute of Automation, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: LI Yinhui, liyinhui@tyut.edu.cn ; BIAN Guibin, guibin.bian@ia.ac.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 Shanxi Province Natural Science Foundation for Youth Scientists, China (Grant No. 20210302124046), the Natural Science Foundation of Shanxi Province, China (Grant No. 20210302123156), and the Key Research and Development Special Projects of Luliang city and University Cooperation, China (Grant No. 2022XDHZ08).

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References

[1]	Rjafallah A, Hajjaji A, Guyomar D, Kandoussi K, Belhora F, Boughaleb Y 2019 J. Compos. Mater. 53 613 Google Scholar
[2]	Chen C, Wen Z, Shi J, Jian X, Li P, Yeow J T W, Sun X 2020 Nat. Commun. 11 4143 Google Scholar
[3]	Hajra S, Panda S, Khanberh H, Vivekananthan V, Chamanehpour E, Mishra Y K, Kim H J 2023 Nano Energy 115 108729 Google Scholar
[4]	Xu Q, Wen J, Qin Y 2021 Nano Energy 86 106080 Google Scholar
[5]	Korkmaz S, Kariper İ A 2021 Nano Energy 84 105888 Google Scholar
[6]	Panda S, Hajra S, Kim H G, Achary P G R, Pakawanit P, Yang Y, Mishra Y K, Kim H J 2023 ACS Appl. Mater. Interfaces 15 36096
[7]	Satyaranjan B, Shahid-ul-Islam M, Mulvihill D M, Wazed A 2023 Nano Energy 111 108414 Google Scholar
[8]	Zhang W, Wu G, Zeng H, Li Z, Wu W, Jiang H, Zhang W, Wu R, Huang Y, Lei Z 2023 Polymers 15 2766 Google Scholar
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Cited By

图 1 (a) MoS₂的XRD图谱; (b) MoS₂质量含量为0%—5.0%的PAN/MoS₂复合纳米纤维膜的XRD图谱与(c) FTIR图

Figure 1. (a) The XRD pattern of MoS₂; (b) the XRD patterns of PAN/MoS₂ composite nanofiber films with MoS₂ weight contents ranging from 0% to 5.0%, as well as (c) the corresponding FTIR spectra.

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图 2 (a) 块状MoS₂的SEM图; (b) 图(a)红色框所示区域的放大图; (c) 分散后MoS₂的SEM图; (d) 图(c)红色框所示区域的放大图; (e) 分散后MoS₂的TEM图; (f) 图(e)红色框所示区域的HR-TEM图

Figure 2. (a) SEM image of bulk MoS₂; (b) magnified view of the region indicated by the red square in panel (a); (c) SEM image of dispersed MoS₂; (d) magnified view of the region indicated by the red square in panel (c); (e) TEM image of dispersed MoS₂; (f) HR-TEM image of the region indicated by the red square in panel (e).

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图 3 不同MoS₂含量的PAN/MoS₂复合纳米纤维膜的SEM图像　(a) 纯PAN; (b) PAN/MoS₂-1; (c) PAN/MoS₂-2; (d) PAN/MoS₂-3; (e) PAN/MoS₂-4; (f) PAN/MoS₂-5

Figure 3. SEM images of PAN/MoS₂ composite nanofiber films with different contents of MoS₂: (a) Pure PAN; (b) PAN/MoS₂-1; (c) PAN/MoS₂-2; (d) PAN/MoS₂-3; (e) PAN/MoS₂-4; (f) PAN/MoS₂-5.

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图 4 PAN/MoS₂复合纳米纤维膜的EDS扫描图

Figure 4. EDS scan of PAN/MoS₂ composite nanofiber film.

