Construction and Application of nanocellulose/graphene/MnO2 three-dimensional composites as potential electrode materials for supercapacitors

  • Yan-Yun Wang
  • Qing-Jin Fu
  • Yuan-Yuan Bai
  • Xiao Ning
  • Chun-Li YaoEmail author


The research on graphene–nanocellulose-based electrodes in supercapacitors has attracted more and more attention. We have innovatively prepared a carbon–biomass–metal oxide ternary aerogel electrode using a green hydrothermal method, successfully combining a graphene–nanocellulose–manganese dioxide electrode (MCGA) by loading MnO2 metal particles into a three-dimensional porous aerogel composed of graphene and nanocellulose. It is found that when the mass ratio of graphene, nanocellulose and MnO2 is 1:1:4, the obtained aerogel electrode MCGA1:1:4 shows the best electrochemical performance. The MCGA1:1:4 electrode exhibits a high specific capacitance of 212.73 F g−1 at 5 mV s−1 and extreme stability of 86.5% capacitance retention ratio after 5000 cycles at 2 A g−1. This ternary hybrid electrode based on biomass, carbon and metal oxides may become a trend in the development of high-performance supercapacitors.



We completed this work with financial support of the National Key R&D Program of China (2017YFD0600804).


  1. 1.
    Z. Lei et al., Functionalization of chemically derived graphene for improving its electrocapacitive energy storage properties. Energy Environ. Sci. 9(6), 1891–1930 (2016)CrossRefGoogle Scholar
  2. 2.
    J. Yan et al., Recent advances in design and fabrication of electrochemical supercapacitors with high energy densities. Adv. Energy Mater. 4(4), 1300816 (2014)CrossRefGoogle Scholar
  3. 3.
    K.H. An et al., Supercapacitors using single-walled carbon nanotube electrodes. Adv. Mater. 13(7), 497–500 (2010)CrossRefGoogle Scholar
  4. 4.
    J. Lake, Z. Tanaka, B. Chen, Graphene composite materials for supercapacitor electrodes. MRS Online Proc. Libr. Arch. 1407, 1–7 (2012)Google Scholar
  5. 5.
    Y. Shao et al., Graphene-based materials for flexible supercapacitors. Chem. Soc. Rev. 44(11), 3639–3665 (2015)CrossRefGoogle Scholar
  6. 6.
    Y. An et al., High-performance symmetric supercapacitors based on carbon nanosheets framework with graphene hydrogel architecture derived from cellulose acetate. J. Power Sources 337, 45–53 (2017)CrossRefGoogle Scholar
  7. 7.
    J. Zhu et al., Graphene and graphene-based materials for energy storage applications. Small 10(17), 3480–3498 (2014)CrossRefGoogle Scholar
  8. 8.
    S. Nie et al., Enzymatic pretreatment for the improvement of dispersion and film properties of cellulose nanofibrils. Carbohydr. Polym. 181, 1136 (2018)CrossRefGoogle Scholar
  9. 9.
    K. Zhang et al., Enzyme-assisted mechanical production of cellulose nanofibrils: thermal stability. Cellulose 25(9), 5049–5061 (2018)CrossRefGoogle Scholar
  10. 10.
    Q. Zheng et al., Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors. ACS Appl. Mater. Interfaces 7(5), 3263–3271 (2015)CrossRefGoogle Scholar
  11. 11.
    N.R.N. Him, C. Apau, N.S. Azmi, Effect of temperature and pH on deinking of laser-jet waste paper using commercial lipase and esterase. J. Life Sci. Technol. 4(2), 79–84 (2016)Google Scholar
  12. 12.
    Z. Gui et al., Natural cellulose fiber as substrate for supercapacitor. ACS Nano 7(7), 6037–6046 (2013)CrossRefGoogle Scholar
  13. 13.
    K. Gao et al., Cellulose nanofibers/reduced graphene oxide flexible transparent conductive paper. Carbohydr. Polym. 97(1), 243–251 (2013)CrossRefGoogle Scholar
  14. 14.
    H. Yan et al., Core-shell structured NaTi2(PO4)3@polyaniline as an efficient electrode material for electrochemical energy storage. Solid State Ion. 336, 95–101 (2019)CrossRefGoogle Scholar
  15. 15.
    Z. Jia et al., Laminated microwave absorbers of A-site cation deficiency perovskite La0.8FeO3 doped at hybrid RGO carbon. Compos. B 176, 107246 (2019)CrossRefGoogle Scholar
  16. 16.
    D. Zhang et al., A three-dimensional macroporous network structured chitosan/cellulose biocomposite sponge for rapid and selective removal of mercury (II) ions from aqueous solution. Chem. Eng. J. 363, 192–202 (2019)CrossRefGoogle Scholar
  17. 17.
    R. Liu et al., Large areal mass, flexible and freestanding polyaniline/bacterial cellulose/graphene film for high-performance supercapacitors. RSC Adv. 6(109), 107426–107432 (2016)CrossRefGoogle Scholar
  18. 18.
    C. Wan, Y. Jiao, J. Li, Flexible, highly conductive, and free-standing reduced graphene oxide/polypyrrole/cellulose hybrid papers for supercapacitor electrodes. J. Mater. Chem. A 5(8), 3819–3831 (2017)CrossRefGoogle Scholar
  19. 19.
    Y. Liu et al., Facile synthesis of bacterial cellulose fibres covalently intercalated with graphene oxide by one-step cross-linking for robust supercapacitors. J. Mater. Chem. C 3(5), 1011–1017 (2015)CrossRefGoogle Scholar
