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

湿纺组装氮掺杂石墨烯薄膜用于高稳定性石墨烯-聚苯胺超级电容器电极

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Abstract

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.

摘要

石墨烯-聚苯胺(GP)复合材料是一种有前途的超级电容器电极材料, 但其稳定性较差, 尤其在负载量高的情况下. 低离子传输效率和严重的粉碎效应是导致这一结果的主要原因. 为了解决这个问题, 我们提出了一种可规模化制备高度可润湿GP电极的方法, 该电极显示出优异的稳定性. 此外, 研究结果表明电极的性能几乎与负载量无关, 因此这种GP电极在实际生产中具有巨大潜力. 通过湿纺技术组装的氮掺杂石墨烯薄膜前驱体使得这种电极材料表现出卓越性能. 这种提高电极间离子渗透效率并阻止粉碎效应的方法, 旨在制备实用型高负载量的GP超级电容器电极.

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References

  1. Liu C, Li F, Ma LP, et al. Advanced materials for energy storage. Adv Mater, 2010, 22: E28–E62

    CAS  Google Scholar 

  2. Zhu Y, Murali S, Cai W, et al. Graphene and graphene oxide: Synthesis, properties, and applications. Adv Mater, 2010, 22: 3906–3924

    CAS  Google Scholar 

  3. Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon, 2001, 39: 937–950

    CAS  Google Scholar 

  4. Du Pasquier A, Laforgue A, Simon P, et al. A nonaqueous asymmetric hybrid Li4Ti5O12/poly(fluorophenylthiophene) energy storage device. J Electrochem Soc, 2002, 149: A302

    CAS  Google Scholar 

  5. Talbi H, Just PE, Dao LH. Electropolymerization of aniline on carbonized polyacrylonitrile aerogel electrodes: Applications for supercapacitors. J Appl Electrochem, 2003, 33: 465–473

    CAS  Google Scholar 

  6. Snook GA, Kao P, Best AS. Conducting-polymer-based supercapacitor devices and electrodes. J Power Sources, 2011, 196: 1–12

    CAS  Google Scholar 

  7. Liu Z, Li Z, Xu Z, et al. Wet-spun continuous graphene films. Chem Mater, 2014, 26: 6786–6795

    CAS  Google Scholar 

  8. Xu Z, Gao C. Graphene in macroscopic order: Liquid crystals and wet-spun fibers. Acc Chem Res, 2014, 47: 1267–1276

    CAS  Google Scholar 

  9. Xu Z, Gao C. Aqueous liquid crystals of graphene oxide. ACS Nano, 2011, 5: 2908–2915

    CAS  Google Scholar 

  10. Huang T, Chu X, Cai S, et al. Tri-high designed graphene electrodes for long cycle-life supercapacitors with high mass loading. Energy Storage Mater, 2019, 17: 349–357

    Google Scholar 

  11. Kudin KN, Ozbas B, Schniepp HC, et al. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett, 2008, 8: 36–41

    CAS  Google Scholar 

  12. Cong HP, Ren XC, Wang P, et al. Flexible graphene–polyaniline composite paper for high-performance supercapacitor. Energy Environ Sci, 2013, 6: 1185

    CAS  Google Scholar 

  13. Huang T, Zheng B, Liu Z, et al. High rate capability supercapacitors assembled from wet-spun graphene films with a CaCO3template. J Mater Chem A, 2015, 3: 1890–1895

    CAS  Google Scholar 

  14. Yan J, Wei T, Fan Z, et al. Preparation of graphene nanosheet/carbon nanotube/polyaniline composite as electrode material for supercapacitors. J Power Sources, 2010, 195: 3041–3045

    CAS  Google Scholar 

  15. Zou Y, Zhang Z, Zhong W, et al. Hydrothermal direct synthesis of polyaniline, graphene/polyaniline and n-doped graphene/polyaniline hydrogels for high performance flexible supercapacitors. J Mater Chem A, 2018, 6: 9245–9256

    CAS  Google Scholar 

  16. Xu Y, Tao Y, Zheng X, et al. A metal-free supercapacitor electrode material with a record high volumetric capacitance over 800 F cm−3. Adv Mater, 2015, 27: 8082–8087

    CAS  Google Scholar 

  17. Wang H, Hao Q, Yang X, et al. A nanostructured graphene/polyaniline hybrid material for supercapacitors. Nanoscale, 2010, 2: 2164–2170

    CAS  Google Scholar 

  18. Zhao J, Jiang Y, Fan H, et al. Porous 3D few-layer graphene-like carbon for ultrahigh-power supercapacitors with well-defined structure-performance relationship. Adv Mater, 2017, 29: 1604569

    Google Scholar 

  19. Wang H, Hao Q, Yang X, et al. Effect of graphene oxide on the properties of its composite with polyaniline. ACS Appl Mater Interfaces, 2010, 2: 821–828

    CAS  Google Scholar 

  20. Chen LF, Zhang XD, Liang HW, et al. Synthesis of nitrogen-doped porous carbon nanofibers as an efficient electrode material for supercapacitors. ACS Nano, 2012, 6: 7092–7102

    CAS  Google Scholar 

  21. Alhabeb M, Beidaghi M, Van Aken KL, et al. High-density freestanding graphene/carbide-derived carbon film electrodes for electrochemical capacitors. Carbon, 2017, 118: 642–649

    CAS  Google Scholar 

  22. Khomenko V, Frackowiak E, Béguin F. Determination of the specific capacitance of conducting polymer/nanotubes composite electrodes using different cell configurations. Electrochim Acta, 2005, 50: 2499–2506

