摩擦纳米发电机用皮芯结构纤维的制备及其性能
Preparation and properties of core-sheath fiber for triboelectric nanogenerator
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收稿日期: 2024-12-17 修回日期: 2025-02-11
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Received: 2024-12-17 Revised: 2025-02-11
作者简介 About authors
于梦菲(2000—),女,硕士生。主要研究方向为离子导体材料的制备与智能应用。
针对具有皮芯结构的摩擦纳米发电机用纤维传统制备工艺复杂的难题,采用微流控纺丝技术,以高介电常数聚偏氟乙烯-六氟丙烯(PVDF-HFP)为皮层材料,丝素蛋白-1-乙基-3-甲基咪唑醋酸盐(EMImAC)离子液体(SE)溶液为导电芯层材料,一步法制备了单电极聚偏氟乙烯-六氟丙烯-丝素蛋白离子液体(PSE)摩擦纳米发电机用纤维(PSE-TENG纤维)。分别借助扫描电子显微镜、万用材料力学测量仪对PSE-TENG纤维的形貌、结构、力学性能进行了表征。使用疲劳测试机进行运动模拟,采用示波器对PSE-TENG纤维的电输出性能进行信号采集。探讨了纺丝参数对PSE-TENG纤维结构的影响,评估了PSE-TENG纤维的力学性能,并探究了PSE-TENG纤维在不同机械运动条件下的输出性能和长期使用稳定性。研究发现:PSE-TENG纤维具有稳定的皮芯结构,拉伸断裂强度为(3.32±0.19)MPa,拉伸断裂应变为(176.83±27.14)%;在不同频率的机械运动下,PSE-TENG纤维的电压信号峰值与频率呈正相关;在超过2万次接触-分离运动后,PSE-TENG纤维仍可稳定输出信号。所制备的PSE-TENG纤维具有优异的能量转换效率和力学稳定性,能够为可穿戴技术提供稳定且高效的自供能解决方案。
关键词:
Objective The triboelectric nanogenerator (TENG) is capable of efficiently converting mechanical energy into electrical energy, showing immense potential in the field of self-powered wearable smart materials. The single-electrode mode, in particular, simplifies the system design and reduces the integration complexity, thereby demonstrating broad applicability across diverse scenarios. However, the conventional fabrication of TENG fibers with a core-sheath structure faces challenges due to the complexity of the preparation process. This study employed microfluidic spinning technology to fabricate single-electrode poly(vinylidene fluoride-hexafluoropropylene)-fibroin ionic liquid triboelectric nanogenerator fibers (PSE-TENG fibers) in a one-step process, using high-dielectric constant poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) as the sheath material and fibroin ionic liquid (SE) solution as the conductive core material.
Method This study explored an innovative method using microfluidic spinning technology to achieve the one-step fabrication of single-electrode PSE-TENG fibers. PVDF-HFP, known for its high dielectric constant, was used as the sheath material, and a silk protein ionic liquid solution, noted for excellent conductivity, stability, and mechanical flexibility, was taken as the core material. The morphology, structure, and mechanical properties of the PSE-TENG fibers were characterized using scanning electron microscopy and a universal mechanical testing machine. A fatigue tester was adopted to simulate motion, and an oscilloscope was employed to collect the electrical output signals of the PSE-TENG fibers. The influences of spinning parameters on the structure of PSE-TENG fibers were thoroughly investigated, their mechanical properties were systematically evaluated, and their output performance and long-term stability under different mechanical motion conditions were explored.
Results SEM images confirmed a well-defined and continuous core-sheath geometry. The core diameter could be tuned by adjusting the flow-rate ratio in the microfluidic spinneret. PSE-TENG fibers exhibited a tensile strength of (3.32±0.19) MPa and an elongation at break of (176.83±27.14) %, indicating excellent flexibility and robustness suitable for textile processing. Under contact-separation motions of different frequencies, the peak open-circuit voltage increased monotonically with frequency, demonstrating a clear correlation between mechanical excitation rate and electrical output. Even after more than 20,000 contact-separation cycles, the voltage signals showed negligible degradation, proving outstanding operational durability.
