Journal of Materials Science

, Volume 54, Issue 17, pp 11574–11584 | Cite as

High-strength electrospun carbon nanofibrous mats prepared via rapid stabilization as frameworks for Li-ion battery electrodes

  • Xue Yang
  • Yichun Ding
  • Zhigang Shen
  • Qian Sun
  • Fan Zheng
  • Hao Fong
  • Zhengtao ZhuEmail author
  • Jie Liu
  • Jieying Liang
  • Xiaoxu WangEmail author
Energy materials


Carbon nanofibrous nonwoven mats (CNFMs) prepared via electrospinning offer excellent electrical and structural properties and have been used as frameworks for electrodes in electrochemical energy storage devices. However, lack of mechanical strength hinders the broad applications of CNFMs in flexible electronics or industry use. In this work, a rapid stabilization method is developed to prepare high-strength and flexible CNFMs. Studies of the effects of stabilization time on the structures of the stabilized polyacrylonitrile (PAN) nanofibers and the subsequent carbon nanofibers reveal that there is an optimal stabilization time for making high-strength CNFMs. Long stabilization time results in excessive oxidation of the stabilized PAN nanofibers and unwanted defects in the carbon nanofibers. Short stabilization time results in carbon nanofibers with less crystalline structures due to insufficient formation of the thermally stable ladder-like structure. Robust and flexible CNFM with the highest tensile strength of 192.7 MPa is obtained using an optimized total stabilization time of 40 min. To demonstrate the application of the flexible CNFMs, they are fabricated as an electrode framework to load TiO2 nanoparticles without use of organic binders. Lithium ion half-cell based on this electrode demonstrates superior rate cycling performance owning to the porous structure and highly conductive fibrous carbon network of CNFM.



This research was supported by the National Natural Science Foundation of China (Grant #: 51602016), the Fundamental Research Funds for the Central Universities (Grant #: PYVZ1704, ZY1607). The research at South Dakota School of Mines and Technology was supported by the National Aeronautics and Space Administration (NASA Cooperative Agreement No. 80NSSC18M0022).

Supplementary material

10853_2019_3698_MOESM1_ESM.docx (2.3 mb)
Supplementary material 1 (DOCX 2361 kb)


