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Improving electrochemical properties of carbon nanotubes/reduced graphene oxide composite fibers by chemical modification

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Abstract

To promote application of graphene fiber as electrode for supercapacitors, carbon nanotubes (CNTs)/reduced graphene oxide (RGO) composite fibers were fabricated with GO/polyacrylonitrile (PAN) fibers using chemical vapor deposition method, and then treated with mixed acid to modify the hydrophilicity of the fiber. Transformation of excellent nano-scale properties of graphene and CNTs into macroscopic material properties was realized. The GO/PAN fiber was prepared by wet spinning and thermal stabilized in advance before in situ growth of CNTs to the fiber. Structures and electrochemical properties of the CNTs/RGO composite fiber were investigated. Interaction between GO and PAN during stabilization resulted in less mass loss of the fiber. The CNTs/RGO composite fibers exhibited a specific surface area of 87.873 m2 g−1 with large quantity of entwined CNTs about 39–130 nm in diameter and centimeters in length. Increase of 37.43% oxygen-containing functional groups greatly improved the hydrophilicity of the fiber after chemical modification. The specific capacitance increased from 34 to 141 F g−1 at 0.1 A g−1 for the CNTs/RGO composite fibers due to improved ionic accessibility and pseudo-capacitance provided by oxygen-containing functional groups. The chemical modified CNTs/RGO fiber is suitable for electrode material of supercapacitors due to its excellent cycle stability with specific capacitance retention of 96% after 2500 cycles of the charge/discharge process and low ESR and Rct. A method for the synthesis of CNTs/RGO composite fibers with good three-dimensional structures and an idea of modifying ionic accessibility to improve the electrochemical performance of the fibers was presented.

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References

  1. B. Wang, L.L. Ji, Y.L. Yu, N.X. Wang, J. Wang, J.B. Zhao, A simple and universal method for preparing N, S co-doped biomass derived carbon with superior performance in supercapacitors, Electrochimica. Acta 309, 34–43 (2019)

    Google Scholar 

  2. S. Osman, R.A. Senthil, J.Q. Pan, Highly activated porous carbon with 3D microspherical structure and hierarchical pores as greatly enhanced cathode material for high-performance supercapacitors. J. Power Sources 391, 162–169 (2018)

    Article  ADS  Google Scholar 

  3. S. Lee, A. Geon-Hyoung, Reversible faradaic reactions involving redox mediators and oxygen-containing groups on carbon fiber electrode for high-performance flexible fibrous supercapacitors. J. Energy Chem. 68, 1–11 (2022)

    Article  Google Scholar 

  4. F. Han, S.Z. Duan, W.X. Jing, Q.W. Tian, Z.K. Zhang, J.S. Liu, Y. Sun, Z.D. Jiang, Synthesis and plasma treatment of nitrogen-doped graphene fibers for high-performance supercapacitors. Ceram. Int. 48, 2050–2067 (2022)

    Google Scholar 

  5. J.H. Liu, X.Y. Xu, J.L. Yu, J.L. Hong, C. Liu, X. Ouyang, S. Lei, X. Meng, J.N. Tang, D.Z. Chen, Facile construction of 3D porous carbon nanotubes/polypyrrole and reduced graphene oxide on carbon nanotube fiber for high-performance asymmetric supercapacitors. Electrochim. Acta 314, 9–19 (2019)

    Article  Google Scholar 

  6. Z. Xu, H.Y. Sun, X.L. Zhao, C. Gao, Ultrastrong fibers assembled from giant graphene oxide sheets. Adv. Mater. 25, 188–193 (2013)

    Article  Google Scholar 

  7. R. Jalili, S.H. Aboutalebi, D. Esrafilzadeh, R.L. Shepherd, J. Chen, S. Aminorroaya-Yamini, K. Konstantinov, A.L. Minett, J.M. Razal, G.G. Wallace, Scalable one-step wet-spinning of graphene fibers and yarns from liquid crystalline dispersions of graphene oxide: towards multifunctional textiles. Adv. Funct. Mater. 23, 5345–5354 (2013)

    Article  Google Scholar 

  8. B. Dan, N. Behabtu, A. Martinez, J.S. Evans, D.V. Kosynkin, J.M. Tour, M. Pasquali, L.L. Smalyukh, Liquid crystals of aqueous, giant graphene oxide flakes. Soft Matter 7, 11154–11150 (2011)