Conclusion The results validate a facile, scalable microfluidic spinning approach for producing mechanically resilient, high-output PSE-TENG fibers in a single step, thereby eliminating the complexity of conventional layer-by-layer or post-coating techniques. The fibers unite 1) a stable core-sheath architecture, 2) high tensile strength and large elongation, 3) frequency-responsive voltage generation, and 4) long-term cycling reliability exceeding 20 000 operations. These attributes translate into superior energy-conversion efficiency and mechanical robustness, making the PSE-TENG fiber an attractive self-powered component for next-generation wearable electronics, smart textiles, and other portable or deformable devices that demand continuous, reliable, and efficient energy harvesting.
Keywords:
本文引用格式
于梦菲, 高文丽, 任婧, 曹雷涛, 彭若铉, 凌盛杰.
YU Mengfei, GAO Wenli, REN Jing, CAO Leitao, PENG Ruoxuan, LING Shengjie.
在TENG纤维设计中,介电皮层材料需具备高介电常数以增强电荷储存能力,而导电芯层需实现电荷高效传导[15-16]。本文选用聚偏氟乙烯-六氟丙烯(PVDF-HFP)作为介电材料,其兼具高介电常数和压电特性,在机械应力下可有效产生/储存电荷,提升能量转换效率[17-18]。该材料良好的柔韧性、耐腐蚀性与易加工性,使其适于作为皮芯结构纤维的皮层[19]。导电芯层采用丝素蛋白-1-乙基-3-甲基咪唑醋酸盐(EMImAc)离子液体(SE)复合体系,通过离子导体特性维持动态环境下的导电稳定性,同时离子液体的高热稳定性和低挥发性保障了器件的可靠性。丝素蛋白的引入提升了纺丝液黏度并降低了雷诺数,确保微流控过程中形成稳定层流,从而获得结构均匀的连续纤维[10]。这种组合不仅优化了材料的力学稳定性,同时也提升了其摩擦电性能。
本文通过微流控纺丝技术,一步法制备了用于单电极摩擦纳米发电机(TENG)的PVDF-HFP-SE皮芯结构纤维(PSE-TENG纤维),并进一步探讨了纺丝参数对纤维结构的影响,评估了纤维的力学性能,且深入分析了不同频率下纤维的输出信号、长期使用稳定性,以及外力大小对纤维输出性能的影响,为开辟可穿戴自供能材料的实践应用新方向提供参考。
1 实验部分
1.1 实验材料
SU-83025光刻胶,美国Microchem公司;丙二醇甲醚醋酸酯,上海阿拉丁生化科技股份有限公司;异丙醇、碳酸氢钠(NaHCO3)、无水乙醇,国药集团化学试剂有限公司;聚二甲基硅氧烷(PDMS)试剂盒SYLGARDTM 184,美国道康宁公司;聚偏氟乙烯-六氟丙烯(PVDF-HFP),上海爱纯生物科技有限公司;N'N-二甲基甲酰胺(DMF),上海泰坦科技股份有限公司;削口蚕茧,嵊州陌桑高科股份有限公司;1-乙基-3-甲基咪唑醋酸盐(EMImAc),青岛奥立科新材料科技有限公司。
1.2 实验仪器
