静电纺丝法制备聚偏二氟乙烯-六氟丙烯电解质膜用于电化学执行器

doi:10.6023/A24020049

化学学报 ›› 2024, Vol. 82 ›› Issue (6): 570-576.DOI: 10.6023/A24020049 上一篇下一篇

研究论文

静电纺丝法制备聚偏二氟乙烯-六氟丙烯电解质膜用于电化学执行器

汪莎莎^a, 孟鹏辉^a, 李阳^a, 邓慧婵^a, 郭志翔^a, 刘一任^a, 石乃恩^b, 魏颖^a^,^*(), 解令海^a^,^*()

a 南京邮电大学信息材料与纳米技术研究院有机电子与信息显示国家重点实验室分子系统与有机器件研究中心南京 210023
b 福建师范大学海峡柔性电子(未来科技)研究院福州 350117

投稿日期:2024-02-07 发布日期:2024-05-28
基金资助:
南京邮电大学自然科学基金(NY222157); 南京邮电大学自然科学基金(NY221085); 有机电子与信息显示国家重点实验室(GZR2022010008); 江苏省低维材料化学重点实验室开放课题(JSKC20022); 国家留学基金(202008320051); 国家基础科学中心(62288102)

Preparation of Polyvinylidene Fluoride-Hexafluoropropylene Electrolyte Membrane by Electrospinning Method for Electrochemical Actuators

Shasha Wang^a, Penghui Meng^a, Yang Li^a, Huichan Deng^a, Zhixiang Guo^a, Yiren Liu^a, Naien Shi^b, Ying Wei^a,*(), Linghai Xie^a,*()

a Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China
b Fujian Cross Strait Institute of Flexible Electronics (Future Technology), Fujian Normal University, Fuzhou 350117, China

Received:2024-02-07 Published:2024-05-28
Contact: * E-mail: iamywei@njupt.edu.cn; iamlhxie@njupt.edu.cn
Supported by:
Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY222157); Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY221085); State Key Laboratory of Organic Electronics and Information Display(GZR2022010008); Key Laboratory of Low-dimensional Materials Chemistry of Jiangsu Province(JSKC20022); National Overseas Study Fund(202008320051); National Basic Science Center(62288102)

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摘要/Abstract

本研究采用静电纺丝法制备了两种具有不同纤维直径的聚偏二氟乙烯-六氟丙烯(PVDF-HFP)电解质薄膜用于电化学执行器. 相比于滴涂薄膜, 电纺薄膜具有出色的柔韧性和大量孔隙结构, 其中粗纤维薄膜(PVDF-HFP 22% (w))表现出更好的拉伸断裂应力(7.52 MPa)、拉伸断裂伸长率(235%)和器件面电容(39.8 mF•cm^-2). 在±0.5 V, 0.1 Hz的低驱动电压下, 粗纤维薄膜制备的电化学执行器的驱动位移为9.6 mm, 相比于细纤维执行器的6.5 mm和滴涂薄膜执行器的2.6 mm分别提升了1.48倍和3.69倍. 当电压升高到±2 V, 0.1 Hz时, 粗纤维薄膜执行器驱动位移为24.3 mm, 分别是细纤维执行器的1.19倍和滴涂样品的1.46倍. 该工作为制备大驱动位移电化学执行器提供了新的思路与方法.

关键词: 静电纺丝, 聚偏二氟乙烯-六氟丙烯, 电解质膜, 电化学执行器, 纤维直径

The microstructure of the electrolyte layer in electrochemical actuators significantly influences ion storage and transport, mechanical properties, and the final actuator deformation performance. In this study, two types of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) electrolyte films with varying fiber diameters were prepared by electrospinning for electrochemical actuators. We controlled the diameters of the fibers by adjusting the concentrations of the polymer solution, while the film is carefully controlled to a consistent size in length, width, and thickness. Subsequently, the fiber film was immersed in the ionic liquid to achieve excellent electrolyte film performance. A poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) electrode thin film was prepared using a drop coating method. Finally, an electrochemical actuator was prepared by hot pressing the electrode and electrolyte films. Compared with the drop-coated electrolyte film, the electrospun counterparts exhibit an excellent flexibility and a porous structure. Among them, the film with a larger fiber diameter (PVDF-HFP 22% (w)) reveals better tensile stress (7.52 MPa), tensile strain (235%), porosity (74%) and surface capacitance (39.8 mF•cm^-2), and its tip displacement is 9.6 mm at ±0.5 V and 0.1 Hz, which is 1.48 times that of the smaller fiber diameter sample (PVDF-HFP 16% (w)) and 3.69 times that of the drop-coated sample, respectively. When at ±2 V and 0.1 Hz, the displacement is as high as 24.3 mm, which is 1.19 times that of the smaller fiber diameter sample (PVDF-HFP 16% (w)) and 1.46 times that of the drop-coated sample, respectively. Under the driving voltage of ±0.5 V and 0.1 Hz, after 10000 cycles, the driving displacement of PVDF-HFP 22% (w) electrochemical actuator can still reach 98% compared with the initial state. By improving the microstructures of electrolyte films through electrospinning, we successfully realized the preparation of high-performance electrochemical actuators, which provides a new idea for the development of soft robots in the future.

