SCIENCE CHINA Materials, Volume 63 , Issue 10 : 1889-1897(2020) https://doi.org/10.1007/s40843-019-9436-1

Wet-spinning assembly of nitrogen-doped graphene film for stable graphene-polyaniline supercapacitor electrodes with high mass loading

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  • ReceivedFeb 26, 2019
  • AcceptedMay 7, 2019
  • PublishedMay 22, 2019


Graphene-polyaniline (GP) composites are promising electrode materials for supercapacitors but possessing unsatisfied stability, especially under high mass loading, due to the low ion transmission efficiency and serious pulverization effect. To address this issue, we propose a scalable method to achieve highly wettable GP electrodes, showing excellent stability. In addition, our results demonstrate that the performance of electrodes is nearly independent of the mass loading, indicating the great potential of such GP electrodes for practical devices. We attribute the remarkable performance of GP to the delicate precursor of nitrogen doped graphene film assembled by wet-spinning technology. This report provides a strategy to promote the ion penetrating efficiency across the electrodes and deter the pulverization effect, aiming at the practical GP supercapacitor electrodes of high mass loading.

Funded by

the National Natural Science Foundation of China(51533008,21325417,51603183,51703194,51803177,21805242)

the National Key R&D Program of China(2016YFA0200200)

Fujian Provincial Science and Technology Major Projects(2018HZ0001-2)

Hundred Talents Program of Zhejiang University(188020*194231701/113)

the Key research and development plan of Zhejiang Province(2018C01049)

and the Fundamental Research Funds for the Central Universities(2017QNA4036,2017XZZX001-04)


This work is supported by the National Natural Science Foundation of China (51533008, 21325417, 51603183, 51703194, 51803177 and 21805242), the National Key R&D Program of China (2016YFA0200200), Fujian Provincial Science and Technology Major Projects (2018HZ0001-2), Hundred Talents Program of Zhejiang University (188020*194231701/113), the Key Research and Development Plan of Zhejiang Province (2018C01049), and the Fundamental Research Funds for the Central Universities (2017QNA4036 and 2017XZZX001-04).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Chu X and Huang T designed the strategy. Chu X, Hu Y, Dong R and Luo J performed the experiments. Chu X wrote the paper with support from Huang T, Cai S, Gao W, Xu Z and Gao C. All authors contributed to the general discussion.

Author information

Tieqi Huang graduated from Shanghai Jiao Tong University (SJTU) in 2011 and obtained his PhD degree from Zhejiang University in 2018. Currently he is doing postdoctoral research at Nanjing Tech University. His research interests focus on the energy storage, especially supercapacitor.

Chao Gao obtained his PhD degree from Shanghai Jiao Tong University (SJTU) in 2001. He was appointed as an Associate Professor at SJTU in 2002. He did postdoctoral research at the University of Sussex with Prof. Sir Harry W. Kroto and AvH research at Bayreuth University with Prof. Axel H. E. Müller during 2003–2006. He joined the Department of Polymer Science and Engineering, Zhejiang University in 2008 and was promoted as a full Professor. His research interests focus on graphene chemistry, macroscopic assembly, and energy storage.


Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    Fabrication procedure of PNGF. (a) Schematic of the scalable preparation of PNGF. (b) Photograph of wet-spinning step. (c) Optical image of PNGF at bending state.

  • Figure 2

    Characterization of NGF, PNGF, GF, PGF and PANi. Cross-section SEM images of GF (a), PGF (b), and NGF (c). (d, e) Cross-section SEM images of PNGF with different magnifications. (f) Top-view SEM image of the surface of PNGF. (g) Raman spectra of GF, PGF, NGF, PNGF and PANi. (h) XRD patterns of NGF, PNGF, GF, PGF and PANi. (i) FTIR spectra of NGF, PNGF, GF, PGF and PANi.

  • Figure 3

    (a) Dynamic contact angle measurements for NGF, PNGF, GF and PGF. (b) The relationship between contact angle and contact time.

  • Figure 4

    Electrochemical performance of NGF-SC, PNGF-SC, GF-SC and PGF-SC. (a) CV curves of NGF-SC, PNGF-SCy, GF-SC and PGF-SC measured at a scan rate of 10 mV s−1. (b) GCD curves of NGF-SC, PNGF-SC, GF-SC and PGF-SC measured at a current density of 1 A g−1. (c) Rate capability of PNGF-SC calculated by GCD curves from 1 to 100 A g−1. (d) Nyquist plots of NGF-SC, PNGF-SC, GF-SC and PGF-SC with the equivalent circuit. The inset shows the magnified high-frequency region. (e) Cycling stability of PNGF-SC at 2 A g−1. The inset shows the schematic of proposed charge-discharge mechanism of PNGF-SC.

  • Figure 5

    (a) Photograph of NGF hydrogels with different thicknesses. (b) Mass loading of the PNGF is nearly proportional to the thickness of its precursor NGF hydrogel. (c) CV curves of PNGF0.88-SC and PNGF10.34-SC at the scan rate of 10 mV s−1. (d) The GCD curves of PNGF0.88-SC and PNGF10.34-SC under the current density of 1 A g−1. (e) Nyquist plots of PNGF0.88-SC and PNGF10.34-SC with the equivalent circuit. The inset shows the magnified high-frequency region. (f) Effects of mass loading on Cg of PNGF-SC. (g) Top-view SEM image of the surface of PNGF. (h) Cycling stability of PNGF10.34-SC at 2 A g−1. The inset is the schematic illustration of ion transport in PNGF10.34-SC.

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