纺织学报 ›› 2023, Vol. 44 ›› Issue (12): 205-215.doi: 10.13475/j.fzxb.20220903902

• 综合述评 • 上一篇    下一篇

微流控纺丝制备石墨烯纤维基柔性超级电容器的研究进展

管图祥, 吴健, 暴宁钟()   

  1. 南京工业大学 化工学院, 江苏 南京 211816
  • 收稿日期:2022-09-16 修回日期:2023-02-01 出版日期:2023-12-15 发布日期:2024-01-22
  • 通讯作者: 暴宁钟(1975—),男,教授,博士。主要研究方向为多维功能材料,结构功能一体化复合材料的制备及其高性能应用。E-mail:nzhbao@njtech.edu.cn
  • 作者简介:管图祥(1994—),男,博士。主要研究方向为纤维柔性储能技术。
  • 基金资助:
    国家自然科学基金项目(51425202);国家自然科学基金项目(51772150);江苏高校优势学科建设工程资助项目(PAPD);江苏省博士后计划项目(2023822)

Research progress in graphene fiber-based flexible supercapacitors prepared by microfluidic spinning

GUAN Tuxiang, WU Jian, BAO Ningzhong()   

  1. College of Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211816, China
  • Received:2022-09-16 Revised:2023-02-01 Published:2023-12-15 Online:2024-01-22

摘要:

为更好解决石墨烯纤维基超级电容器在柔性储能领域所面临的微结构调控困难、电化学性能不足的问题,对微流控纺丝制备石墨烯纤维基柔性超级电容器的研究展开论述。介绍了微流体纺丝通道的类型及其构筑方法,随后聚焦于微流体在微通道中的流体流动行为和凝固机制;在此基础上,围绕纤维结构-性能关系和柔性储能应用介绍了微流控纺丝技术在制备石墨烯纤维基柔性超级电容器方面的研究进展。分析认为:石墨烯纤维基超级电容器具有能量密度高、柔性好、安全性高等特点,在可穿戴电子设备供能领域拥有巨大潜力;为进一步优化纤维微观结构与化学组成,未来发展微流控纺丝制备石墨烯纤维基电极需要综合考量纺丝芯片设计加工、流体数值模拟、纤维微结构构筑3个方面因素。

关键词: 微通道, 流体力学, 石墨烯纤维, 柔性超级电容器, 柔性储能, 微流控纺织技术

Abstract:

