Abstract
Industrial scale manufacturing with tunable properties of graphene nano-sheets has been a practical concern in many applications. This study focuses on, a physical electro-chemistry approach for the synthesis of few-layer graphene nano-sheets (FLGNSs) in a scalable manner. The intercalates are bias-driven anions towards the working electrode of bulk pyrolytic graphite sheet followed by their exfoliations as FLGNSs. In-situ electrochemical studies confirm a higher rate of exfoliation with an increase in the concentration of intercalates. Based on colloidal conductivity and particle size analyses, the degree of crystallinity and effect of variation in intercalates is explored. Rate of oxidation, defects, morphological variation, and number of layers with variation of intercalate concentration have been studied by XRD, Raman spectroscopy, FTIR, UV–Vis spectroscopy, XPS, and electron microscope based analyses. Cost-effectiveness of the electrochemical process in producing FLGNSs is assessed by considering cost of raw materials used in this laboratory process.
Graphic abstract
Schematics of Industrial scalable process for manufacturing FLGNSs.
Similar content being viewed by others
References
Geim AK (2009) Graphene: status and prospects. Science 324:1530–1534. https://doi.org/10.1126/science.1158877
Sahoo SK, Mallik A (2019) Fundamentals of fascinating graphene nanosheets: a comprehensive study. NANO 14:1930003. https://doi.org/10.1142/S1793292019300032
Alonso ET, Rodrigues DP, Khetani M et al (2018) Graphene electronic fibres with touch-sensing and light-emitting functionalities for smart textiles. NPJ Flex Electron 2:25. https://doi.org/10.1038/s41528-018-0040-2
Kim H, Ahn J-H (2017) Graphene for flexible and wearable device applications. Carbon 120:244–257. https://doi.org/10.1016/j.carbon.2017.05.041
Liu S, Ou J, Wang J et al (2011) A simple two-step electrochemical synthesis of graphene sheets film on the ITO electrode as supercapacitors. J Appl Electrochem 41:881–884. https://doi.org/10.1007/s10800-011-0304-1
Wang Z, Zhu Y, Jiang Y et al (2018) Graphene modified Li1.2Ni0.133Co0.133Mn0.534O2 cathode material for high capacity lithium-ion batteries. J Appl Electrochem 48:1273–1283. https://doi.org/10.1007/s10800-018-1251-x
Ganash AA, Alqarni SA, Hussein MA (2019) Poly(aniline-co-o-anisidine)/graphene oxide Au nanocomposites for dopamine electrochemical sensing application. J Appl Electrochem 49:179–194. https://doi.org/10.1007/s10800-018-1260-9
Pasakon P, Mensing JP, Phokaratkul D et al (2019) A high-performance, disposable screen-printed carbon electrode modified with multi-walled carbon nanotubes/graphene for ultratrace level electrochemical sensors. J Appl Electrochem 49:217–227. https://doi.org/10.1007/s10800-018-1268-1
Kazemi AS, Hosseini SM, Abdi Y (2019) Large total area membrane of suspended single layer graphene for water desalination. Desalination 451:160–171. https://doi.org/10.1016/j.desal.2017.12.050
Yang Y, Asiri AM, Tang Z et al (2013) Graphene based materials for biomedical applications. Mater Today 16:365–373. https://doi.org/10.1016/j.mattod.2013.09.004
Shen J, He Y, Wu J et al (2015) Liquid phase exfoliation of two-dimensional materials by directly probing and matching surface tension components. Nano Lett 15:5449–5454. https://doi.org/10.1021/acs.nanolett.5b01842
Blomquist N, Engström AC, Hummelgård M et al (2016) Large-scale production of nanographite by tube-shear exfoliation in water. PLoS ONE 11:e0154686. https://doi.org/10.1371/journal.pone.0154686
