Abstract
Herein, an efficient, facile, scalable production of graphene dispersions via exfoliation of graphite in an environment-friendly PVA/H2O solvent system is reported. To warrant the impact of processing parameters on exfoliation efficiency, a systematic investigation is carried out using UV–visible spectroscopy. Under the optimal shearing parameters (1 h, 10 k rpm) with the PVA-to-fed graphite mass ratio of 10, a high concentration graphene dispersion (3.36 mg mL−1) is achieved. The estimated graphene yield is found to be 33% that further increases to 90% after sediment recycling. With the aim of detailed quality analysis, centrifugal cascading is adopted to predominately sort the graphene flakes from the upper end of the distribution. Through various characterization techniques, it is confirmed that the resulting dispersion comprises high-quality graphene flakes (1–5 layers) having thickness up to 1.48 nm, lateral dimension ranging from 0.3 to 4 µm, and quite a low level of defects (ID/IG = 0.1). The statistical distribution histogram reveals that most flakes are single-layer (41%), including some bi-layer (21%) and tri-layer (28%), while the remaining can be said five or multi-layer graphene. Meanwhile, the efficacy of the PVA/H2O solvent system is also demonstrated using ultrasonic exfoliation, providing a high concentration of graphene (1.1 mg mL−1) in a relatively short time (8 h). Furthermore, the applicability of the PVA-stabilized graphene dispersion is addressed by fabricating various graphene products such as graphene paper electrodes, graphene composites, and graphene thin films. Impressively, the graphene paper electrode imparts an exceptionally high specific capacitance of 199.63 F g−1 in a potential window range of 0 to 2 V, and hence could be a promising alternative to traditional electrodes in supercapacitors. Conclusively, the exfoliation of graphite in a green polymer–solvent system offers to produce highly concentrated graphene dispersions at a minimal cost that could be widely applicable in different research areas, thus holding the potential for commercial viability.
Similar content being viewed by others
Data availability
The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.
References
Ago H, Ito Y, Mizuta N, Yoshida K, Hu B, Orofeo CM et al (2010) Epitaxial chemical vapor deposition growth of single-layer graphene over cobalt film crystallized on sapphire. ACS Nano 4(12):7407–7414
Amiri A, Naraghi M, Ahmadi G, Soleymaniha M, Shanbedi M (2018) A review on liquid-phase exfoliation for scalable production of pure graphene, wrinkled, crumpled and functionalized graphene and challenges. FlatChem 8:40–71
Arao Y, Mori F, Kubouchi M (2017) Efficient solvent systems for improving production of few-layer graphene in liquid phase exfoliation. Carbon 118:18–24
Cai X, Jiang Z, Zhang X, Zhang X (2018) Effects of tip sonication parameters on liquid phase exfoliation of graphite into graphene nanoplatelets. Nanoscale Res Lett 13(1):1–10
Calderon-Ayala G, Cortez-Valadez M, Acosta-Elías M, Mani-Gonzalez PG, Zayas ME, Castillo SJ, Flores-Acosta M (2019) Graphite to graphene: green synthesis using opuntia ficus-indica. J Electron Mater 48(3):1553–1561
Çelik Y, Flahaut E, Suvacı E (2017) A comparative study on few-layer graphene production by exfoliation of different starting materials in a low boiling point solvent. FlatChem 1:74–88
Chabot V, Kim B, Sloper B, Tzoganakis C, Yu A (2013) High yield production and purification of few layer graphene by Gum Arabic assisted physical sonication. Sci Rep 3(1):1–7
Chen J, Shi W, Fang D, Wang T, Huang J, Li Q et al (2015) A binary solvent system for improved liquid phase exfoliation of pristine graphene materials. Carbon 94:405–411
Dreyer DR, Ruoff RS, Bielawski CW (2010a) From conception to realization: an historial account of graphene and some perspectives for its future. Angew Chem Int Ed 49(49):9336–9344
Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010b) The chemistry of graphene oxide. Chem Soc Rev 39:228–240
Du W, Lu J, Sun P, Zhu Y, Jiang X (2013) Organic salt-assisted liquid-phase exfoliation of graphite to produce high-quality graphene. Chem Phys Lett 568:198–201