Significance Corresponding to the increasing demand for the electronics with higher portability, intelligence, and conformability, wearable devices present a fast-growing market and application prospect. The application scenarios of these wearable devices normally present features of high flexibility, deformability and complexity that restrict the service of traditional rigid energy storage systems. In this context, fiber shaped flexible supercapacitors have aroused vast interests for their distinctive advances in flexibility, power density, operation safety and cycling life. Thereinto, graphene fiber-based supercapacitors show the characteristics of high energy density, good flexibility and high safety, presenting great potential to power wearable devices. To date, remarkable progress has been achieved in designing and fabricating graphene-based fiber via different spinning methods such as wet spinning, dry spinning and hydrothermal spinning. However, to accommodate simultaneously the requirements of high electrochemical property and mechanical robustness of electrode materials that originate from the complex application scenarios, it is still highly demanded to develop new spinning approaches to further control the chemical component and structure of graphene-based fiber.
Progress Microfluidic spinning method, as a new generation of spinning approach evolving from microfluidic chip technology, has aroused wide attention for its advantages in preparing refined hetero-structured fibers, and a number of studies have been reported. Precise control of primitive structure and chemical component can be facilitated on graphene fiber through simulating fluid flow of graphene oxide (GO) dispersion, through designing spinneret with different structures and adjusting spinning solution composition and fluid flow state. Typically, for fiber structure adjustment, converging, expanding and coaxial spinning channels have been developed to prepare graphene fibers with high axial order degree, vertical sheet alignment and core-shell structure, respectively. Correspondingly, the as-prepared graphene fibers present high mechanical strength, short ion transport pathway and multi-scenario application capability. For chemical component adjustment, coagulation methods including chemical crosslinking, ionic crosslinking, solvent exchange and solvent vaporing are selected to fabricate graphene based composite fiber with capacitance reinforcement phase. On this basis, heteroatom doping, porous structure and core-shell structured graphene-based composite fibers have been subsequently developed. Through structure and component adjustments, graphene-based fibers exhibit large ion accessible surface, improved ion/electron transport ability, high electrochemical activity and great mechanical stability. Accordingly, the graphene fiber-based supercapacitor prepared by microfluidic spinning technology present high energy density and desirable dynamic output, which can steadily drive multi-color display.
Conclusion and Prospect Predominant progresses have been acquired in preparing hetero-structured graphene based composite fibers that show ideal mechanical-electrochemical performance via microfluidic spinning technology. Basing on the computational fluid dynamics simulation, structure design of spinneret, and spinning solution compound regulation, microfluidic spinning technology can effectively control the flow behavior and composition. The resultant programmable chemical component adjustments combined with accurate regulation in fiber structure endow graphene-based fiber one of the best candidates in flexible energy storage application. In this regard, with the persistent growth of wearable device, microfluidic spinning technology will become an indispensable method for preparing high performance graphene fiber-based supercapacitor. In this process, it would be helpful to consider the following issues. Exploration of appropriate methods and materials for microfluidic channel fabrication. To date, numerous materials and fabrication methods have been developed to prepare spinning channel. Nevertheless, with the consideration that structure design of the spinning channel is the primary approach to control the fluid flow, and it is still necessary to further explore relevant preparation methods and materials to realize the refined channel structure. Simulation of the flow behavior of GO dispersion in microchannels. The complex rheological behaviors of GO dispersion led to difficulty in formulating flow equations to describe solution process, and thus numerical simulation remains the fundamental method for investigation, where, unfortunately, the research in this regard appears to be limited. It is hence highly necessary to simulate and predict the flow behavior of GO dispersion in microchannels based on the experiences of computational fluid dynamics in other fields. Development of graphene fiber-based electrode with novel structure and chemical composition. Although graphene presents the advantages of high conductivity, high strength, and large specific surface area, its assemblies suffer from the severe restacking structure and inferior electrochemical activity. To this end, exploration of graphene fiber-based electrode with novel structure and electrochemical active composition is of profound significance to narrow the Laboratory-Factory gap in the area of flexible energy storage.

Key words: microchannel, fluid mechanic, graphene fiber, flexible supercapacitor, flexible energy storage, microfluidic spinning technology

中图分类号: 

  • TQ028.8

图1

微流控纺丝芯片的构型"

图2

GO分散液在不同微通道中的流动行为"

图3

微流控纺丝制备纤维的凝固机制示意图"

表1

微流控纺丝制备石墨烯纤维基柔性超级电容器的结构及性能"

