Role of electrolyte at the interface and in the dispersion of graphene in organic solvents

  • Muhammad Mohsin Hossain
  • Sae Youn Lee
  • Hemraj Mahipati Yadav
  • Jae-Joon LeeEmail author


The electrochemical exfoliation of graphene is a very useful technique to prepare highly conductive graphene with a low defect level. However, low dispersion stability is a barrier to this process being used to prepare graphene directly in a wide range of applications. Even though the dispersion stability and concentration of graphene are important, the reasons for the lower dispersion stability and lower concentration of electrochemically exfoliated graphene have not yet been clarified. In this study, we identified that the strong electrostatic attractive interaction between charged ions from electrolytes at the interfaces of graphene layers substantially deteriorated the dispersion stability. Both the stability and the concentration of graphene dispersions were substantially enhanced upon removal of the residual electrolytes from the organic solvents used in this study.



This research was supported by the Technology Development Program to Solve Climate Changes of the National Research Foundation, funded by the Ministry of Science, ICT & Future Planning (Grant NRF-2016M1A2A2940912 and NRF-2015M1A2A2054996). This work was also supported by the Dongguk University Research Fund of 2017 and 2019 (S-2019-G0001-00030).

Compliance with ethical standards

Conflict of interest

All authors declare that they have no conflict of interest.

Supplementary material

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Supplementary material 1 (DOCX 4228 kb)