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图 5 PAN/MoS₂复合纳米纤维膜的EDS分析图

Figure 5. EDS analysis of PAN/MoS₂ composite nanofiber film

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图 6 (a) 纯PAN的TEM图; (b), (c) PAN/MoS₂复合纳米纤维的TEM图; (d) 图(a)红色框所示区域的HR-TEM图; (e) 图(b)红色框所示区域的HR-TEM图; (f) 图(c)红色框所示区域的HR-TEM图

Figure 6. (a) TEM image of pure PAN; (b), (c) TEM images of PAN/MoS₂ composite nanofibers; (d) HR-TEM image of the region indicated by the red square in panel (a); (e) HR-TEM image of the region indicated by the red square in panel (b); (f) HR-TEM image of the region indicated by the red square in panel (c).

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图 7 不同MoS₂质量含量(1.0%, 2.0%, 3.0%, 4.0%, 5.0%)的PAN/MoS₂复合纳米纤维膜和纯PAN纳米纤维膜的输出性能　(a) 开路电压; (c) 短路电流; (b), (d) 电压和电流最大值图

Figure 7. Output performance of the PAN/MoS₂ composite nanofiber film with different weight content of MoS₂ 1.0%, 2.0%, 3.0%, 4.0%, 5.0% and pure PAN nanofiber film: (a) Open-circuit voltage; (c) short-circuit current; (b), (d) diagram of the maximum value of voltage and current.

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图 8 (a) 不同外部负载电阻的PAN/MoS₂-3的开路电压和瞬时功率; (b) 正向和反向连接中PAN/MoS₂-3的开路电压; (c) 不同机械力作用下PAN/MoS₂-3的输出电压; (d) PAN/MoS₂-3的输出电压值和施加的机械力拟合曲线图

Figure 8. (a) Open-circuit voltage and instantaneous power of PAN/MoS₂-3 with different external load resistors; (b) open-circuit voltage of PAN/MoS₂-3 in forward and reverse connections; (c) output voltage of PAN/MoS₂-3 under different applied mechanical forces; (d) plot of output voltage values of PAN/MoS₂-3 and applied mechanical forces fitting curve.

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图 9 PAN/MoS₂复合纳米纤维膜的铁电性能　(a) 介电常数随频率的变化; (b) 极化-电场磁滞回线(P-E); (c) 室温下介电常数(10³ Hz下的ε_r)和剩余极化强度随MoS₂含量增加的变化; (d) 压电系数(d₃₃)

Figure 9. Ferroelectric properties of the PAN/MoS₂ composite nanofiber films: (a) Variation of dielectric constant with frequency; (b) polarization–electric field hysteresis loops (P-E); (c) variation of dielectric constant (ε_rat 10³ Hz) and remnant polarization with increasing MoS₂ content at room temperature; (d) piezoelectric coefficient (d₃₃).

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图 10 (a) 由PAN/MoS₂-3充电的电容器的充电曲线. 插图左图: 包含电容器的桥式整流器电路的示意图. 右图: 充电电容器点亮LED的光学照片; (b) PAN/MoS₂-3作为自行车传感器的示意图; (c) 膝盖弯曲时PAN/MoS₂-3输出电压随时间变化; (d) 车轮运动时不同负载下PAN/MoS₂-3的电压输出图; (e) 车轮移动时不同速度下PAN/MoS₂-3的电压输出图

Figure 10. (a) Charging curve of a capacitor charged by the PAN/MoS₂-3. Inset left: schematic illustration of a bridge rectifier circuit containing the capacitor. Inset right: Optical photograph of a LED lighted by the charged capacitor; (b) schematic diagram of PAN/MoS₂-3 as a sensor applied to bicycles; (c) PAN/MoS₂-3 output voltage variation over time as the knee is flexed; (d) voltage output diagram of PAN/MoS₂-3 under various loads during forward wheel movement; (e) voltage output diagram of PAN/MoS₂-3 at different speeds during forward wheel movement.

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图 11 PAN/MoS₂复合纳米纤维膜传感器工作原理示意图

Figure 11. Schematic diagram of the working principle of PAN/MoS₂ composite nanofiber film sensor.

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图 12 PAN/MoS₂-3在10000次施压-释放循环中的输出性能

Figure 12. Output performance of PAN/MoS₂-3 for pressing-releasing 10000 cycles.