电极材料 结构 电解质 电压窗口/V 比电容 能量密度 参考文献
石墨烯纤维 多孔结构 H2SO4 0~1 409 F/g 14 W·h/kg [47]
石墨烯纤维 多孔结构 H2SO4 0~1 279 F/g 5.76 W·h/kg [48]
碳黑/石墨烯纤维 多孔结构 H3PO4 0~1 79 F/cm3 1.73 mW·h/cm3 [53]
碳多面体/石墨烯纤维 多孔结构 H3PO4 0~0.8 2 760 mF/cm2 335.8 μW·h/cm2 [55]
聚苯胺/石墨烯纤维 核壳结构 H3PO4 0~0.8 230 mF/cm2 37.2 μW·h/cm2 [56]
氧化镍/石墨烯纤维 核壳结构 KOH 0~0.8 605.9 mF/cm2 120.3 μW·h/cm2 [57]
同轴石墨烯纤维 核壳结构 H3PO4 0~1 269 mF/cm2 5.91 μW·h/cm2 [59]
MoS2石墨烯纤维 核壳结构 H2SO4 -0.1~0.5 1 330 mF/cm2 69.44 μW·h/cm2 [61]
[1] 王霁龙, 刘岩, 景媛媛, 等. 纤维基可穿戴电子设备的研究进展[J]. 纺织学报, 2020, 41(12): 157-165.
WANG Jilong, LIU Yan, JING Yuanyuan, et al. Advances in fiber-based wearable electronic devices[J]. Journal of Textile Research, 2020, 41(12): 157-165.
[2] 王栋, 卿星, 蒋海青, 等. 纤维材料与可穿戴技术的融合与创新[J]. 纺织学报, 2018, 39(5): 150-154.
WANG Dong, QING Xing, JIANF Haiqing, et al. Integration and innovation of fiber materials and wearable technology[J] Journal of Textile Research, 2018, 39(5): 150-154.
[3] 聂文琪, 孙江东, 许帅, 等. 柔性纺织纤维基超级电容器研究进展[J]. 纺织学报, 2022, 47(7): 200-206.
NIE Wenqi, SUN Jiangdong, XU Shuai, et al. Research progress in supercapacitors based on flexible textile fibers[J]. Journal of Textile Research, 2022, 43(7): 200-206.
[4] LIU Wei, SONG Minsang, KONG Biao, et al. Flexible and stretchable energy storage: recent advances and future perspectives[J]. Advanced Materials, 2017. DOI: 10.1002/adma.201603436.
[5] TAO Jiayou, LIU Nishuang, MA Wenzhen, et al. Solid-state high performance flexible supercapacitors based on polypyrrole-MnO2-carbon fiber hybrid structure[J]. Scientific Reports, 2013. DOI: 10.1038/srep02286.
[6] PAN Zhenghui, YANG Jie, ZHANG Qichong, et al. All-solid-state fiber supercapacitors with ultrahigh volumetric energy density and outstanding flexibility[J]. Advanced Energy Materials, 2019. DOI: 10.1002/aenm.201802753.
[7] XIAO Wei, HUANG Jing, ZHOU Wenjie, et al. Surface modification of commercial cotton yarn as electrode for construction of flexible fiber-shaped supercapacitor[J]. Coatings, 2021. DOI: ARTN 108610.3390/coatings11091086.
[8] 庞雅莉, 孟佳意, 李昕, 等. 石墨烯纤维的湿法纺丝制备及其性能[J]. 纺织学报, 2020, 41(9): 1-7.
PANG Yali, MENG Jiayi, LI Xin, et al. Preparation of graphene fibers by wet spinning and fiber characterization[J]. Journal of Textile Research, 2020, 41(9): 1-7.
[9] FANG Bo, CHANG Dan, XU Zhen, et al. A review on graphene fibers: expectations, advances, and pros-pects[J]. Advanced Materials, 2020. DOI: 10.1002/adma.201902664.
[10] 何大方, 吴健, 刘战剑, 等. 面向应用的石墨烯制备研究进展[J]. 化工学报, 2015, 66(8): 2888-2894.
HE Dafang, WU Jian, LIU Zhanjian, et al. Recent advances in preparation of graphene for applications[J]. CIESC Journal, 2015, 66(8): 2888-2894.
[11] XU Zhen, GAO Chao. Graphene chiral liquid crystals and macroscopic assembled fibres[J]. Nature Communications, 2011. DOI: 10.1038/ncomms1583.
[12] TIAN Qishi, XU Zhen, LIU Yingjun, et al. Dry spinning approach to continuous graphene fibers with high toughness[J]. Nanoscale, 2017, 9(34): 12335-12342.
[13] DONG Zelin, JIANG Changcheng, CHENG Huhu, et al. Facile fabrication of light, flexible and multifunctional graphene fibers[J]. Advanced Materials, 2012, 24(14): 1856-1861.