    CAS  Google Scholar 

  23. Mishra AK, Ramaprabhu S. Functionalized graphene-based nanocomposites for supercapacitor application. J Phys Chem C, 2011, 115: 14006–14013

    CAS  Google Scholar 

  24. Wu Q, Xu Y, Yao Z, et al. Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. ACS Nano, 2010, 4: 1963–1970

    CAS  Google Scholar 

  25. Li R, Ren X, Zhang F, et al. Synthesis of Fe3O4@SnO2 core–shell nanorod film and its application as a thin-film supercapacitor electrode. Chem Commun, 2012, 48: 5010–5012

    CAS  Google Scholar 

  26. Li L, Raji ARO, Fei H, et al. Nanocomposite of polyaniline nanorods grown on graphene nanoribbons for highly capacitive pseudocapacitors. ACS Appl Mater Interfaces, 2013, 5: 6622–6627

    CAS  Google Scholar 

  27. Li ZF, Zhang H, Liu Q, et al. Fabrication of high-surface-area graphene/polyaniline nanocomposites and their application in supercapacitors. ACS Appl Mater Interfaces, 2013, 5: 2685–2691

    CAS  Google Scholar 

  28. Xu Y, Schwab MG, Strudwick AJ, et al. Screen-printable thin film supercapacitor device utilizing graphene/polyaniline inks. Adv Energy Mater, 2013, 3: 1035–1040

    CAS  Google Scholar 

  29. Hao Q, Xia X, Lei W, et al. Facile synthesis of sandwich-like polyaniline/boron-doped graphene nano hybrid for supercapacitors. Carbon, 2015, 81: 552–563

    CAS  Google Scholar 

  30. Lee T, Yun T, Park B, et al. Hybrid multilayer thin film supercapacitor of graphene nanosheets with polyaniline: Importance of establishing intimate electronic contact through nanoscale blending. J Mater Chem, 2012, 22: 21092–21099

    CAS  Google Scholar 

  31. Xie Y, Liu Y, Zhao Y, et al. Stretchable all-solid-state supercapacitor with wavy shaped polyaniline/graphene electrode. J Mater Chem A, 2014, 2: 9142–9149

    CAS  Google Scholar 

  32. Zhang J, Zhao XS. Conducting polymers directly coated on reduced graphene oxide sheets as high-performance supercapacitor electrodes. J Phys Chem C, 2012, 116: 5420–5426

    CAS  Google Scholar 

  33. Dong X, Wang J, Wang J, et al. Supercapacitor electrode based on three-dimensional graphene–polyaniline hybrid. Mater Chem Phys, 2012, 134: 576–580

    CAS  Google Scholar 

  34. Hsia B, Marschewski J, Wang S, et al. Highly flexible, all solid-state micro-supercapacitors from vertically aligned carbon nanotubes. Nanotechnology, 2014, 25: 055401

    Google Scholar 

  35. Li X, Rong J, Wei B. Electrochemical behavior of single-walled carbon nanotube supercapacitors under compressive stress. ACS Nano, 2010, 4: 6039–6049

    CAS  Google Scholar 

  36. Luo J, Jang HD, Huang J. Effect of sheet morphology on the scalability of graphene-based ultracapacitors. ACS Nano, 2013, 7: 1464–1471

    CAS  Google Scholar 

  37. Bo Z, Zhu W, Ma W, et al. Vertically oriented graphene bridging active-layer/current-collector interface for ultrahigh rate supercapacitors. Adv Mater, 2013, 25: 5799–5806

    CAS  Google Scholar 

  38. Zhao J, Lai H, Lyu Z, et al. Hydrophilic hierarchical nitrogendoped carbon nanocages for ultrahigh supercapacitive performance. Adv Mater, 2015, 27: 3541–3545

    CAS  Google Scholar 

  39. Zhang K, Zhang LL, Zhao XS, et al. Graphene/polyaniline nanofiber composites as supercapacitor electrodes. Chem Mater, 2010, 22: 1392–1401

    CAS  Google Scholar 

  40. Sun Y, Shi G. Graphene/polymer composites for energy applications. J Polym Sci B Polym Phys, 2013, 51: 231–253

    CAS  Google Scholar 

  41. Tang C, Yin X, Gong H. Superior performance asymmetric supercapacitors based on a directly grown commercial mass 3D Co3O4@Ni(OH)2 core–shell electrode. ACS Appl Mater Interfaces, 2013, 5: 10574–10582

    CAS  Google Scholar 

  42. Yu S, Wang X, Ai Y, et al. Experimental and theoretical studies on competitive adsorption of aromatic compounds on reduced graphene oxides. J Mater Chem A, 2016, 4: 5654–5662

    CAS  Google Scholar 

  43. He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/Mn2 composite networks as ultralight and flexible supercapacitor electrodes. ACS Nano, 2013, 7: 174–182

    CAS  Google Scholar 

  44. Ates M, El-Kady M, Kaner RB. Three-dimensional design and fabrication of reduced graphene oxide/polyaniline composite hydrogel electrodes for high performance electrochemical supercapacitors. Nanotechnology, 2018, 29: 175402

    Google Scholar 

Download references

Acknowledgements

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).

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Correspondence to Tieqi Huang  (黄铁骑) or Chao Gao  (高超).

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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. Muller 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.

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

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Chu, X., Huang, T., Hu, Y. et al. Wet-spinning assembly of nitrogen-doped graphene film for stable graphene-polyaniline supercapacitor electrodes with high mass loading. Sci. China Mater. 63, 1889–1897 (2020). https://doi.org/10.1007/s40843-019-9436-1

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