Fang X, Shashurin A, Keidar M (2015) Role of substrate temperature at graphene synthesis in an arc discharge. J Appl Phys 118:103304. https://doi.org/10.1063/1.4930177
Sahoo SK, Mallik A (2015) Simple, fast and cost-effective electrochemical synthesis of few layer graphene nanosheets. NANO 10:1550019. https://doi.org/10.1142/S1793292015500198
Pei S, Cheng H-M (2012) The reduction of graphene oxide. Carbon 50:3210–3228. https://doi.org/10.1016/j.carbon.2011.11.010
Su C-Y, Lu A-Y, Xu Y et al (2011) High-quality thin graphene films from fast electrochemical exfoliation. ACS Nano 5:2332–2339. https://doi.org/10.1021/nn200025p
Abdelkader AM, Cooper AJ, Dryfe RAW, Kinloch IA (2015) How to get between the sheets: a review of recent works on the electrochemical exfoliation of graphene materials from bulk graphite. Nanoscale 7:6944–6956. https://doi.org/10.1039/C4NR06942K
Parvez K, Wu Z-S, Li R et al (2014) Exfoliation of graphite into graphene in aqueous solutions of inorganic salts. J Am Chem Soc 136:6083–6091. https://doi.org/10.1021/ja5017156
Cooper AJ, Wilson NR, Kinloch IA, Dryfe RAW (2014) Single stage electrochemical exfoliation method for the production of few-layer graphene via intercalation of tetraalkylammonium cations. Carbon 66:340–350. https://doi.org/10.1016/j.carbon.2013.09.009
Liu J, Poh CK, Zhan D et al (2013) Improved synthesis of graphene flakes from the multiple electrochemical exfoliation of graphite rod. Nano Energy 2:377–386. https://doi.org/10.1016/j.nanoen.2012.11.003
Chen D, Wang F, Li Y et al (2019) Programmed electrochemical exfoliation of graphite to high quality graphene. Chem Commun 55:3379–3382. https://doi.org/10.1039/C9CC00393B
Ejigu A, Miller B, Kinloch IA, Dryfe RAW (2018) Optimisation of electrolytic solvents for simultaneous electrochemical exfoliation and functionalisation of graphene with metal nanostructures. Carbon 128:257–266. https://doi.org/10.1016/j.carbon.2017.11.081
Li L, Wang M, Cao M et al (2017) Regulation of radicals from electrochemical exfoliation for production of graphene and its electrochemical properties. Electrochim Acta 258:1484–1492. https://doi.org/10.1016/j.electacta.2017.12.021
Zhou Q, Lu Y, Xu H (2019) High-yield production of high-quality graphene by novel electrochemical exfoliation at air-electrolyte interface. Mater Lett 235:153–156. https://doi.org/10.1016/j.matlet.2018.10.016
Shinde DB, Brenker J, Easton CD et al (2016) Shear assisted electrochemical exfoliation of graphite to graphene. Langmuir 32:3552–3559. https://doi.org/10.1021/acs.langmuir.5b04209
Gewirth AA, Bard AJ (1988) In situ scanning tunneling microscopy of the anodic oxidation of highly oriented pyrolytic graphite surfaces. J Phys Chem 92:5563–5566. https://doi.org/10.1021/j100331a006
Hathcock KW, Brumfield JC, Goss CA et al (1995) Incipient electrochemical oxidation of highly oriented pyrolytic graphite: correlation between surface blistering and electrolyte anion intercalation. Anal Chem 67:2201–2206. https://doi.org/10.1021/ac00109a045
Hirschfelder JO, Curtiss CF, Bird RB, Mayer MG (1964) Molecular theory of gases and liquids. Wiley, New York
Simoes MC, Hughes KJ, Ingham DB et al (2017) Estimation of the thermochemical radii and ionic volumes of complex ions. Inorg Chem 56:7566–7573. https://doi.org/10.1021/acs.inorgchem.7b01205
Marcus Y (2012) Volumes of aqueous hydrogen and hydroxide ions at 0 to 200 °C. J Chem Phys 137:154501. https://doi.org/10.1063/1.4758071