  20. 20.
    Q. Zheng et al., A freestanding cellulose nanofibril–reduced graphene oxide–molybdenum oxynitride aerogel film electrode for all-solid-state supercapacitors with ultrahigh energy density. J. Mater. Chem. A 5(24), 12528–12541 (2017)CrossRefGoogle Scholar
  21. 21.
    W. Guo et al., Strategies and insights towards the intrinsic capacitive properties of MnO2 for supercapacitors: challenges and perspectives. Nano Energy 57, 459–472 (2019)CrossRefGoogle Scholar
  22. 22.
    X. Yang et al., Cellulose nanocrystal aerogels as universal 3D lightweight substrates for supercapacitor materials. Adv. Mater. 27(40), 6104–6109 (2015)CrossRefGoogle Scholar
  23. 23.
    Z.-H. Huang et al., High mass loading MnO2 with hierarchical nanostructures for supercapacitors. ACS Nano 12(4), 3557–3567 (2018)CrossRefGoogle Scholar
  24. 24.
    W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide. J. Am. Chem. Soc. 80(6), 1339–1339 (1958)CrossRefGoogle Scholar
  25. 25.
    A. Isogai, T. Saito, H. Fukuzumi, TEMPO-oxidized cellulose nanofibers. Nanoscale 3(1), 71–85 (2011)CrossRefGoogle Scholar
  26. 26.
    W. Chen, H. Yu, Y. Liu, Preparation of millimeter-long cellulose I nanofibers with diameters of 30–80 nm from bamboo fibers. Carbohydr. Polym. 86(2), 453–461 (2011)CrossRefGoogle Scholar
  27. 27.
    Y. Liu et al., Hydrothermal self-assembly of manganese dioxide/manganese carbonate/reduced graphene oxide aerogel for asymmetric supercapacitors. Electrochim. Acta 164, 154–162 (2015)CrossRefGoogle Scholar
  28. 28.
    J. Wen et al., Flexible coaxial-type fiber solid-state asymmetrical supercapacitor based on Ni3S2 nanorod array and pen ink electrodes. J. Power Sources 324, 325–333 (2016)CrossRefGoogle Scholar
  29. 29.
    M. Masjedi-Arani, M. Salavati-Niasari, Cd2SiO4/graphene nanocomposite: ultrasonic assisted synthesis, characterization and electrochemical hydrogen storage application. Ultrason. Sonochem. 43, 136–145 (2018)CrossRefGoogle Scholar
  30. 30.
    Y. Zhou et al., Hydrothermal dehydration for the “green” reduction of exfoliated graphene oxide to graphene and demonstration of tunable optical limiting properties. Chem. Mater. 21(13), 2950–2956 (2009)CrossRefGoogle Scholar
  31. 31.
    J. Xing et al., Nanocellulose-graphene composites: a promising nanomaterial for flexible supercapacitors. Carbohydr. Polym. 207, 447–459 (2019)CrossRefGoogle Scholar
  32. 32.
    G. Xu et al., Binder-free activated carbon/carbon nanotube paper electrodes for use in supercapacitors. Nano Res. 4(9), 870–881 (2011)CrossRefGoogle Scholar
  33. 33.
    L. Xu et al., Natural organic phytate modified graphene hydrogel for flexible supercapacitor electrodes. J. Electrochem. Soc. 164(14), A3614–A3619 (2017)CrossRefGoogle Scholar
  34. 34.
    W. Du et al., A surfactant-free water-processable all-carbon composite and its application to supercapacitor. Electrochim. Acta 146, 353–358 (2014)CrossRefGoogle Scholar
  35. 35.
    L. Wang et al., Facile synthesis of 3-D composites of MnO2 nanorods and holey graphene oxide for supercapacitors. J. Mater. Sci. 50(19), 6313–6320 (2015)CrossRefGoogle Scholar
  36. 36.
    Z. Weng et al., Graphene–cellulose paper flexible supercapacitors. Adv. Energy Mater. 1(5), 917–922 (2011)CrossRefGoogle Scholar
  37. 37.
    J. Xu et al., A highly atom-efficient strategy to synthesize reduced graphene oxide-Mn3O4 nanoparticles composites for supercapacitors. J. Alloys Compd. 685, 949–956 (2016)CrossRefGoogle Scholar
  38. 38.
    Y. Chai et al., Construction of hierarchical holey graphene/MnO2 composites as potential electrode materials for supercapacitors. J. Alloys Compd. 775, 1206–1212 (2019)CrossRefGoogle Scholar
  39. 39.
    P. Wu et al., Synthesis and characterization of self-standing and high flexible δ-MnO2@CNTs/CNTs composite films for direct use of supercapacitor electrodes. ACS Appl. Mater. Interfaces 8(36), 23721 (1944)CrossRefGoogle Scholar
  40. 40.
    S. Chen et al., Graphene oxide−MnO2 nanocomposites for supercapacitors. ACS Nano 4(5), 2822–2830 (2010)CrossRefGoogle Scholar
  41. 41.
    Z. Li et al., Synthesis of hydrothermally reduced graphene/MnO2 composites and their electrochemical properties as supercapacitors. J. Power Sources 196(19), 8160–8165 (2011)CrossRefGoogle Scholar
  42. 42.
    Z. Lei, J. Zhang, X. Zhao, Ultrathin MnO2 nanofibers grown on graphitic carbon spheres as high-performance asymmetric supercapacitor electrodes. J. Mater. Chem. 22(1), 153–160 (2012)CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.Beijing Key Laboratory of Lignocellulosic ChemistryBeijing Forestry UniversityBeijingChina
  2. 2.National Engineering Lab for Pulp and PaperChina National Pulp and Paper Research Institute Co. Ltd.BeijingChina

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