Key words: electrospinning, polyvinylidene fluoride-hexafluoropropylene, electrolyte membrane, electrochemical actuator, fiber diameter

引用此文

汪莎莎, 孟鹏辉, 李阳, 邓慧婵, 郭志翔, 刘一任, 石乃恩, 魏颖, 解令海. 静电纺丝法制备聚偏二氟乙烯-六氟丙烯电解质膜用于电化学执行器[J]. 化学学报, 2024, 82(6): 570-576.

Shasha Wang, Penghui Meng, Yang Li, Huichan Deng, Zhixiang Guo, Yiren Liu, Naien Shi, Ying Wei, Linghai Xie. Preparation of Polyvinylidene Fluoride-Hexafluoropropylene Electrolyte Membrane by Electrospinning Method for Electrochemical Actuators[J]. Acta Chimica Sinica, 2024, 82(6): 570-576.

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图/表 4

图1. (a)静电纺丝法制备PVDF-HFP纤维薄膜; (b) PVDF-HFP纤维薄膜; (c) PVDF-HFP纤维薄膜浸泡在EMIMBF4; (d)电化学执行器器件结构; (e)施加电压下的电化学执行器

Figure 1. (a) PVDF-HFP fiber film prepared by electrospinning method; (b) PVDF-HFP fiber film; (c) PVDF-HFP fiber film soaked in EMIMBF4; (d) the device structure of the electrochemical actuator; (e) the electrochemical actuator under applied voltage (a) PVDF-HFP fiber film prepared by electrospinning method; (b) PVDF-HFP fiber film; (c) PVDF-HFP fiber film soaked in EMIMBF4; (d) the device structure of the electrochemical actuator; (e) the electrochemical actuator under applied voltage

图2. (a) PVDF-HFP 22% (w)纤维薄膜实物图像; (b)滴涂薄膜实物图像; (c) PVDF-HFP 16% (w)纤维薄膜的SEM图像; (d) PVDF-HFP 16% (w)纤维薄膜直径统计图; (e) PVDF-HFP 22% (w)纤维薄膜的SEM图像; (f) PVDF-HFP 22% (w)纤维薄膜直径统计图; (g) PVDF-HFP 22% (w)电解质纤维薄膜SEM图像; (h) PVDF-HFP 22% (w)纤维薄膜截面SEM图像

Figure 2. (a) Physical image of PVDF-HFP 22% (w) fiber film; (b) physical image of drop-coating film; (c) SEM image of PVDF-HFP 16% (w) fiber film; (d) diameter statistical diagram of PVDF-HFP 16% (w) fiber film; (e) SEM image of PVDF-HFP 22% (w) fiber film; (f) diameter statistical diagram of PVDF-HFP 22% (w) fiber film; (g) SEM image of PVDF-HFP 22% (w) electrolyte fiber film; (h) cross-sectional SEM image of PVDF-HFP 22% (w) fiber film

图3. (a) PVDF-HFP 16% (w)和PVDF-HFP 22% (w)纤维薄膜的应力应变图; (b) PEDOT:PSS薄膜的应力应变图; (c) PVDF-HFP 16% (w)纤维薄膜电化学执行器、PVDF-HFP 22% (w)纤维薄膜电化学执行器和滴涂薄膜电化学执行器的应力应变图; (d) PVDF-HFP 16% (w)纤维薄膜、PVDF-HFP 22% (w)纤维薄膜和滴涂薄膜的阻抗测试

Figure 3. (a) Stress-strain diagram of PVDF-HFP 16% (w) and PVDF-HFP 22% (w) fiber films; (b) stress-strain diagram of PEDOT:PSS film; (c) stress-strain diagram of PVDF-HFP 16% (w) fiber film electrochemical actuator, PVDF-HFP 22% (w) fiber film electrochemical actuator and drop-coated film electrochemical actuator; (d) impedance test of PVDF-HFP 16% (w) fiber film, PVDF-HFP 22% (w) fiber film and drop-coated film

图4. PVDF-HFP 16% (w)纤维薄膜电化学执行器、PVDF-HFP 22% (w)纤维薄膜电化学执行器和滴涂薄膜电化学执行器: (a)阻抗测试; (b)在25 mV?s-1条件下的CV曲线; (c)在±2 V, 0.1~10 Hz条件下的位移曲线; (d)在±0.5 V, 0.1~10 Hz条件下的位移图

Figure 4. PVDF-HFP 16% (w) fiber film electrochemical actuator, PVDF-HFP 22% (w) fiber film electrochemical actuator and drop-coated film electrochemical actuator: (a) impedance test; (b) CV curve at 25 mV?s-1; (c) the displacement curve under the condition of ±2 V, 0.1~10 Hz; (d) displacement diagram at ±0.5 V, 0.1~10 Hz

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静电纺丝法制备聚偏二氟乙烯-六氟丙烯电解质膜用于电化学执行器

Preparation of Polyvinylidene Fluoride-Hexafluoropropylene Electrolyte Membrane by Electrospinning Method for Electrochemical Actuators

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