Journal of Materials Science: Materials in Electronics

, Volume 29, Issue 21, pp 18614–18621 | Cite as

Low content reduced graphene oxide as the reinforcement in cellulosic conductive paper via a hetero-reduction

  • Ruibin Wang
  • Qianli Ma
  • Liqing Wei
  • Rendang YangEmail author


Cellulosic conductive paper/film reinforced by graphene is a promising substrate for energy storage applications due to its comparable conductivity, great flexibility and low cost. However, how to balance the content ratio of graphene/cellulose well is still a challenge. Because conductive paper of low graphene content usually has poor electrical property, while high graphene content is also discouraged owing to the decrease in other properties though electrically improved. Based on this, we developed a different method to produce the graphene/cellulose composite conductive paper. Instead of a separate intermediate-fabrication, starting materials here are continuously one-pot processed, in prior to casting the intermediate paper (solid phase). Next, it is reduced by the l-ascorbic acid solution (liquid phase), followed by a filtration to give the hetero-reduced conductive paper (HRCP). Our results indicate that HRCP possesses high conductivity up to 376 ± 4 S/m, along with good thermal and dynamic behaviors, at a relatively low graphene content of 20 wt%. Therefore, HRCP is expected to be utilized in the field of emerging energy storage.



This work was supported by the Chinese Scholarship Council, National Key Technology R&D Program (2017YFB0307900); Fundamental Research Funds for the Central Universities (2017PY007) and Open Foundation of Zhejiang Provincial Key Lab. for Chem. & Bio. Processing Technology of Farm Products and Zhejiang Provincial Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing (2016KF0201). All authors would like to thank Prof JY Zhu (Forest Products Laboratory, US Forest Service, USDA) for his advice of the experimental details!

Supplementary material

10854_2018_9979_MOESM1_ESM.docx (21 kb)
Supplementary material 1 (DOCX 20 KB)