[14] HUA Chunfei, SHANG Yuanyuan, LI Xiying, et al. Helical graphene oxide fibers as a stretchable sensor and an electrocapillary sucker[J]. Nanoscale, 2016, 8(20): 10659-10668.
[15] LIU Qiang, ZHOU Jingwen, SONG Chenhui, et al. 2.2V high performance symmetrical fiber-shaped aqueous supercapacitors enabled by "water-in-salt" gel electrolyte and N-doped graphene fiber[J]. Energy Storage Mater, 2020, 24: 495-503.
[16] WANG Chunya, XIA Kailun, WANG Huimin, et al. Advanced carbon for flexible and wearable elec-tronics[J]. Advanced Materials, 2019. DOI: 10.1002/adma.201801072.
[17] SACKMANN Eric K, FULTON Anna L, BEEBE David J. The present and future role of microfluidics in biomedical research[J]. Nature, 2014, 507(7491): 181-189.
[18] JUN Yesl, KANG Edward, CHAE Sukyoung, et al. Microfluidic spinning of micro- and nano-scale fibers for tissue engineering[J]. Lab on A Chip, 2014, 14(13): 2145-2160.
[19] KANG Edward, JEONG Gi Seok, CHOI Yoon Young, et al. Digitally tunable physicochemical coding of material composition and topography in continuous microfibres[J]. Nature Materials, 2011, 10(11): 877-883.
[20] MANZ A, GRABER N, WIDMER H M. Miniaturized total chemical-analysis systems: a novel concept for chemical sensing[J]. Sensors and Actuators B-Chemical, 1990, 1(1): 244-248.
[21] MCDONALD J Cooper, DUFFY David C, ANDERSON Janelle R, et al. Fabrication of microfluidic systems in poly(dimethylsiloxane)[J]. Electrophoresis, 2000, 21(1): 27-40.
[22] THORSEN Todd, MAERKL Sebastian J, QUAKE Stephen R. Microfluidic large-scale integration[J]. Science, 2002, 298(5593): 580-584.
[23] ZHANG Mengfan, PENG Xiaotong, FAN Penghui, et al. Recent progress in preparation and application of fibers using microfluidic spinning technology[J]. Macromolecular Chemistry and Physics, 2022. DOI: 10.1002/macp.202100451.
[24] JIA Luanluan, HAN Fengxuan, YANG Huili, et al. Microfluidic fabrication of biomimetic helical hydrogel microfibers for blood-vessel-on-a-chip applications[J]. Advanced Healthcare Materials, 2019. DOI: 10.1002/adhm.201900435.
[25] SONG Helen, CHEN Delai L, ISMAGILOV Rustem F. Reactions in droplets in microfluidic channels[J]. Angewandte Chemie-International Edition, 2006, 45(44): 7336-7356.
[26] HE Yong, WU Yan, FU Jianzhong, et al. Fabrication of paper-based microfluidic analysis devices: a review[J]. RSC Advances, 2015, 5(95): 78109-78127.
[27] 蒋艳, 马翠翠, 胡贤巧, 等. 微流控纸芯片的加工技术及其应用[J]. 化学进展, 2014, 26(1): 167-177.
JIANG Yan, MA Cuicui, HU Xianqiao, et al. Fabrication techniques of microfluidic paper-based chips and their applications[J]. Progress in Chemistry, 2014, 26(1): 167-177.
[28] WHITESIDES George M. The origins and the future of microfluidics[J]. Nature, 2006, 442(7101): 368-373.
[29] KIM Jaemyung, COTE Laura J, HUANG Jiaxing. Two dimensional soft material: new faces of graphene oxide[J]. Accounts of Chemical Research, 2012, 45(8): 1356-1364.
[30] DEL Giudice, SHEN Amy Q. Shear rheology of graphene oxide dispersions[J]. Current Opinion in Chemical Engineering, 2017, 16: 23-30.
[31] VALLÉS Cristina, YOUNG Robert J, LOMAX Deborah J, et al. The rheological behaviour of concentrated dispersions of graphene oxide[J]. Journal of Materials Science, 2014, 49(18): 6311-6320.