  1. 1.
    Inagaki M, Yang Y, Kang F (2012) Carbon nanofibers prepared via electrospinning. Adv Mater 24:2547–2566. CrossRefGoogle Scholar
  2. 2.
    Jiang S, Chen Y, Duan G, Mei C, Greiner A, Agarwal S (2018) Electrospun nanofiber reinforced composites: a review. Polym Chem 9:2685–2720. CrossRefGoogle Scholar
  3. 3.
    Yang Z, Ren J, Zhang Z, Chen X, Guan G, Qiu L et al (2015) Recent advancement of nanostructured carbon for energy applications. Chem Rev 115:5159–5223. CrossRefGoogle Scholar
  4. 4.
    Jung J-W, Lee C-L, Yu S, Kim I-D (2015) Electrospun nanofibers as a platform for advanced secondary batteries: a comprehensive review. J Mater Chem A 4:703–750. CrossRefGoogle Scholar
  5. 5.
    Zhang B, Kang F, Tarascon J, Kim J (2016) Recent advances in electrospun carbon nanofibers and their application in electrochemical energy storage. Prog Mater Sci 76:319–380. CrossRefGoogle Scholar
  6. 6.
    Adams RA, Syu JM, Zhao Y, Lo CT, Varma A, Pol VG (2017) Binder-free N- and O-rich carbon nanofiber anodes for long cycle life K-ion batteries. ACS Appl Mater Interfaces 9:17872–17881. CrossRefGoogle Scholar
  7. 7.
    Chen X, Yuan L, Hao Z, Liu X, Xiang J, Zhang Z et al (2018) Free-standing Mn3O4@CNF/S paper cathodes with high sulfur loading for lithium–sulfur batteries. ACS Appl Mater Interfaces 10:13406–13412. CrossRefGoogle Scholar
  8. 8.
    Zussman E, Chen X, Ding W, Calabri L, Dikin DA, Quintana JP et al (2005) Mechanical and structural characterization of electrospun PAN-derived carbon nanofibers. Carbon 43:2175–2185. CrossRefGoogle Scholar
  9. 9.
    Arshad SN, Naraghi M, Chasiotis I (2011) Strong carbon nanofibers from electrospun polyacrylonitrile. Carbon 49:1710–1719. CrossRefGoogle Scholar
  10. 10.
    Liu J, Yue Z, Fong H (2009) Continuous nanoscale carbon fibers with superior mechanical strength. Small 5:536–542. CrossRefGoogle Scholar
  11. 11.
    Bailey JE, Clarke AJ (1971) Carbon fibre formation—the oxidation treatment. Nature 234:529–531. CrossRefGoogle Scholar
  12. 12.
    Zhang W, Liu J, Gang W (2003) Evolution of structure and properties of PAN precursors during their conversion to carbon fibers. Carbon 41:2805–2812. CrossRefGoogle Scholar
  13. 13.
    Frank E, Steudle LM, Ingildeev D, Spörl JM, Buchmeiser MR (2014) Carbon fibers: precursor systems, processing, structure, and properties. Angew Chem Int Ed 53:5262–5298. CrossRefGoogle Scholar
  14. 14.
    Lian F, Liu J, Ma Z, Liang J (2012) Stretching-induced deformation of polyacrylonitrile chains both in quasicrystals and in amorphous regions during the in situ thermal modification of fibers prior to oxidative stabilization. Carbon 50:488–499. CrossRefGoogle Scholar
  15. 15.
    Yang J, Liu Y, Liu J, Shen Z, Liang J, Wang X (2018) Rapid and continuous preparation of polyacrylonitrile-based carbon fibers with electron-beam irradiation pretreatment. Materials 11:1270–1279. CrossRefGoogle Scholar
  16. 16.
    Liu J, Zhou P, Zhang L, Ma Z, Liang J, Fong H (2009) Thermo-chemical reactions occurring during the oxidative stabilization of electrospun polyacrylonitrile precursor nanofibers and the resulting structural conversions. Carbon 47:1087–1095. CrossRefGoogle Scholar
  17. 17.
    Nunna S, Naebe M, Hameed N, Fox BL, Creighton C (2017) Evolution of radial heterogeneity in polyacrylonitrile fibres during thermal stabilization: an overview. Polym Degrad Stab 136:20–30. CrossRefGoogle Scholar
  18. 18.
    Wang MX, Huang ZH, Shimohara T, Kang F, Liang K (2011) NO removal by electrospun porous carbon nanofibers at room temperature. Chem Eng J 170:505–511. CrossRefGoogle Scholar
  19. 19.
    Li M, Han G, Yang B (2008) Fabrication of the catalytic electrodes for methanol oxidation on electrospinning-derived carbon fibrous mats. Electrochem Commun 10:880–883. CrossRefGoogle Scholar
  20. 20.
    Sauder C, Lamon J, Pailler R (2004) The tensile behavior of carbon fibers at high temperatures up to 2400 °C. Carbon 42:715–725. CrossRefGoogle Scholar
  21. 21.
    Liu J, Wang PH, Li RY (1994) Continuous carbonization of polyacrylonitrile-based oxidized fibers: aspects on mechanical properties and morphological structure. J Appl Polym Sci 52:945–950. CrossRefGoogle Scholar
  22. 22.
    Colvin BG, Storr P (1974) The crystal structure of polyacrylonitrile. Eur Polym J 10:337–340. CrossRefGoogle Scholar
  23. 23.
    Sui G, Sun F, Yang X, Ji J, Zhong W (2013) Highly aligned polyacrylonitrile-based nano-scale carbon fibres with homogeneous structure and desirable properties. Compos Sci Technol 87:77–85. CrossRefGoogle Scholar
  24. 24.
    Molnar K, Vas LM, Czigany T (2012) Determination of tensile strength of electrospun single nanofibers through modeling tensile behavior of the nanofibrous mat. Compos B 43:15–21. CrossRefGoogle Scholar
  25. 25.
    Wang X, Xi M, Fong H, Zhu Z (2014) Flexible, transferable, and thermal-durable dye-sensitized solar cell photoanode consisting of TiO2 nanoparticles and electrospun TiO2/SiO2 nanofibers. ACS Appl Mater Interfaces 6:15925–15932. CrossRefGoogle Scholar
  26. 26.
    Wang X, Xi M, Wang X, Fong H, Zhu Z (2016) Flexible composite felt of electrospun TiO2 and SiO2 nanofibers infused with TiO2 nanoparticles for lithium ion battery anode. Electrochim Acta 190:811–816. CrossRefGoogle Scholar
  27. 27.
    Youe WJ, Lee SM, Lee SS, Lee SH, Kim YS (2016) Characterization of carbon nanofiber mats produced from electrospun lignin-g-polyacrylonitrile copolymer. Int J Biol Macromol 82:497–504. CrossRefGoogle Scholar
  28. 28.
    Ding R, Wu H, Thunga M, Bowler N, Kessler MR (2016) Processing and characterization of low-cost electrospun carbon fibers from organosolv lignin/polyacrylonitrile blends. Carbon 100:126–136. CrossRefGoogle Scholar
  29. 29.
    Li M, Zhao S, Han G, Yang B (2009) Electrospinning-derived carbon fibrous mats improving the performance of commercial Pt/C for methanol oxidation. J Power Sour 191:351–356. CrossRefGoogle Scholar
  30. 30.
    Koh CT, Strange DGT, Tonsomboon K, Oyen ML (2013) Failure mechanisms in fibrous scaffolds. Acta Biomater 9:7326–7334. CrossRefGoogle Scholar
  31. 31.
    Wan LY, Wang H, Gao W, Ko F (2015) An analysis of the tensile properties of nanofiber mats. Polymer 73:62–67. CrossRefGoogle Scholar
  32. 32.
    Salim NV, Blight S, Creighton C, Nunna S, Atkiss S, Razal JM (2018) The role of tension and temperature for efficient carbonization of polyacrylonitrile fibers: toward low cost carbon fibers. Ind Eng Chem Res 57:4268–4276. CrossRefGoogle Scholar
  33. 33.
    Ma S, Liu J, Qu M, Wang X, Huang R, Liang J (2016) Effects of carbonization tension on the structural and tensile properties of continuous bundles of highly aligned electrospun carbon nanofibers. Mater Lett 183:369–373. CrossRefGoogle Scholar
  34. 34.
    Lafont U, Carta D, Mountjoy G, Chadwick AV, Kelder EM (2010) In situ structural changes upon electrochemical lithium insertion in nanosized anatase TiO2. J Phys Chem C 114:1372–1378. CrossRefGoogle Scholar
  35. 35.
    Wang J, Polleux J, Lim J, Dunn B (2007) Pseudocapacitive contributions to electrochemical energy storage in TiO2 (Anatase) nanoparticles. J Phys Chem C 111:14925–14931. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of EducationBeijing University of Chemical TechnologyChao-Yang District, BeijingChina
  2. 2.Department of Chemistry and Applied Biological SciencesSouth Dakota School of Mines and TechnologyRapid CityUSA
  3. 3.SINOPEC Shanghai Research Institute of Petrochemical TechnologyShanghaiChina

Personalised recommendations