  1. 1.
    B.-H. Wee, W.-H. Khoh, A.K. Sarker, C.-H. Lee, J.-D. Hong, A high-performance moisture sensor based on ultralarge graphene oxide. Nanoscale 7, 17805–17811 (2015). CrossRefGoogle Scholar
  2. 2.
    V. León, A.M. Rodriguez, P. Prieto, M. Prato, E. Vázquez, Exfoliation of graphite with triazine derivatives under ball-milling conditions: preparation of few-layer graphene via selective noncovalent interactions. ACS Nano 8, 563–571 (2014). CrossRefGoogle Scholar
  3. 3.
    R.S. Edwards, K.S. Coleman, Graphene synthesis: relationship to applications. Nanoscale 5, 38–51 (2013). CrossRefGoogle Scholar
  4. 4.
    Z.-S. Wu, S. Pei, W. Ren, D. Tang, L. Gao, B. Liu, F. Li, C. Liu, H.-M. Cheng, Field emission of single-layer graphene films prepared by electrophoretic deposition. Adv. Mater. 21, 1756–1760 (2009). CrossRefGoogle Scholar
  5. 5.
    J.I. Paredes, J.M. Munuera, Recent advances and energy-related applications of high quality/chemically doped graphenes obtained by electrochemical exfoliation methods. J. Mater. Chem. A 5, 7228–7242 (2017). CrossRefGoogle Scholar
  6. 6.
    L.G. Cançado, K. Takai, T. Enoki, M. Endo, Y.A. Kim, H. Mizusaki, N.L. Speziali, A. Jorio, M.A. Pimenta, Measuring the degree of stacking order in graphite by Raman spectroscopy. Carbon N. Y. 46, 272–275 (2008). CrossRefGoogle Scholar
  7. 7.
    S. Park, J. An, I. Jung, R.D. Piner, S.J. An, X. Li, A. Velamakanni, R.S. Ruoff, Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents. Nano Lett. 9, 1593–1597 (2009). CrossRefGoogle Scholar
  8. 8.
    H.K. Jeong, Y.P. Lee, R.J.W.E. Lahaye, M.H. Park, K.H. An, I.J. Kim, C.W. Yang, C.Y. Park, R.S. Ruoff, Y.H. Lee, Evidence of graphitic AB stacking order of graphite oxides. J. Am. Chem. Soc. (2008). CrossRefGoogle Scholar
  9. 9.
    G. Eda, M. Chhowalla, Chemically derived graphene oxide: towards large-area thin-film electronics and optoelectronics. Adv. Mater. 22, 2392–2415 (2010). CrossRefGoogle Scholar
  10. 10.
    H.-X. Wang, Q. Wang, K.-G. Zhou, H.-L. Zhang, Graphene in light: design, synthesis and applications of photo-active graphene and graphene-like materials. Small 9, 1266–1283 (2013). CrossRefGoogle Scholar
  11. 11.
    V.C. Tung, M.J. Allen, Y. Yang, R.B. Kaner, High-throughput solution processing of large-scale graphene. Nat. Nanotechnol. 4, 25–29 (2009). CrossRefGoogle Scholar
  12. 12.
    A. Bagri, C. Mattevi, M. Acik, Y.J. Chabal, M. Chhowalla, V.B. Shenoy, Structural evolution during the reduction of chemically derived graphene oxide. Nat. Chem. 2, 581–587 (2010). CrossRefGoogle Scholar
  13. 13.
    A. Ciesielski, P. Samorì, Grapheneviasonication assisted liquid-phase exfoliation. Chem. Soc. Rev. 43, 381–398 (2014). CrossRefGoogle Scholar
  14. 14.
    M. Yi, Z. Shen, A review on mechanical exfoliation for the scalable production of graphene. J. Mater. Chem. A 3, 11700–11715 (2015). CrossRefGoogle Scholar
  15. 15.
    H. Shima, M.M. Hossain, J.R. Hahn, Highly dispersed graphene ribbons produced from ZnO–C core–shell nanorods and their use as a filler in polyimide composites. RSC Adv. 4, 41204–41211 (2014). CrossRefGoogle Scholar
  16. 16.
    S. Liang, Z. Shen, M. Yi, L. Liu, X. Zhang, S. Ma, In-situ exfoliated graphene for high-performance water-based lubricants. Carbon N. Y. 96, 1181–1190 (2016). CrossRefGoogle Scholar
  17. 17.
    S. Wang, M. Yi, Z. Shen, The effect of surfactants and their concentration on the liquid exfoliation of graphene. RSC Adv. 6, 56705–56710 (2016). CrossRefGoogle Scholar
  18. 18.
    M. Yi, Z. Shen, Kitchen blender for producing high-quality few-layer graphene. Carbon N. Y. 78, 622–626 (2014). CrossRefGoogle Scholar
  19. 19.
    M. Yi, Z. Shen, S. Liang, L. Liu, X. Zhang, S. Ma, Water can stably disperse liquid-exfoliated graphene. Chem. Commun. 49, 11059 (2013). CrossRefGoogle Scholar
  20. 20.
    L. Liu, Z. Shen, M. Yi, X. Zhang, S. Ma, A green, rapid and size-controlled production of high-quality graphene sheets by hydrodynamic forces. RSC Adv. 4, 36464–36470 (2014). CrossRefGoogle Scholar
  21. 21.
    M. Yi, Z. Shen, J. Zhu, A fluid dynamics route for producing graphene and its analogues. Chin. Sci. Bull. 59, 1794–1799 (2014). CrossRefGoogle Scholar
  22. 22.
    M. Yi, Z. Shen, X. Zhang, S. Ma, Achieving concentrated graphene dispersions in water/acetone mixtures by the strategy of tailoring Hansen solubility parameters. J. Phys. D 46, 025301 (2013). CrossRefGoogle Scholar