[32] XU Tong, ZHANG Zhipan, QU Liangti. Graphene-based fibers: recent advances in preparation and applica-tion[J]. Advanced materials, 2020. DOI: 10.1002/adma.201901979.
[33] XU Zhen, PENG Li, LIU Yingjun, et al. Experimental guidance to graphene macroscopic wet-spun fibers, continuous papers, and ultralightweight aerogels[J]. Chem Mater, 2016, 29(1): 319-330.
[34] CAI Weihua, LAI Ting, YE Jianshan. A spinneret as the key component for surface-porous graphene fibers in high energy density micro-supercapacitors[J]. Journal of Materials Chemistry A, 2015, 3(9): 5060-5066.
[35] XIN Guoqing, ZHU Weiguang, DENG Yanxiang, et al. Microfluidics-enabled orientation and microstructure control of macroscopic graphene fibres[J]. Nature Nanotechnology, 2019, 14(2): 168-175.
[36] FANG Bo, XIAO Youhua, XU Zhen, et al. Handedness-controlled and solvent-driven actuators with twisted fibers[J]. Materials Horizons, 2019, 6(6): 1207-1214.
[37] GUAN Tuxiang, SHEN Shuo, CHENG Zhisheng, et al. Microfluidic-assembled hierarchical macro-microporous graphene fabrics towards high-performance robust supercapacitors[J]. Chemical Engineering Journal, 2022. DOI: ARTN13587810.1016/j.cej.2022.135878.
[38] PARK H, LEE K H, KIM Y B, et al. Dynamic assembly of liquid crystalline graphene oxide gel fibers for ion transport[J]. Science Advances, 2018. DOI: 10.1126/sciadv.aau2104.
[39] XIA Yu, MATHIS Tyler S, ZHAO Mengqiang, et al. Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes[J]. Nature, 2018, 557(7705): 409-412.
[40] DU Xiangyun, LI Qing, WU Guan, et al. Multifunctional micro/nanoscale fibers based on microfluidic spinning technology[J]. Advanced Materials, 2019. DOI: 10.1002/adma.201903733.
[41] HONG Yu Lim, RYU Seongwoo, JEONG Hyeon Su, et al. Surface functionalization effect of graphene oxide on its liquid crystalline and assembly behaviors[J]. Applied Surface Science, 2019. DOI: 10.1016/j.apsusc.2019.03.023.
[42] SHAO Feng, HU Nantao, SU Yanjie, et al. Non-woven fabric electrodes based on graphene-based fibers for areal-energy-dense flexible solid-state supercapa-citors[J]. Chemical Engineering Journal, 2020. DOI: 10.1016/j.cej.2019.123692.
[43] KANG Edward, CHOI Yoon Young, CHAE Su Kyoung, et al. Microfluidic spinning of flat alginate fibers with grooves for cell-aligning scaffolds[J]. Advanced Materials, 2012, 24(31): 4271-4277.
[44] XIN Guoqing, YAO Tiankai, SUN Hongtao, et al. Highly thermally conductive and mechanically strong graphene fibers[J]. Science, 2015, 349(6252): 1083-1087.
[45] XU Zhen, SUN Haiyan, ZHAO Xiaoli, et al. Ultrastrong fibers assembled from giant graphene oxide sheets[J]. Advanced Materials, 2013, 25(2): 188-193.
[46] CAO Jun, ZHANG Yongyi, MEN Chuanling, et al. Programmable writing of graphene oxide/reduced graphene oxide fibers for sensible networks with in situ welded junctions[J]. ACS Nano, 2014, 8(5): 4325-4333.
[47] ABOUTALEBI Seyed Hamed, JALILI Rouhollah, ESRAFILZADEH Dorna, et al. High-performance multifunctional graphene yarns: toward wearable all-carbon energy storage textiles[J]. ACS Nano, 2014, 8(3): 2456-2466.
[48] CHEN Shaohua, MA Wujun, CHENG Yanhua, et al. Scalable non-liquid-crystal spinning of locally aligned graphene fibers for high-performance wearable supercapacitors[J]. Nano Energy, 2015, 15: 642-653.