    Article  ADS  Google Scholar 

  9. S.H. Chen, W.J. Ma, H.X. Xiang, Y.H. Cheng, S.Y. Yang, W. Weng, M.F. Zhu, Conductive, tough, hydrophilic poly(vinyl alcohol)/graphene hybrid fibers for wearable supercapacitors. J. Power Sources 319, 271–280 (2016)

    Article  ADS  Google Scholar 

  10. S.Y. Wang, K.W. Cao, L.H. Xu, D.L. Zhao, Y.J. Tong, Carbon nanotubes/reduced graphene oxide composites as electrode materials for supercapacitors. Appl. Phys. A 128, 81 (2021)

    Article  ADS  Google Scholar 

  11. C.G. Liu, Z.N. Yu, D. Neff, A. Zhamu, B.Z. Jang, Graphene-based supercapacitor with an ultrahigh energy density. Nano Lett. 10, 4863–4868 (2010)

    Article  ADS  Google Scholar 

  12. N.F. He, W.T. Shan, J.L. Wang, Q. Pan, J.G. Qu, G.F. Wang, W. Gao, Mordant inspired wet-spinning of graphene fibers for high performance flexible supercapacitors. J. Mater. Chem. A 7, 6869–6876 (2019)

    Article  Google Scholar 

  13. C.Q. Li, X.L. Wang, L.H. Xu, A.J. Gao, D.H. Xu, Preparation of graphene oxide/polyacrylonitrile fiber from graphene oxide solution with high dispersivity. Compos. Interfaces 8, 1–14 (2019)

    ADS  Google Scholar 

  14. W. Eom, S.H. Lee, H. Shin, W. Jeong, K.H. Koh, T.H. Han, Microstructure-controlled polyacrylonitrile/graphene fibers over 1 gigapascal strength. ACS Nano 15, 13055–13064 (2021)

    Article  Google Scholar 

  15. N.V. Salim, X. Jin, J.M. Razal, Polyacrylonitrile/liquid crystalline graphene oxide composite fibers—towards high performance carbon fiber precursors. Compos. Sci. Techno. 182, 107781 (2019)

    Article  Google Scholar 

  16. W.J. Ma, M. Li, X. Zhou, J.H. Li, Y.M. Dong, M.F. Zhu, Three-dimensional porous carbon nanotubes/reduced graphene oxide fiber from rapid phase separation for a high-rate all-solid-state supercapacitor. ACS Appl. Mater. Interfaces 11, 9283–9290 (2019)

    Article  Google Scholar 

  17. D.S. Yu, K.L. Goh, H. Wang, L. Wei, W.C. Jiang, Q. Zhang, L.M. Dai, Y. Chen, Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage. Nat. Nanotechnol. 9, 555–562 (2014)

    Article  ADS  Google Scholar 

  18. H.H. Cheng, Z.L. Dong, C.G. Hu, Y. Zhao, Y. Hu, L.T. Qu, N. Chen, L.M. Dai, Textile electrodes woven by carbon nanotube–graphene hybrid fibers for flexible electrochemical capacitors. Nanoscale 5, 3428–3434 (2013)

    Article  ADS  Google Scholar 

  19. R.V. Salvatierra, D. Zakhidov, J.W. Sha, N.D. Kim, S.K. Lee, A.O. Raji, N.Q. Zhao, J.M. Tour, Graphene carbon nanotube carpets grown using binary catalysts for high-performance lithium-ion capacitors. ACS Nano 11, 2724 (2017)

    Article  Google Scholar 

  20. T.X. Guan, L.M. Shen, N.Z. Bao, Hydrophilicity improvement of graphene fibers for high-performance flexible supercapacitor. Ind. Eng. Chem. Res. 58, 17338–17345 (2019)

    Article  Google Scholar 

  21. Q. Liu, J.W. Zhou, C.H. Song, 2.2V high performance symmetrical fiber-shaped aqueous supercapacitors enabled by “water-in-salt” gel electrolyte and N-Doped graphene fiber. Energy Storage Mater. 24, 495–503 (2020)

    Article  Google Scholar 

  22. Y.J. Chen, L. Sun, Z.E. Liu, Y.Y. Jiang, K.L. Zhuo, Synthesis of nitrogen/sulfur co-doped reduced graphene oxide aerogels for high-performance supercapacitors with ionic liquid electrolyte. Mater. Chem. Phys. 238, 121932 (2019)