Sahoo SK, Mallik A (2015) Synthesis and characterization of conductive few layered graphene nanosheets using an anionic electrochemical intercalation and exfoliation technique. J Mater Chem C 3:10870–10878. https://doi.org/10.1039/C5TC01893E
Levi MD, Markevich E, Wang C, Aurbach D (2007) Chronoamperometric measurements and modeling of nucleation and growth, and moving boundary stages during electrochemical lithiation of graphite electrode. J Electroanal Chem 600:13–22. https://doi.org/10.1016/j.jelechem.2005.11.037
Morales GM, Schifani P, Ellis G et al (2011) High-quality few layer graphene produced by electrochemical intercalation and microwave-assisted expansion of graphite. Carbon 49:2809–2816. https://doi.org/10.1016/j.carbon.2011.03.008
Beck F, Junge H, Krohn H (1981) Graphite intercalation compounds as positive electrodes in galvanic cells. Electrochim Acta 26:799–809. https://doi.org/10.1016/0013-4686(81)85038-4
Beck F, Krohn H (1983) Reversible electrochemical intercalation of anions from aqueous solutions in polymer bound graphite electrodes. Synth Met 7:193–199. https://doi.org/10.1016/0379-6779(83)90047-4
Besenhard JO, Wudy E, Möhwald H et al (1983) Anodic oxidation of graphite in H2SO4 dilatometry-in situ X-ray diffraction-impedance spectroscopy. Synth Met 7:185–192. https://doi.org/10.1016/0379-6779(83)90046-2
Zhang J, Wang E (1995) STM investigation of HOPG superperiodic features caused by electrochemical pretreatment. J Electroanal Chem 399:83–89. https://doi.org/10.1016/0022-0728(95)04175-3
Zhang B, Wang E (1995) Effects of anodic oxidation on the surface structure of highly oriented pyrolytic graphite revealed by in situ electrochemical scanning tunnelling microscopy in H2SO4 solution. Electrochim Acta 40:2627–2633. https://doi.org/10.1016/0013-4686(95)00111-Q
Alanyalıoğlu M, Segura JJ, Oró-Solè J, Casañ Pastor N (2012) The synthesis of graphene sheets with controlled thickness and order using surfactant-assisted electrochemical processes. Carbon 50:142–152. https://doi.org/10.1016/j.carbon.2011.07.064
Chuang C-H, Su C-Y, Hsu K-T et al (2015) A green, simple and cost-effective approach to synthesize high quality graphene by electrochemical exfoliation via process optimization. RSC Adv 5:54762–54768. https://doi.org/10.1039/C5RA07710A
Bose S, Kuila T, Mishra AK et al (2012) Dual role of glycine as a chemical functionalizer and a reducing agent in the preparation of graphene: an environmentally friendly method. J Mater Chem 22:9696–9703. https://doi.org/10.1039/c2jm00011c
Blanton TN, Majumdar D (2012) X-ray diffraction characterization of polymer intercalated graphite oxide. Powder Diff 27:104–107. https://doi.org/10.1017/S0885715612000292
Coroş M, Pogăcean F, Roşu M-C et al (2016) Simple and cost-effective synthesis of graphene by electrochemical exfoliation of graphite rods. RSC Adv 6:2651–2661. https://doi.org/10.1039/C5RA19277C
Xie R, Fan G, Ma Q et al (2014) Facile synthesis and enhanced catalytic performance of graphene-supported Ni nanocatalyst from a layered double hydroxide-based composite precursor. J Mater Chem A 2:7880–7889. https://doi.org/10.1039/c4ta00395k
Iqbal MW, Singh AK, Iqbal MZ, Eom J (2012) Raman fingerprint of doping due to metal adsorbates on graphene. J physics Condens matter 24:335301. https://doi.org/10.1088/0953-8984/24/33/335301
