Abstract
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.
Similar content being viewed by others
References
Inagaki M, Yang Y, Kang F (2012) Carbon nanofibers prepared via electrospinning. Adv Mater 24:2547–2566. https://doi.org/10.1002/adma.201104940
Jiang S, Chen Y, Duan G, Mei C, Greiner A, Agarwal S (2018) Electrospun nanofiber reinforced composites: a review. Polym Chem 9:2685–2720. https://doi.org/10.1039/c8py00378e
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. https://doi.org/10.1021/cr5006217
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. https://doi.org/10.1039/C5TA06844D
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. https://doi.org/10.1016/j.pmatsci.2015.08.002
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. https://doi.org/10.1021/acsami.7b02476
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. https://doi.org/10.1021/acsami.7b18154
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. https://doi.org/10.1016/j.carbon.2005.03.031
Arshad SN, Naraghi M, Chasiotis I (2011) Strong carbon nanofibers from electrospun polyacrylonitrile. Carbon 49:1710–1719. https://doi.org/10.1016/j.carbon.2010.12.056
Liu J, Yue Z, Fong H (2009) Continuous nanoscale carbon fibers with superior mechanical strength. Small 5:536–542. https://doi.org/10.1002/smll.200801440
Bailey JE, Clarke AJ (1971) Carbon fibre formation—the oxidation treatment. Nature 234:529–531. https://doi.org/10.1038/234529a0
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. https://doi.org/10.1016/s0008-6223(03)00391-9
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. https://doi.org/10.1002/anie.201306129
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. https://doi.org/10.1016/j.carbon.2011.09.003
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. https://doi.org/10.3390/ma11081270
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. https://doi.org/10.1016/j.carbon.2008.12.033
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. https://doi.org/10.1016/j.polymdegradstab.2016.12.007
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. https://doi.org/10.1016/j.cej.2011.01.017
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. https://doi.org/10.1016/j.elecom.2008.04.002
Sauder C, Lamon J, Pailler R (2004) The tensile behavior of carbon fibers at high temperatures up to 2400 °C. Carbon 42:715–725. https://doi.org/10.1016/j.carbon.2003.11.020
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. https://doi.org/10.1002/app.1994.070520712
Colvin BG, Storr P (1974) The crystal structure of polyacrylonitrile. Eur Polym J 10:337–340. https://doi.org/10.1016/0014-3057(74)90147-5
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. https://doi.org/10.1016/j.compscitech.2013.08.001
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. https://doi.org/10.1016/j.compositesb.2011.04.024
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. https://doi.org/10.1021/am503542g
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. https://doi.org/10.1016/j.electacta.2015.12.123
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. https://doi.org/10.1016/j.ijbiomac.2015.10.022
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. https://doi.org/10.1016/j.carbon.2015.12.078
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. https://doi.org/10.1016/j.jpowsour.2009.01.089
Koh CT, Strange DGT, Tonsomboon K, Oyen ML (2013) Failure mechanisms in fibrous scaffolds. Acta Biomater 9:7326–7334. https://doi.org/10.1016/j.actbio.2013.02.046
Wan LY, Wang H, Gao W, Ko F (2015) An analysis of the tensile properties of nanofiber mats. Polymer 73:62–67. https://doi.org/10.1016/j.polymer.2015.07.018
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. https://doi.org/10.1021/acs.iecr.7b05336
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. https://doi.org/10.1016/j.matlet.2016.07.144
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. https://doi.org/10.1021/jp908786t
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. https://doi.org/10.1021/jp074464w
Acknowledgements
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).
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Yang, X., Ding, Y., Shen, Z. et al. High-strength electrospun carbon nanofibrous mats prepared via rapid stabilization as frameworks for Li-ion battery electrodes. J Mater Sci 54, 11574–11584 (2019). https://doi.org/10.1007/s10853-019-03698-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-019-03698-z