  23. 23.
    M.M. Hossain, H. Shima, I. Lee, J.R. Hahn, In situ preparation of graphene-ZnO composites for enhanced graphite exfoliation and graphene-nylon-6 composite films. J. Appl. Polym. Sci. 134, 45034 (2017). CrossRefGoogle Scholar
  24. 24.
    M.M. Hossain, J.R. Hahn, B.C. Ku, Synthesis of highly dispersed and conductive graphene sheets by exfoliation of preheated graphite in a sealed bath and its applications to polyimide nanocomposites. Bull. Korean Chem. Soc. (2014). CrossRefGoogle Scholar
  25. 25.
    M.M. Hossain, O.-K. Park, J.R. Hahn, B.-C. Ku, High yield and high concentration few-layer graphene sheets using solvent exfoliation of graphite with pre-thermal treatment in a sealed bath. Mater. Lett. 123, 90–92 (2014). CrossRefGoogle Scholar
  26. 26.
    J.N. Coleman, Liquid exfoliation of defect-free graphene. Acc. Chem. Res. 46, 14–22 (2013). CrossRefGoogle Scholar
  27. 27.
    Y. Hernandez, V. Nicolosi, M. Lotya, F.M. Blighe, Z. Sun, S. De, I.T. McGovern, B. Holland, M. Byrne, Y.K. Gun’Ko, J.J. Boland, P. Niraj, G. Duesberg, S. Krishnamurthy, R. Goodhue, J. Hutchison, V. Scardaci, A.C. Ferrari, J.N. Coleman, High-yield production of graphene by liquid-phase exfoliation of graphite. Nat. Nanotechnol. 3, 563–568 (2008). CrossRefGoogle Scholar
  28. 28.
    C.-J. Shih, S. Lin, M.S. Strano, D. Blankschtein, Understanding the stabilization of liquid-phase-exfoliated graphene in polar solvents: molecular dynamics simulations and kinetic theory of colloid aggregation. J. Am. Chem. Soc. 132, 14638–14648 (2010). CrossRefGoogle Scholar
  29. 29.
    A.A. Green, M.C. Hersam, Solution phase production of graphene with controlled thickness via density differentiation. Nano Lett. 9, 4031–4036 (2009). CrossRefGoogle Scholar
  30. 30.
    M. Lotya, P.J. King, U. Khan, S. De, J.N. Coleman, High-concentration, surfactant-stabilized graphene dispersions. ACS Nano 4, 3155–3162 (2010). CrossRefGoogle Scholar
  31. 31.
    D. Ager, V. Arjunan Vasantha, R. Crombez, J. Texter, Aqueous graphene dispersions–optical properties and stimuli-responsive phase transfer. ACS Nano 8, 11191–11205 (2014). CrossRefGoogle Scholar
  32. 32.
    A.S. Wajid, S. Das, F. Irin, H.S.T. Ahmed, J.L. Shelburne, D. Parviz, R.J. Fullerton, A.F. Jankowski, R.C. Hedden, M.J. Green, Polymer-stabilized graphene dispersions at high concentrations in organic solvents for composite production. Carbon N. Y. 50, 526–534 (2012). CrossRefGoogle Scholar
  33. 33.
    P. May, U. Khan, J.M. Hughes, J.N. Coleman, Role of solubility parameters in understanding the steric stabilization of exfoliated two-dimensional nanosheets by adsorbed polymers. J. Phys. Chem. C 116, 11393–11400 (2012). CrossRefGoogle Scholar
  34. 34.
    V. Chabot, B. Kim, B. Sloper, C. Tzoganakis, A. Yu, High yield production and purification of few layer graphene by Gum Arabic assisted physical sonication. Sci. Rep. 3, 1378 (2013). CrossRefGoogle Scholar
  35. 35.
    S. Das, F. Irin, H.S. Tanvir Ahmed, A.B. Cortinas, A.S. Wajid, D. Parviz, A.F. Jankowski, M. Kato, M.J. Green, Non-covalent functionalization of pristine few-layer graphene using triphenylene derivatives for conductive poly (vinyl alcohol) composites. Polym. (Guildf) 53, 2485–2494 (2012). CrossRefGoogle Scholar
  36. 36.
    L. Guardia, M.J. Fernández-Merino, J.I. Paredes, P. Solís-Fernández, S. Villar-Rodil, A. Martínez-Alonso, J.M.D. Tascón, High-throughput production of pristine graphene in an aqueous dispersion assisted by non-ionic surfactants. Carbon N. Y. 49, 1653–1662 (2011). CrossRefGoogle Scholar
  37. 37.
    S. Pei, J. Zhao, J. Du, W. Ren, H.-M. Cheng, Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids. Carbon N. Y. 48, 4466–4474 (2010). CrossRefGoogle Scholar
  38. 38.
    P. He, J. Sun, S. Tian, S. Yang, S. Ding, G. Ding, X. Xie, M. Jiang, Processable aqueous dispersions of graphene stabilized by graphene quantum dots. Chem. Mater. 27, 218–226 (2015). CrossRefGoogle Scholar
  39. 39.
    T.C. Achee, W. Sun, J.T. Hope, S.G. Quitzau, C.B. Sweeney, S.A. Shah, T. Habib, M.J. Green, High-yield scalable graphene nanosheet production from compressed graphite using electrochemical exfoliation. Sci. Rep. (2018). CrossRefGoogle Scholar
  40. 40.