Dresselhaus MS, Jorio A, Souza Filho AG, Saito R (2010) Defect characterization in graphene and carbon nanotubes using Raman spectroscopy. Philos Trans R Soc A 368:5355–5377. https://doi.org/10.1098/rsta.2010.0213
Srinivas G, Zhu Y, Piner R et al (2010) Synthesis of graphene-like nanosheets and their hydrogen adsorption capacity. Carbon 48:630–635. https://doi.org/10.1016/j.carbon.2009.10.003
Lu J, Yang J, Wang J et al (2009) One-pot synthesis of fluorescent carbon nanoribbons, nanoparticles, and graphene by the exfoliation of graphite in ionic liquids. ACS Nano 3:2367–2375. https://doi.org/10.1021/nn900546b
Ferrari AC, Meyer JC, Scardaci V et al (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97:187401. https://doi.org/10.1103/PhysRevLett.97.187401
Koh ATT, Foong YM, Chua DHC (2012) Comparison of the mechanism of low defect few-layer graphene fabricated on different metals by pulsed laser deposition. Diam Relat Mater 25:98–102. https://doi.org/10.1016/j.diamond.2012.02.014
Sadezky A, Muckenhuber H, Grothe H et al (2005) Raman microspectroscopy of soot and related carbonaceous materials: spectral analysis and structural information. Carbon 43:1731–1742. https://doi.org/10.1016/j.carbon.2005.02.018
Abdolmaleki A, Mallakpour S, Borandeh S (2016) Improving interfacial interaction of L-phenylalanine-functionalized graphene nanofiller and poly(vinyl alcohol) nanocomposites for obtaining significant membrane properties: morphology, thermal, and mechanical studies. Polym Compos 37:1924–1935. https://doi.org/10.1002/pc.23371
Fu Y, Zhang J, Liu H et al (2013) Ionic liquid-assisted exfoliation of graphite oxide for simultaneous reduction and functionalization to graphenes with improved properties. J Mater Chem A 1:2663–2674. https://doi.org/10.1039/c2ta00353h
Kaniyoor A, Jafri RI, Arockiadoss T, Ramaprabhu S (2009) Nanostructured Pt decorated graphene and multi walled carbon nanotube based room temperature hydrogen gas sensor. Nanoscale 1:382–386. https://doi.org/10.1039/b9nr00015a
Sudesh, Kumar N, Das S, Bernhard C, Varma GD (2013) Effect of graphene oxide doping on superconducting properties of bulk MgB2. Supercond Sci Technol 26:095008. https://doi.org/10.1088/0953-2048/26/9/095008
Kumar NA, Choi H-J, Shin YR et al (2012) Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors. ACS Nano 6:1715–1723. https://doi.org/10.1021/nn204688c
Das M, Datta J, Dey A et al (2015) One step hydrothermal synthesis of a rGO-TiO2 nanocomposite and its application on a Schottky diode: improvement in device performance and transport properties. RSC Adv 5:101582–101592. https://doi.org/10.1039/C5RA17795B
Nethravathi C, Rajamathi M (2008) Chemically modified graphene sheets produced by the solvothermal reduction of colloidal dispersions of graphite oxide. Carbon 46:1994–1998. https://doi.org/10.1016/j.carbon.2008.08.013
Zhou K, Zhu Y, Yang X et al (2011) Preparation of graphene–TiO2 composites with enhanced photocatalytic activity. New J Chem 35:353–359. https://doi.org/10.1039/c0nj00623h
Galande C, Mohite AD, Naumov AV et al (2011) Quasi-molecular fluorescence from graphene oxide. Sci Rep 1:85. https://doi.org/10.1038/srep00085
Singh VV, Gupta G, Batra A et al (2012) Greener electrochemical synthesis of high quality graphene nanosheets directly from pencil and its SPR sensing application. Adv Funct Mater 22:2352–2362. https://doi.org/10.1002/adfm.201102525
Singhbabu YN, Sahu KK, Dadhich D et al (2013) Capsule-embedded reduced graphene oxide: synthesis, mechanism and electrical properties. J Mater Chem C 1:958–966. https://doi.org/10.1039/C2TC00304J