Ferrari AC, Meyer JC, Scardaci V, Casiraghi C, Lazzeri M, Mauri F et al (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97(18):187401
Gao Y, Shi W, Wang W, Wang Y, Zhao Y, Lei Z, Miao R (2014) Ultrasonic-assisted production of graphene with high yield in supercritical CO2 and its high electrical conductivity film. Ind Eng Chem Res 53(7):2839–2845
Geim AK, Novoselov KS (2010) The rise of graphene. In: Nanoscience and technology: a collection of reviews from nature journals (pp 11–19)
Godoy AP, Ecorchard P, Beneš H, Tolasz J, Smržová D, Seixas L et al (2019) Ultrasound exfoliation of graphite in biphasic liquid systems containing ionic liquids: a study on the conditions for obtaining large few-layers graphene. Ultrason Sonochem 55:279–288
Guardia L, Fernández-Merino MJ, Paredes JI, Solís-Fernández P, Villar-Rodil S, Martínez-Alonso A, Tascón JMD (2011) High-throughput production of pristine graphene in an aqueous dispersion assisted by non-ionic surfactants. Carbon 49(5):1653–1662
Guerra V, Wan C, Degirmenci V, Sloan J, Presvytis D, Watson M, McNally T (2019) Characterisation of graphite nanoplatelets (GNP) prepared at scale by high-pressure homogenisation. J Mat Chem C 7(21):6383–6390
Hao Y, Wang Y, Wang L, Ni Z, Wang Z, Wang R et al (2010) Probing layer number and stacking order of few‐layer graphene by Raman spectroscopy. Small 6(2):195–200
Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun Z, De S et al (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotechnol 3(9):563–568
Ismail Z, Kassim NFA, Abdullah AH, Abidin ASZ, Ismail FS, Yusoh K (2017) Black tea assisted exfoliation using a kitchen mixer allowing one-step production of graphene. Mat Res Exp 4(7):075607
Khan U, O’Neill A, Lotya M, De S, Coleman JN (2010) High-Concentration Solvent Exfoliation of Graphene. Small 6(7):864–871
Khan U, O’Neill A, Porwal H, May P, Nawaz K, Coleman JN (2012) Size selection of dispersed, exfoliated graphene flakes by controlled centrifugation. Carbon 50(2):470–475
Khanam Z, Liu J, Song S (2020) Flexible graphene paper electrode prepared via polyvinyl alcohol-assisted shear-exfoliation for all-solid-state polymer supercapacitor application. Electrochimica Acta 363:137208
Le Fevre LW, Cao J, Kinloch IA, Forsyth AJ, Dryfe RA (2019) Systematic comparison of graphene materials for supercapacitor electrodes. ChemistryOpen 8(4):418
Lee HC, Liu WW, Chai SP, Mohamed AR, Aziz A, Khe CS et al (2017) Review of the synthesis, transfer, characterization and growth mechanisms of single and multilayer graphene. RSC Adv 7(26):15644–15693
Li B, Nan Y, Zhang P, Song X (2016a) Structural characterization of individual graphene sheets formed by arc discharge and their growth mechanisms. RSC Adv 6(24):19797–19806
Li W, Liu J, Zhao D (2016b) Mesoporous materials for energy conversion and storage devices. Nat Rev Mater 1(6):1–17
Liu L, Shen Z, Yi M, Zhang X, Ma S (2014) A green, rapid and size-controlled production of high-quality graphene sheets by hydrodynamic forces. RSC Adv 4(69):36464–36470
Lotya M, Hernande Y, King PJ, Smith RJ, Nicolosi V, Karlsson LS et al (2009) Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions. J Am Chem Soc 131(10):3611–3620
Lund S, Kauppila J, Sirkiä S, Palosaari J, Eklund O, Latonen RM et al (2021) Fast high-shear exfoliation of natural flake graphite with temperature control and high yield. Carbon 174:123–131
Malard LM, Pimenta MA, Dresselhaus G, Dresselhaus MS (2009) Raman spectroscopy in graphene. Phys Rep 473(5–6):51–87
May P, Khan U, Hughes JM, Coleman JN (2012) Role of solubility parameters in understanding the steric stabilization of exfoliated two-dimensional nanosheets by adsorbed polymers. J Phys Chem C 116(20):11393–11400
Niu L, Li M, Tao X, Xie Z, Zhou X, Raju AP et al (2013) Salt-assisted direct exfoliation of graphite into high-quality, large-size, few-layer graphene sheets. Nanoscale 5(16):7202–7208
Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV et al (2004) Electric field effect in atomically thin carbon films. Science 306(5696):666–669