  1. 1.
    S.K. Mahadeva, K. Walus, B. Stoeber, Paper as a platform for sensing applications and other devices: a review. ACS Appl. Mater. Interfaces 7(16), 8345–8362 (2015)CrossRefGoogle Scholar
  2. 2.
    H. Xu, Y.F. Lu, J.X. Xiang et al., A multifunctional wearable sensor based on a graphene/inverse opal cellulose film for simultaneous, in situ monitoring of human motion and sweat. Nanoscale 10(4), 2090–2098 (2018)CrossRefGoogle Scholar
  3. 3.
    A. Kafy, K.K. Sadasivuni, A. Akther et al., Cellulose/graphene nanocomposite as multifunctional electronic and solvent sensor material. Mater. Lett. 159, 20–23 (2015)CrossRefGoogle Scholar
  4. 4.
    M. Ioniță, L.E. Crică, S.I. Voicu et al., Synergistic effect of carbon nanotubes and graphene for high performance cellulose acetate membranes in biomedical applications. Carbohydr. Polym. 183, 50–61 (2018)CrossRefGoogle Scholar
  5. 5.
    M. Agarwal, Q. Xing, B.S. Shim et al., Conductive paper from lignocellulose wood microfibers coated with a nanocomposite of carbon nanotubes and conductive polymers. Nanotechnology 20(21), 215602 (2009)CrossRefGoogle Scholar
  6. 6.
    K. Gao, Z. Shao, X. Wu et al., Cellulose nanofibers/reduced graphene oxide flexible transparent conductive paper. Carbohydr. Polym. 97(1), 243–251 (2013)CrossRefGoogle Scholar
  7. 7.
    L. Hu, G. Zheng, J. Yao et al., Transparent and conductive paper from nanocellulose fibers. Energy Environ. Sci. 6(2), 513–518 (2013)CrossRefGoogle Scholar
  8. 8.
    F. Wang, L.T. Drzal, Y. Qin et al., Multifunctional graphene nanoplatelets/cellulose nanocrystals composite paper. Compos. Part B 79, 521–529 (2015)CrossRefGoogle Scholar
  9. 9.
    L.N. Dang, J. Seppälä, Electrically conductive nanocellulose/graphene composites exhibiting improved mechanical properties in high-moisture condition. Cellulose 22(3), 1799–1812 (2015)CrossRefGoogle Scholar
  10. 10.
    Z. Weng, Y. Su, D.W. Wang et al., Graphene–cellulose paper flexible supercapacitors. Adv. Energy Mater. 1(5), 917–922 (2011)CrossRefGoogle Scholar
  11. 11.
    L. Valentini, S. Bittolo Bon, E. Fortunati et al., Preparation of transparent and conductive cellulose nanocrystals/graphene nanoplatelets films. J. Mater. Sci. 49(3), 1009–1013 (2014)CrossRefGoogle Scholar
  12. 12.
    X. Du, Z. Zhang, W. Liu et al., Nanocellulose-based conductive materials and their emerging applications in energy devices—a review. Nano Energy, (2017)Google Scholar
  13. 13.
    W. Ouyang, J. Sun, J. Memon et al., Scalable preparation of three-dimensional porous structures of reduced graphene oxide/cellulose composites and their application in supercapacitors. Carbon 62, 501–509 (2013)CrossRefGoogle Scholar
  14. 14.
    Y.-R. Kang, Y.-L. Li, F. Hou et al., Fabrication of electric papers of graphene nanosheet shelled cellulose fibres by dispersion and infiltration as flexible electrodes for energy storage. Nanoscale 4(10), 3248–3253 (2012)CrossRefGoogle Scholar
  15. 15.
    L. Ma, R. Liu, L. Liu et al., Facile synthesis of Ni (OH) 2/graphene/bacterial cellulose paper for large areal mass, mechanically tough and flexible supercapacitor electrodes. J. Power Sources 335, 76–83 (2016)CrossRefGoogle Scholar
  16. 16.
    Y. Li, H. Zhu, F. Shen et al., Highly conductive microfiber of graphene oxide templated carbonization of nanofibrillated cellulose. Adv. Funct. Mater. 24(46), 7366–7372 (2014)CrossRefGoogle Scholar
  17. 17.
    R. Ccorahua, O.P. Troncoso, S. Rodriguez et al., Hydrazine treatment improves conductivity of bacterial cellulose/graphene nanocomposites obtained by a novel processing method. Carbohydr. Polym. 171(Supplement C), 68–76 (2017)Google Scholar
  18. 18.
    R. Xiong, K. Hu, A.M. Grant et al., Ultrarobust transparent cellulose nanocrystal-graphene membranes with high electrical conductivity. Adv. Mater. 28(7), 1501–1509 (2016)CrossRefGoogle Scholar
  19. 19.
    R. Wang, L. Chen, J.Y. Zhu et al., Tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) through maleic acid hydrolysis. ChemNanoMat 3(5), 328–335 (2017)CrossRefGoogle Scholar
  20. 20.
    W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide. JACS 80(6), 1339–1339 (1958)CrossRefGoogle Scholar
  21. 21.