Kwan YCG, Ng GM, Huan CHA (2015) Identification of functional groups and determination of carboxyl formation temperature in graphene oxide using the XPS O 1s spectrum. Thin Solid Films 590:40–48. https://doi.org/10.1016/j.tsf.2015.07.051
Hsu H-C, Shown I, Wei H-Y et al (2013) Graphene oxide as a promising photocatalyst for CO2 to methanol conversion. Nanoscale 5:262–268. https://doi.org/10.1039/c2nr31718d
Woo S, Kim Y-R, Chung TD et al (2012) Synthesis of a graphene-carbon nanotube composite and its electrochemical sensing of hydrogen peroxide. Electrochim Acta 59:509–514. https://doi.org/10.1016/j.electacta.2011.11.012
Tu Q, Pang L, Chen Y et al (2014) Effects of surface charges of graphene oxide on neuronal outgrowth and branching. Analyst 139:105–115. https://doi.org/10.1039/c3an01796f
Huang Z-D, Zhang B, Oh S-W et al (2012) Self-assembled reduced graphene oxide/carbon nanotube thin films as electrodes for supercapacitors. J Mater Chem 22:3591–3599. https://doi.org/10.1039/c2jm15048d
Kumar NA, Nolan H, McEvoy N et al (2013) Plasma-assisted simultaneous reduction and nitrogen doping of graphene oxide nanosheets. J Mater Chem A 1:4431–4435. https://doi.org/10.1039/c3ta10337d
Senthilnathan J, Liu Y-F, Rao KS, Yoshimura M (2014) Submerged liquid plasma for the synchronized reduction and functionalization of graphene oxide. Sci Rep 4:4395. https://doi.org/10.1038/srep04395
Zhong YL, Swager TM (2012) Enhanced electrochemical expansion of graphite for in situ electrochemical functionalization. J Am Chem Soc 134:17896–17899. https://doi.org/10.1021/ja309023f
Ossonon BD, Belanger D (2017) Functionalization of graphene sheets by the diazonium chemistry during electrochemical exfoliation of graphite. Carbon 111:83–93. https://doi.org/10.1016/j.carbon.2016.09.063
Chen C-H, Yang S-W, Chuang M-C et al (2015) Towards the continuous production of high crystallinity graphene via electrochemical exfoliation with molecular in situ encapsulation. Nanoscale 7:15362–15373. https://doi.org/10.1039/c5nr03669k
Lu X, Zhao C (2013) Controlled electrochemical intercalation, exfoliation and in situ nitrogen doping of graphite in nitrate-based protic ionic liquids. Phys Chem Chem Phys 15:20005–20009. https://doi.org/10.1039/c3cp53917b
Alliata D, Haring P, Haas O et al (1999) Anion intercalation into highly oriented pyrolytic graphite studied by electrochemical atomic force microscopy. Electrochem Commun 1:5–9
Noel M, Santhanam R (1998) Electrochemistry of graphite intercalation compounds. J Power Sources 72:53–65. https://doi.org/10.1016/S0378-7753(97)02675-X
Acknowledgements
SKS would like to acknowledge the Ministry of Human Resource Development, Govt. of India and National Institute of Technology Rourkela for their financial and infrastructure support during the doctoral research study. The authors also gratefully acknowledge the financial support of this work by the Science and Engineering Research Board (SERB, India) for the Grant Number EEQ/2018/001452.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
No potential conflict of interest was reported by the authors.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Sahoo, S.K., Behera, A.K., Chandran, R. et al. Industrial scale synthesis of few-layer graphene nanosheets (FLGNSs): an exploration of electrochemical exfoliation approach. J Appl Electrochem 50, 673–688 (2020). https://doi.org/10.1007/s10800-020-01422-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-020-01422-3