菲林掩膜版,深圳极显光电有限公司;硅片,深圳瑞格锐思科技有限公司;玻璃片,合肥易铭科学仪器有限公司;JHG-2/W氮气枪,乔索科技(深圳)有限公司;P20导管,美国Scientific Commodities公司;注射器,浙江康德莱医疗器械股份有限公司;EZ4-S-PP匀胶机,江苏雷博科学仪器有限公司;HP550LED数显加热板,大龙兴创实验仪器(北京)股份公司;M365L2-C1 360 nm紫外灯,美国Thoelabs公司;LDO-9076A电热恒温鼓风干燥箱,上海龙跃仪器设备有限公司;LDO-9076A等离子清洗机,美国Harrick Plasma公司;MS-0212磁力搅拌器、VD-R6真空干燥箱、XPB-4双级旋片泵,上海泰坦科技股份有限公司;NE-510恒流注射泵,美国New Era公司;Xtl220体式显微镜,上海天省仪器有限公司;MV- XG51GM-T高速摄像机,深圳迈德威视科技有限公司;57XG04收丝电动机,无锡三拓电气设备有限公司;ISC150离子溅射仪,深圳市速普仪器有限公司;JSM-7800F扫描电子显微镜,日本电子株式会社;万用材料力学测量仪,美国Instron公司;MK-9635-1疲劳测试机,东莞市迈科仪器设备有限公司;TBS-1052EDU示波器,美国Keithley公司。
1.3 试样制备
1.3.1 微流控芯片的制备
采用PDMS软光刻技术制备微流控芯片。首先,为了制备母版,将SU-83025光刻胶以1 400 r/min的速度自旋涂在直径为7.62 cm的硅片上,形成约80 μm厚的均匀SU-8层。在95 ℃温度下前烘20 min后,盖上菲林掩膜版,在120 mW紫外灯下曝光5 min。随后在95 ℃温度下后烘约10 min。重复上述“旋涂—前烘—曝光—后烘”过程2次,以2 000 r/min速度旋涂,获得240 μm厚的均匀SU-8层。然后在丙二醇甲醚醋酸酯中显影12 min。依次用异丙醇和无水乙醇清洗制作好的母版,并用氮气枪吹干。然后,将PDMS前驱体与固化剂以10:1的质量比混合,倒在母版上,在60 ℃温度下固化12 h。将固化后的PDMS从母版上剥离,并使用0.7 mm打孔器打孔获得进口和出口。最后,通过等离子体处理将PDMS黏合到干净的玻璃基底上,获得微流控芯片。
1.3.2 PVDF-HFP纺丝液的制备
将2 g PVDF-HFP粉末加入到14 g DMF中,室温搅拌至完全溶解,获得质量分数为12.5%的PVDF-HFP纺丝液(PVDF-HFP/DMF)。
1.3.3 脱胶丝的制备
使用4 L NaHCO3(质量分数为0.5%)溶液将20 g削口蚕茧先后进行2次持续30 min的煮沸脱胶。脱胶后的蚕丝用去离子水洗涤,在60 ℃的烘箱内烘干12 h,获得脱胶丝。
1.3.4 丝素蛋白离子液体纺丝液的制备
将0.31 g脱胶丝加入到10 g EMImAc中,在100 ℃温度下搅拌至脱胶丝完全溶解。溶液冷却至室温后,使用真空法除去溶液中的气泡,获得质量分数为3%的丝素蛋白-EMImAc离子液体(SE)纺丝液。
1.3.5 PSE-TENG纤维的制备
皮层纺丝液基础参数:质量分数为12.5%的PVDF-HFP/DMF,注射速率为2.4 mL/h;芯层纺丝液基础参数:质量分数为3%的SE,注射速率为0.1 mL/h。将2种溶液分别转移到10 mL和1 mL注射器中。将2个注射器分别用P20导管与微流控芯片连接。随后在室温下,通过注射泵将2种溶液分别按各自注射速率泵入微流控芯片中。纺丝液挤入去离子水中后,立即生成具有皮芯结构的PVDF-HFP-SE纤维。通过收丝电动机,同步将纤维收集在卷轴上,获得PSE-TENG纤维。收丝速度分别为10、15、20 m/h。微流控芯片通道长度分别为1.5、3 cm。改变收丝速度或微流控芯片通道长度时,保持纺丝液基础参数不变。具体纺丝参数如表1所示。
表1 PSE-TENG纤维纺丝参数
Tab.1
| 纺丝方案 | 皮层纺丝液 | 芯层纺丝液 | 收丝速度/ (m·h-1) | 微流控芯片 通道长度/cm | ||
|---|---|---|---|---|---|---|
| 质量分数/% | 流速/(mL·h-1) | 质量分数/% | 流速/(mL·h-1) | |||
| 基础参数 | 12.5 | 2.4 | 3 | 0.1 | 20 | 1.5 |