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表 1 不同MoS₂质量含量PAN/MoS₂复合纳米纤维膜传感器电学性能

Table 1. Electrical properties of PAN/MoS₂ composite nanofiber film sensor with different MoS₂ weight contents.

MoS₂ weight content/%	Voltage/V	Current/μA	ε_r(at 10³ Hz)	P_r/(μC·cm^–2)	d₃₃/(pC·N^–1)
0	1.92	1.03	1.19	0.56	1.25
1	2.36	1.61	1.50	0.97	2.58
2	3.56	2.42	2.05	1.20	4.36
3	4.64	2.69	2.46	1.39	6.08
4	4.02	2.34	2.32	1.36	5.59
5	2.80	2.07	1.62	1.14	3.28

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[1]	Rjafallah A, Hajjaji A, Guyomar D, Kandoussi K, Belhora F, Boughaleb Y 2019 J. Compos. Mater. 53 613 Google Scholar
[2]	Chen C, Wen Z, Shi J, Jian X, Li P, Yeow J T W, Sun X 2020 Nat. Commun. 11 4143 Google Scholar
[3]	Hajra S, Panda S, Khanberh H, Vivekananthan V, Chamanehpour E, Mishra Y K, Kim H J 2023 Nano Energy 115 108729 Google Scholar
[4]	Xu Q, Wen J, Qin Y 2021 Nano Energy 86 106080 Google Scholar
[5]	Korkmaz S, Kariper İ A 2021 Nano Energy 84 105888 Google Scholar
[6]	Panda S, Hajra S, Kim H G, Achary P G R, Pakawanit P, Yang Y, Mishra Y K, Kim H J 2023 ACS Appl. Mater. Interfaces 15 36096
[7]	Satyaranjan B, Shahid-ul-Islam M, Mulvihill D M, Wazed A 2023 Nano Energy 111 108414 Google Scholar
[8]	Zhang W, Wu G, Zeng H, Li Z, Wu W, Jiang H, Zhang W, Wu R, Huang Y, Lei Z 2023 Polymers 15 2766 Google Scholar
[9]	Ma X, Zhukov S, von Seggern H, Sessler G M, Ben Dali O, Kupnik M, Dai Y, He P, Zhang X 2023 Adv. Electron. Mater. 9 2201070 Google Scholar
[10]	Qi F, Xu L, He Y, Yan H, Liu H 2023 Cryst. Res. Technol. 58 2300119 Google Scholar
[11]	Guo H, Li L, Wang F, Kim S, Sun H 2022 ACS Appl. Mater. Interfaces 14 34733
[12]	Bhadwal N, Ben Mrad R, Behdinan K 2023 Nanomaterials 13 3170 Google Scholar
[13]	Tao J, Wang Y, Zheng X, Zhao C, Jin X, Wang W, Lin T 2023 Nano Energy 118 108987 Google Scholar
[14]	Song K, Zhao R, Wang Z L, Yang Y 2019 Adv. Mater. 31 1902831 Google Scholar
[15]	Kim M, Fan J 2021 Adv. Fiber Mater. 3 160 Google Scholar
[16]	Bhatt A, Singh V, Bamola P, Aswal D, Rawat S, Rana S, Dwivedi C, Singh B, Sharma H 2023 J. Alloys Compd. 960 170664 Google Scholar
[17]	Srivastava M, Banerjee S, Bairagi S, Singh P, Kumar B, Singh P, Kale R D, Mulvihill D M, Ali S W 2024 Chem. Eng. J. 480 147963 Google Scholar
[18]	Zhang M, Howe R C T, Woodward R I, Kelleher E J R, Torrisi F, Hu G, Popov S V, Taylor J R, Hasan T 2015 Nano Res. 8 1522 Google Scholar
[19]	Aji A S, Nishi R, Ago H, Ohno Y 2020 Nano Energy 68 104370 Google Scholar
[20]	Evans J M, Lee K S, Yan E X, Thompson A C, Morla M B, Meier M C, Ifkovits Z P, Carim A I, Lewis N S 2022 ACS Mater. Lett. 4 1475 Google Scholar
[21]	Maity K, Mahanty B, Sinha T K, Garain S, Biswas A, Ghosh S K, Manna S, Ray S K, Mandal D 2017 Energy Technol. 5 234 Google Scholar