    A. Ejigu, L.W. Le Fevre, K. Fujisawa, M. Terrones, A.J. Forsyth, R.A.W. Dryfe, Electrochemically exfoliated graphene electrode for high-performance rechargeable chloroaluminate and dual-ion batteries. ACS Appl. Mater. Interfaces (2019). CrossRefGoogle Scholar
  41. 41.
    K. Parvez, Z.-S. Wu, R. Li, X. Liu, R. Graf, X. Feng, K. Müllen, Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J. Am. Chem. Soc. 136, 6083–6091 (2014). CrossRefGoogle Scholar
  42. 42.
    C.Y. Lee, D.R.G. Mitchell, P. Molino, A. Fahy, G.G. Wallace, Tunable solution-processable anodic exfoliated graphene. Appl. Mater. Today 15, 290–296 (2019). CrossRefGoogle Scholar
  43. 43.
    Y.Z.N. Htwe, W.S. Chow, Y. Suda, A.A. Thant, M. Mariatti, Effect of electrolytes and sonication times on the formation of graphene using an electrochemical exfoliation process. Appl. Surf. Sci. 469, 951–961 (2019). CrossRefGoogle Scholar
  44. 44.
    A. Ejigu, I.A. Kinloch, R.A.W. Dryfe, Single stage simultaneous electrochemical exfoliation and functionalization of graphene. ACS Appl. Mater. Interfaces 9, 710–721 (2017). CrossRefGoogle Scholar
  45. 45.
    K. Parvez, R.A. Rincón, N.-E. Weber, K.C. Cha, S.S. Venkataraman, One-step electrochemical synthesis of nitrogen and sulfur co-doped, high-quality graphene oxide. Chem. Commun. 52, 5714–5717 (2016). CrossRefGoogle Scholar
  46. 46.
    Z. Liu, Z.-S. Wu, S. Yang, R. Dong, X. Feng, K. Müllen, Ultraflexible in-plane micro-supercapacitors by direct printing of solution-processable electrochemically exfoliated graphene. Adv. Mater. 28, 2217–2222 (2016). CrossRefGoogle Scholar
  47. 47.
    A. Ambrosi, M. Pumera, Electrochemically exfoliated graphene and graphene oxide for energy storage and electrochemistry applications. Chem. A 22, 153–159 (2016). CrossRefGoogle Scholar
  48. 48.
    H.M. Yadav, J.-S. Kim, Solvothermal synthesis of anatase TiO2-graphene oxide nanocomposites and their photocatalytic performance, J. Alloys Compd. 688, 123–129 (2016). Accessed 8 Sept 2016CrossRefGoogle Scholar
  49. 49.
    R. Muzyka, S. Drewniak, T. Pustelny, M. Chrubasik, G. Gryglewicz, Characterization of graphite oxide and reduced graphene oxide obtained from different graphite precursors and oxidized by different methods using raman spectroscopy. Materials (Basel, Switzerland) (2018). CrossRefGoogle Scholar
  50. 50.
    A. Ilnicka, M. Skorupska, P. Kamedulski, J.P. Lukaszewicz, Electro-exfoliation of graphite to graphene in an aqueous solution of inorganic salt and the stabilization of its sponge structure with poly(furfuryl alcohol). Nanomaterials (Basel, Switzerland) (2019). CrossRefGoogle Scholar
  51. 51.
    K. Chen, D. Xue, Preparation of colloidal graphene in quantity by electrochemical exfoliation. J. Colloid Interface Sci. 436, 41–46 (2014). CrossRefGoogle Scholar
  52. 52.
    C.E. Hamilton, J.R. Lomeda, Z. Sun, J.M. Tour, A.R. Barron, High-yield organic dispersions of unfunctionalized graphene. Nano Lett. 9, 3460–3462 (2009). CrossRefGoogle Scholar
  53. 53.
    L. Xu, J.-W. McGraw, F. Gao, M. Grundy, Z. Ye, Z. Gu, J.L. Shepherd, Production of high-concentration graphene dispersions in low-boiling-point organic solvents by liquid-phase noncovalent exfoliation of graphite with a hyperbranched polyethylene and formation of graphene/ethylene copolymer composites. J. Phys. Chem. C 117, 10730–10742 (2013). CrossRefGoogle Scholar
  54. 54.
    M. Lotya, Y. Hernandez, P.J. King, R.J. Smith, V. Nicolosi, L.S. Karlsson, F.M. Blighe, S. De, Z. Wang, I.T. McGovern, G.S. Duesberg, J.N. Coleman, Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. J. Am. Chem. Soc. 131, 3611–3620 (2009). CrossRefGoogle Scholar
  55. 55.
    S. Barwich, U. Khan, J.N. Coleman, A technique to pretreat graphite which allows the rapid dispersion of defect-free graphene in solvents at high concentration. J. Phys. Chem. C 117, 19212–19218 (2013). CrossRefGoogle Scholar
  56. 56.
    D. Li, M.B. Müller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous dispersions of graphene nanosheets. Nat. Nanotechnol. 3, 101–105 (2008). CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.Department of Energy and Materials Engineering, Research Center for Photoenergy Harvesting & Conversion Technology (phct)Dongguk UniversitySeoulRepublic of Korea

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