    Y. Tang, Z. He, J.A. Mosseler et al., Production of highly electro-conductive cellulosic paper via surface coating of carbon nanotube/graphene oxide nanocomposites using nanocrystalline cellulose as a binder. Cellulose 21(6), 4569–4581 (2014)CrossRefGoogle Scholar
  22. 22.
    G. Borel, Fabric for the sheet forming section of a papermaking machine. U.S. Patent No. 4,739,803 (1988)Google Scholar
  23. 23.
    Y. Gong, X. Liu, Y. Gong et al., Synthesis of defect-rich palladium-tin alloy nanochain networks for formic acid oxidation. J. Colloid Interface Sci. 530, 189–195 (2018)CrossRefGoogle Scholar
  24. 24.
    M. Acik, G. Lee, C. Mattevi et al., Unusual infrared-absorption mechanism in thermally reduced graphene oxide. Nat. Mater. 9(10), 840–845 (2010)CrossRefGoogle Scholar
  25. 25.
    J. Zhang, H. Yang, G. Shen et al., Reduction of graphene oxide via l-ascorbic acid. Chem. Commun. 46(7), 1112–1114 (2010)CrossRefGoogle Scholar
  26. 26.
    I.K. Moon, J. Lee, R.S. Ruoff et al., Reduced graphene oxide by chemical graphitization. Nat. Commun. 1, 73 (2010)CrossRefGoogle Scholar
  27. 27.
    A.D. French, Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2), 885–896 (2014)CrossRefGoogle Scholar
  28. 28.
    L.Y. Zhang, Z. Liu, B. Xu et al., Thermal treated 3D graphene as a highly efficient metal-free electrocatalyst toward oxygen reduction reaction. Int. J. Hydrogen Energy 42(47), 28278–28286 (2017)CrossRefGoogle Scholar
  29. 29.
    L. Zhang, F. Zhang, X. Yang et al., Porous 3D graphene-based bulk materials with exceptional high surface area and excellent conductivity for supercapacitors. Sci. Rep. 3, 1408 (2013)CrossRefGoogle Scholar
  30. 30.
    Y. Liu, J. Zhou, E. Zhu 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
  31. 31.
    K.K. Sadasivuni, A. Kafy, L. Zhai et al., Transparent and flexible cellulose nanocrystal/reduced graphene oxide film for proximity sensing. Small 11(8), 994–1002 (2015)CrossRefGoogle Scholar
  32. 32.
    Y.-S. Ye, H.-X. Zeng, J. Wu et al., Biocompatible reduced graphene oxide sheets with superior water dispersibility stabilized by cellulose nanocrystals and their polyethylene oxide composites. Green Chem. 18(6), 1674–1683 (2016)CrossRefGoogle Scholar
  33. 33.
    Z. Yu, Q. Zhang, L. Li et al., Highly flexible silver nanowire electrodes for shape-memory polymer light-emitting diodes. Adv. Mater. 23(5), 664–668 (2011)CrossRefGoogle Scholar
  34. 34.
    S. Stankovich, D.A. Dikin, R.D. Piner et al., Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45(7), 1558–1565 (2007)CrossRefGoogle Scholar
  35. 35.
    Y. Qiu, S. Moore, R. Hurt et al., Influence of external heating rate on the structure and porosity of thermally exfoliated graphite oxide. Carbon 111, 651–657 (2017)CrossRefGoogle Scholar
  36. 36.
    Y. Qiu, F. Guo, R. Hurt et al., Explosive thermal reduction of graphene oxide-based materials: mechanism and safety implications. Carbon 72, 215–223 (2014)CrossRefGoogle Scholar
  37. 37.
    P. Cataldi, F. Bonaccorso, A. Esau del Rio Castillo. et al., Cellulosic graphene biocomposites for versatile high-performance flexible electronic applications. Adv. Electron. Mater. 2(11), 1600245 (2016)CrossRefGoogle Scholar
  38. 38.
    Z. Xu, C. Wei, Y. Gong et al., Efficient dispersion of carbon nanotube by synergistic effects of sisal cellulose nano-fiber and graphene oxide. Compos. Interfaces 24(3), 1–15 (2016)Google Scholar
  39. 39.
    F. Xiao, J. Song, H. Gao et al., Coating graphene paper with 2D-assembly of electrocatalytic nanoparticles: a modular approach toward high-performance flexible electrodes. ACS Nano 6(1), 100–110 (2011)CrossRefGoogle Scholar
  40. 40.
    S.J. I’Anson, W.W. Sampson, Competing Weibull and stress-transfer influences on the specific tensile strength of a bonded fibrous network. Compos. Sci. Technol. 67(7), 1650–1658 (2007)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Ruibin Wang
    • 1
    • 2
  • Qianli Ma
    • 1
    • 3
  • Liqing Wei
    • 3
  • Rendang Yang
    • 1
    Email author
  1. 1.State Key Laboratory of Pulp and Paper EngineeringSouth China University of TechnologyGuangzhouChina
  2. 2.School of Materials and Energy, Center of Emerging Material and TechnologyGuangdong University of TechnologyGuangzhouChina
  3. 3.Forest Products Laboratory, U.S. Forest ServiceU.S. Department of AgricultureMadisonUSA

Personalised recommendations