| 改变收丝速度 | 12.5 | 2.4 | 3 | 0.1 | 10、15、20 | 1.5 |
| 改变皮层纺丝液含量 | 12.5、20.0 | 2.4 | 3 | 0.1 | 20 | 1.5 |
| 改变芯片通道长度 | 12.5 | 2.4 | 3 | 0.1 | 20 | 1.5、3 |
1.4 测试与表征
1.4.1 PSE-TENG纤维的形貌观察
将PSE-TENG纤维放入液氮中,用锋利刀片切断,获得平整切面,用于观察纤维截面。将PSE-TENG纤维固定在铜胶带基底上,用于观察纤维表面。先用离子溅射仪喷金处理30 s,再用扫描电子显微镜观察PSE-TENG纤维的截面和表面形貌。
1.4.2 PSE-TENG纤维的力学性能测试
1.4.3 PSE-TENG纤维摩擦发电机的性能表征
2 结果与讨论
2.1 PSE-TENG纤维的设计与制备及结构
在本文实验中,采用微流控湿法纺丝技术制备PSE-TENG纤维(见图1)。纺丝装置由纺丝液注入部分、微流控芯片、收丝部分组成,可以实现自动化批量纺丝—收丝。PVDF-HFP溶液和丝素蛋白离子液体在微流控通道中形成分层,经过纺丝出口后,PVDF-HFP快速发生相变固化形成皮层,紧密包裹芯层的丝素蛋白离子液体。
图1
图1
PSE-TENG纤维制备过程示意图
Fig.1
Schematic diagram of preparation process of PSE-TENG fiber
通过对微流控芯片的设计,综合考虑溶液可纺性能,可以获得直径在200~400 μm之间的纤维。较小的直径有利于提升PSE-TENG纤维的比表面积,提高摩擦电发电效率,同时更有利于将PSE-TENG纤维集成为轻量化织物。图2为PSE-TENG纤维SEM照片。可看出,PSE-TENG纤维具有典型的皮芯结构。由于芯层为丝素蛋白离子液体,因此并未在SEM照片中呈现。PVDF皮层具有致密的表面,内部为多孔结构。致密表面作为一种屏障,有助于防止外部水分和污染物的渗入。这不仅能保护纤维内部多孔结构,还能降低环境因素对其电学性能的影响。同时可减少物理和化学环境损害,提高纤维的耐久性,继而延长摩擦纳米发电机的使用寿命。材料内部的多孔结构有利于PSE-TENG纤维吸收机械压力,使纤维具有更好的抗破裂性和柔韧性,有利于其经受TENG应用中反复的机械变形。
图2
图2
PSE-TENG纤维的SEM照片
Fig.2
SEM images of PSE-TENG fiber.
(a) Surface of PSE-TENG fiber; (b) Cross section of PSE-TENG fiber
图3
图4
图4
纺丝参数对纤维结构的调控
Fig.4
PSE-TENG fiber structure regulated by concentration of sheath spinning solution (a) and channel length of microfluidic chip (b)
由图3可知,当收丝速度增加时,纤维的芯层空间会逐渐变小,纤维宏观结构从无规弯曲变为直线型。这是因为收丝速度的增加导致纤维在凝固浴中受到更大的拉伸牵引作用,使芯层被压缩,纤维被拉直。由图4(a)可知,仅提高PVDF-HFP纺丝液质量分数(20% PVDF-HFP/DMF),此时纺丝液含量过高,纤维在凝固浴中难以充分固化,使得纤维在收丝过程中变形,无法形成预设的皮芯结构。由图4(b)可知,仅增加芯片通道长度时,因为芯层与皮层溶液之间存在较长的接触时间,且存在微小湍流或扰动的可能性增加,提升了二者之间扩散的机会,同时流体速度的变化以及剪切效应的增加,共同导致芯层与皮层之间存在界面不稳定,发生部分混合,使得纤维难以形成稳定的皮芯结构[22]。因此,为了稳定制备具有皮芯结构的PSE纤维,本文最终采用收丝速度为20 m/h、PVDF-HFP纺丝液质量分数为12.5%、芯片通道长度为1.5 cm的纺丝参数。
2.2 PSE-TENG纤维的力学性能
图5
图5
PSE-TENG纤维的力学性能
Fig.5
Mechanical properties of PSE-TENG fiber.