[22]	Han S A, Kim T H, Kim S K, Lee K H, Ho H J, Lee J H, Kim S W 2018 Adv. Mater. 30 1800342 Google Scholar
[23]	Zhu H, Wang Y, Xiao J, Liu M, Xiong S, Wong Z J, Ye Z, Ye Y, Yin X, Zhang X 2015 Nat. Nanotechnol. 10 151 Google Scholar
[24]	Wu W, Wang L, Li Y, Zhang F, Lin L, Niu S, Chenet D, Zhang X, Hao Y, Heinz T F, Hone J, Wang Z L 2014 Nature 514 470 Google Scholar
[25]	Jiang L, Xie H, Hou Y, Wang S, Xia Y, Li Y, Hu G H, Yang Q L, Xiong C, Gao Z D 2019 Ceram. Int. 45 11347 Google Scholar
[26]	Chen S L, Li J L, Song Y H, Yang Q L, Shi Z Q, Xiong C X 2021 Cellulose 28 6513 Google Scholar
[27]	Cao S, Zou H, Jiang B, Li M, Yuan Q 2022 Nano Energy 102 107635 Google Scholar
[28]	Singh A K, Kumar P, Late D, Kumar A, Patel S, Singh J 2018 Appl. Mater. Today 13 242 Google Scholar
[29]	Yin R Y, Li Y H, Li W D, Gao F, Chen X, Li T, Liang J, Zhang H, Gao H, Li P, Zhou Y 2024 Nano Energy 124 109488 Google Scholar
[30]	Han Y, Huang D, Ma Y, He G, Hu J, Zhang J, Hu N, Su Y, Zhou Z, Zhang Y, Yang Z 2018 ACS Appl. Mater. Interfaces 10 22640 Google Scholar
[31]	Zhang J, Han D, Wang Y, Wang L, Chen X, Qiao X, Yu X 2020 Microchim. Acta 187 321 Google Scholar
[32]	Li X, Li Y, Li Y, Tan J, Zhang J, Zhang H, Liang J, Li T, Liu Y, Jiang H, Li P 2022 ACS Appl. Mater. Interfaces 14 46789
[33]	Wang W, Zheng Y, Jin X, Sun Y, Lu B, Wang H, Fang J, Shao H, Lin T 2019 Nano Energy 56 588 Google Scholar
[34]	Ren X, Fan H, Zhao Y, Liu Z 2016 ACS Appl. Mater. Interfaces 8 26190
[35]	Li Y, Su X, Liang K, Luo C, Li P, Hu J, Li G, Jiang H, Wang K 2021 Microelectron. Eng. 244 111557 Google Scholar
[36]	Ning M, Lu M, Li J, Chen Z, Dou Y, Wang C, F Rehman, Cao M, Jin H 2015 Nanoscale 7 15734 Google Scholar
[37]	Zhang W, Zhang V, Wu H, Yan H, Qi S 2018 J. Alloys Compd. 751 34 Google Scholar
[38]	Bowen C R, Kim H A, Weaver P M, Dunn S 2014 Energy Environ. Sci. 7 25 Google Scholar
[39]	Luo C, Hu S, Xia M, Li P, Hu J, Li G, Jiang H, Zhang W 2018 Energy Technol. 6 922 Google Scholar

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Vol. 74, Issue 7 - 2025-04-05

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Piezoelectric sensing properties of PAN/MoS₂ flexible composite nanofiber film

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Corresponding author: LI Yinhui, liyinhui@tyut.edu.cn ; BIAN Guibin, guibin.bian@ia.ac.cn

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Piezoelectric sensing properties of PAN/MoS2 flexible composite nanofiber film

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Corresponding author: LI Yinhui, liyinhui@tyut.edu.cn ; BIAN Guibin, guibin.bian@ia.ac.cn

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Piezoelectric sensing properties of PAN/MoS₂ flexible composite nanofiber film