Novoselov KS, Fal’ko VI, Colombo L, Gellert PR, Schwab MG, Kim K (2012) A roadmap for graphene. Nature 490:192–200
Paredes JI, Villar-Rodil S (2016) Biomolecule-assisted exfoliation and dispersion of graphene and other two-dimensional materials: a review of recent progress and applications. Nanoscale 8(34):15389–15413
Park S, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4(4):217–224
Parvez K, Wu ZS, Li R, Liu X, Graf R, Feng X, Mullen K (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Chem Soc 136(16):6083–6091
Paton KR, Varrla E, Backes C, Smith RJ, Khan U, O’Neill A et al (2014) Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids. Nature Mat 13(6):624–630
Phiri J, Gane P, Maloney TC (2017) High-concentration shear-exfoliated colloidal dispersion of surfactant–polymer-stabilized few-layer graphene sheets. J Mater Sci 52(13):8321–8337
Pollard AJ, Paton KR, Clifford CA, Legge E (2017) Good practice guide no. 145: characterization of the structure of graphene, National Physical Laboratory, Middlesex
Qiu X, Bouchiat V, Colombet D, Ayela F (2019) Liquid-phase exfoliation of graphite into graphene nanosheets in a hydrocavitating ‘lab-on-a-chip.’ RSC Adv 9(6):3232–3238
Sadak O, Sundramoorthy AK, Gunasekaran S (2018) Facile and green synthesis of highly conducting graphene paper. Carbon 138:108–117
Simon DA, Bischoff E, Buonocore GG, Cerruti P, Raucci MG, Xia H et al (2017) Graphene-based masterbatch obtained via modified polyvinyl alcohol liquid-shear exfoliation and its application in enhanced polymer composites. Mater Des 134:103–110
Song N, Jia J, Wang W, Gao Y, Zhao Y, Chen Y (2016) Green production of pristine graphene using fluid dynamic force in supercritical CO2. Chem Eng J 298:198–205
Tao H, Zhang Y, Gao Y, Sun Z, Yan C, Texter J (2017) Scalable exfoliation and dispersion of two-dimensional materials–an update. Phys Chem Chem Phys 19(2):921–960
Varrla E, Paton KR, Backes C, Harvey A, Smith RJ, McCauley J, Coleman JN (2014) Turbulence-assisted shear exfoliation of graphene using household detergent and a kitchen blender. Nanoscale 6(20):11810–11819
Wang S, Yi M, Shen Z (2016) The effect of surfactants and their concentration on the liquid exfoliation of graphene. RSC Adv 6(61):56705–56710
Wei Y, Sun Z (2015) Liquid-phase exfoliation of graphite for mass production of pristine few-layer graphene. Curr Opin Colloid Interface Sci 20(5–6):311–321
Xu L, McGraw JW, Gao F, Grundy M, Ye Z, Gu Z, Shepherd JL (2013) 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(20):10730–10742
Zhou H, Yu WJ, Liu L, Cheng R, Chen Y, Huang X et al (2013) Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nat Commun 4(1):1–8
Zhu L, Zhao X, Li Y, Yu X, Li C, Zhang Q (2013) High-quality production of graphene by liquid-phase exfoliation of expanded graphite. Mater Chem Phys 137(3):984–990
Zurutuza A, Marinelli C (2014) Challenges and opportunities in graphene commercialization. Nat Nanotechnol 9(10):730–734
Acknowledgements
Z. Khanam is thankful to Dr. A.P.A. Raju, Centre of Graphene, University of Manchester, UK, for his help in graphene characterization. Z. Khanam greatly acknowledges Dr. S. Gupta, University of KwaZulu-Natal, S. Africa, and Dr. N. Gogoi, University of Sydney, Australia, for their continuous support and motivation.
Funding
This work was supported by the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices, Huizhou University, China (Grant No. EFMD2020003Z). The financial support from the Harbin Institute of Technology and Shenzhen Postdoctoral Fellowship is hereby acknowledged.
Author information
Authors and Affiliations
Contributions
Zeba Khanam: conceptualization, investigation, analysis, writing. Jianghe Liu: investigation, analysis. Shenhua Song: supervision, editing. All authors reviewed and approved the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Khanam, Z., Liu, J. & Song, S. High-concentration graphene dispersions prepared via exfoliation of graphite in PVA/H2O green solvent system using high-shear forces. J Nanopart Res 23, 170 (2021). https://doi.org/10.1007/s11051-021-05294-2
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-021-05294-2