(a) Stress-strain curve of PSE-TENG fiber; (b) True stress-elongation curves of PSE-TENG fiber, thermoplastic materials and rubber; (c) Ashby plots of strain and strength of PSE-TENG fiber, representative conductive materials and skin
在初始拉伸阶段,PSE-TENG纤维发生较小的应变变化,就会产生较大的应力变化。在这段应变范围内,纤维发生的是弹性形变,符合胡克定律,应力会随应变的增加以恒定的斜率增加,通过计算得到纤维的弹性模量为(66.9±14.6)MPa。应力-应变曲线达到一定应力值后,纤维开始进入塑性形变阶段。随着塑性形变的增加,纤维的应力水平也随之增加,纤维强度提升、更难以形变。最终,当应力达到纤维的断裂强度(3.32±0.19)MPa时,纤维发生断裂,断裂应变为(176.83±27.14)%。
2.3 PSE-TENG的功能应用
图6示出TENG的工作原理。SE芯层作为导电电极材料,PVDF-HFP皮层作为负摩擦电材料。可看出,当PSE-TENG与丁腈远离时,二者表面未发生电荷转移。当PSE-TENG与丁腈靠近时,由于PVDF-HFP的高表面电子亲和力, 丁腈表面与PSE-TENG的PVDF-HFP皮层表面产生极性相反的电荷,负电荷从丁腈表面转移至PVDF-HFP表面。PVDF-HFP表面上未屏蔽的负电荷吸引SE中的正电荷移动到SE/PVDF-HFP界面,进行电荷补偿。而SE中的负电荷移动到SE与铜导体之间的界面,铜导体中的自由电子流向地面。当PSE-TENG与丁腈完全接触时,系统整体电荷得到平衡。但如果PSE-TENG与丁腈重新分离,电荷的运动逆转,自由电子从地面流向铜导体。当PSE-TENG与丁腈完全远离时,系统整体电荷得到平衡,没有电信号输出。总之,如果PSE-TENG与丁腈反复接触-分离,则输出信号是循环的,且符号相反[26-27]。图7(a)示出用于自动循环测试的设备。该设备用于定量评估PSE-TENG性能在恒定频率(0.5~3 Hz)下响应恒定负载压力(2~12 N)的长期稳定性。由图7(b)可知,在相同压力下,输出电压V与接触频率呈正相关。V=QR/t,其中Q为每个接触产生的传递电荷,t为接触时间[28]。在这种情况下,Q被当作常数,因为接触面积本质上是常数。也就是说,该式表明,工作频率越高,PSE-TENG电极与地之间的电荷转移越快,从而输出电压随着外部负载频率的增加而增加。这种特性适用于高频(例如瞬时运动或振动)传感应用,因为信号强度随着测试频率的增加而呈线性增加。
图6
图6
PSE-TENG单电极工作原理
Fig.6
Working principle of PSE-TENG in single-electrode mode
图7
图7
PSE-TENG的电输出特性
Fig.7
Characterization of electrical output from PSE-TENG.
(a) Schematic illustration of automatic cyclic contact test device; (b) Output voltages of PSE-TENG at different working frequencies; (c) Stability and reliability of PSE-TENG at 27 000 cycles with working frequency of 0.5 Hz; (d) Output voltages of PSE-TENG in response to periodic compression with different contact forces applied; (e) Fitting diagram of linear relationship between external force and peak output voltage
3 结论
本文通过微流控湿法纺丝技术制备的用于摩擦纳米发电机的具有皮芯结构的纤维(PSE-TENG纤维),由聚偏氟乙烯-六氟丙烯(PVDF-HFP)皮层和丝素蛋白离子液体(SE)芯层组成,其具有良好的柔韧性和力学强度,可确保纤维在使用过程中的力学完整性以及满足可穿戴摩擦纳米发电机织物所需具有的柔软性。PSE-TENG纤维在不同频率的接触-分离动作下,会产生不同峰值的信号,且电压值与频率呈线性正相关。此外,PSE-TENG纤维还具有长期稳定性,在2万多次的接触-分离动作下,仍稳定输出信号。同时,纤维输出的信号仅与触觉相关,受外力大小影响较小。所制备的PSE-TENG纤维有潜力作为摩擦纳米发电机应用到自供能的可穿戴智能织物领域。
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