[49] WU Changcun, WANG Xia, ZHUO Qiqi, et al. A facile continuous wet-spinning of graphene oxide fibers from aqueous solutions at high pH with the introduction of ammonia[J]. Carbon, 2018, 138: 292-299.
[50] GUAN Tuxiang, SHEN Liming, BAO Ningzhong. Hydrophilicity improvement of graphene fibers for high-performance flexible supercapacitor[J]. Industrial & Engineering Chemistry Research, 2019, 58(37): 17338-17345.
[51] SIMON Patrice, GOGOTSI Yury. Perspectives for electrochemical capacitors and related devices[J]. Nature materials, 2020, 19(11): 1151-1163.
[52] MING X, WEI A, LIU Y, et al. 2D-topology-seeded graphitization for highly thermally conductive carbon fibers[J]. Advanced Materials, 2022. DOI: 10.1002/adma.202201867.
[53] MA Wujun, CHEN Shaohua, YANG Shengyuan, et al. Hierarchically porous carbon black/graphene hybrid fibers for high performance flexible supercapacitors[J]. RSC Advances, 2016, 6(55): 50112-50118.
[54] ZHU Y, MURALI S, STOLLER M D, et al. Carbon-based supercapacitors produced by activation of gra-phene[J]. Science, 2011, 332(6037): 1537-1541.
[55] QIU Hui, CHENG Hengyang, MENG Jinku, et al. Magnetothermal microfluidic-assisted hierarchical microfibers for ultrahigh energy density supercapa-citors[J]. Angewandte Chemie-International Edition, 2020, 59(20): 7934-7943.
[56] WU X J, WU G, TAN P F, et al. Construction of microfluidic oriented polyaniline nanorod arrays/graphene composite fibers for application in wearable micro-supercapacitors[J]. Journal of Materials Chemistry A, 2018, 6(19): 8940-8946.
[57] MENG Jinku, WU Guan, WU Xingjiang, et al. Microfluidic-architected nanoarrays/porous core-shell fibers toward robust micro energy storage[J]. Advanced Science, 2020. DOI: 10.1002/advs.201901931.
[58] XU Tong, DING Xiaoteng, LIANG Yuan, et al. Direct spinning of fiber supercapacitor[J]. Nanoscale, 2016, 8(24): 12113-12117.
[59] KOU Liang, HUANG Tieqi, ZHENG Bingna, et al. Coaxial wet-spun yarn supercapacitors for high energy density and safe wearable electronics[J]. Nature Communications, 2014. DOI: 10.1038/ncomms4754.
[60] LI Hongfei, TANG Zijie, LIU Zhuoxin, et al. Evaluating flexibility and wearability of flexible energy storage devices[J]. Joule, 2019, 3(3): 613-619.
[61] KHUDIYEV Tural, LEE Jung Tae, COX Jason R, et al. 100 m long thermally drawn supercapacitor fibers with applications to 3D printing and textiles[J]. Advanced Materials, 2020. DOI: 10.1002/adma.202004971.
[62] SEYEDIN Shayan, ROMANO Mark S, MINETT Andrew I, et al. Towards the knittability of graphene oxide fibres[J]. Scientific Reports, 2015. DOI: 10.1038/srep14946.
[63] LI Zheng, XU Zhen, LIU Yingjun, et al. Multifunctional non-woven fabrics of interfused graphene fibres[J]. Nature Communications, 2016. DOI: 10.1038/ncomms13684.
[64] GUAN Tuxiang, CHENG Zhisheng, LI Zemei, et al. Hydrothermal-assisted in situ growth of vertically aligned MoS2 nanosheets on reduced graphene oxide fiber fabrics toward high-performance flexible supercapacitors[J]. Industrial & Engineering Chemistry Research, 2022, 61(11): 3840-3849.
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