    Article  Google Scholar 

  23. N. Ucar, M. Olmez, B.K. Kayaoglu, A. Onen, N.K. Yavuz, O. Eksik, Structural properties of graphene oxide fibers: from graphene oxide dispersion until continuous graphene oxide fiber. J. Text. I(109), 1642–1652 (2018)

    Google Scholar 

  24. A.J. Gao, D.H. Xu, C.Q. Li, Y. Wang, L.H. Xu, Interfacial reactions in graphene oxide/polyacrylonitrile composite films. Comps. Interfaces 28, 159–173 (2020)

    Article  ADS  Google Scholar 

  25. R. Devasia, C.P.R. Nair, Copolymerization of acrylonitrile with itaconic acid in dimethylformamide: effect of triethylamine. Eur. Polym. J. 39, 537–544 (2003)

    Article  Google Scholar 

  26. Q. Ouyang, L. Cheng, H.J. Wang, K.X. Li, Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile. Polym. Degrad. and Stabil. 93, 1415–1421 (2008)

    Article  Google Scholar 

  27. R.V. Salvatierra, D. Zakhidov, J. Sha, D.K. Nam, S.K. Lee, A.O. Raji, N.Q. Zhao, J.M. Tour, Graphene carbon nanotube carpets grown using binary catalysts for high-performance lithium-ion capacitors[J]. ACS Nano 11(3), 2724 (2017)

    Article  Google Scholar 

  28. R. Sayyad, M. Ghambari, T. Ebadzadeh, A.H. Oakseresht, E. Ghasali, Preparation of Ag/reduced graphene oxide reinforced copper matrix composites through spark plasma sintering: an investigation of microstructure and mechanical properties. Ceram. Int. 46, 13569–13579 (2020)

    Article  Google Scholar 

  29. A.A. Babaev, M.E. Zobov, E.I. Terukov, V.S. Levitskii, Features of the temperature dependence of graphene oxide resistivity. Bull. Acad. Sci. Phys. 82, 815–816 (2018)

    Article  Google Scholar 

  30. R. Rasuli, Z. Mokarian, R. Karimi, H. Shabanzadeh, Y. Abedini, Wettability modification of graphene oxide by removal of carboxyl functional groups using non-thermal effects of microwave. Thin Solid Films 589, 364–368 (2015)

    Article  ADS  Google Scholar 

  31. Y.J. Hsiao, L.Y. Lin, Enhanced surface area, graphene quantum dots and functional groups for the simple acid-treated carbon fiber electrode of flexible fiber-type solid-state supercapacitors without active materials. ACS Sustain. Chem. Eng. 8, 2453–2461 (2020)

    Article  Google Scholar 

  32. Y. Fang, B. Luo, Y.Y. Jia, X.L. Li, B. Wang, Q. Song, F.Y. Kang, L.J. Zhi, Renewing functionalized graphene as electrodes for high-performance supercapacitors. Adv. Mater. 24, 6348–6355 (2012)

    Article  Google Scholar 

  33. X. Li, W. Xing, S.P. Zhuo, J. Zhou, F. Li, S.Z. Qiao, G.Q. Lu, Preparation of capacitor’s electrode from sunflower seed shell. Bioresource Technol. 102(2), 1118–1123 (2011)

    Article  Google Scholar 

  34. C. Zheng, X.F. Zhou, H.L. Cao, G.H. Wang, Z.P. Liu, Synthesis of porous graphene/activated carbon composite with high packing density and large specific surface area for supercapacitor electrode material. J. Power Sources 258, 290–296 (2014)

    Article  ADS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China

    Songyan Wang, Kaiwen Cao & Yuanjian Tong

  2. Key Laboratory of Carbon Fiber and Functional Polymer, Ministry of Education, Beijing University of Chemical Technology, Beijing, 100029, China

    Songyan Wang, Kaiwen Cao, Lianghua Xu & Yuanjian Tong

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  1. Songyan Wang
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Correspondence to Yuanjian Tong.

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Wang, S., Cao, K., Xu, L. et al. Improving electrochemical properties of carbon nanotubes/reduced graphene oxide composite fibers by chemical modification. Appl. Phys. A 129, 56 (2023). https://doi.org/10.1007/s00339-022-06340-z

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