Liquid-Phase Exfoliation of Graphene: An Overview on Exfoliation Media, Techniques, and Challenges

Graphene, a two-dimensional (2D) carbon nanomaterial, has attracted worldwide attention owing to its fascinating properties. One of critical bottlenecks on some important classes of applications, such as printed electronics, conductive coatings, and composite fillers, is the lack of industrial-scale methods to produce high-quality graphene in the form of liquid suspensions, inks, or dispersions. Since 2008, when liquid-phase exfoliation (LPE) of graphene via sonication was initiated, huge progress has been made in the past decade. This review highlights the latest progress on the successful preparation of graphene in various media, including organic solvents, ionic liquids, water/polymer or surfactant solutions, and some other green dispersants. The techniques of LPE, namely sonication, high-shear mixing, and microfluidization are reviewed subsequently. Moreover, several typical devices of high-shear mixing and exfoliation mechanisms are introduced in detail. Finally, we give perspectives on future research directions for the development of green exfoliation media and efficient techniques for producing high-quality graphene. This systematic exploratory study of LPE will potentially pave the way for the scalable production of graphene, which can be also applied to produce other 2D layered materials, such as BN, MoS2, WS2, etc.

[1]  Y. Hayashi,et al.  Simple Technique of Exfoliation and Dispersion of Multilayer Graphene from Natural Graphite by Ozone-Assisted Sonication , 2017, Nanomaterials.

[2]  Min Yi,et al.  Kitchen blender for producing high-quality few-layer graphene , 2014 .

[3]  M. Naraghi,et al.  A review on liquid-phase exfoliation for scalable production of pure graphene, wrinkled, crumpled and functionalized graphene and challenges , 2018 .

[4]  Min Yi,et al.  Morphology and structure of mono- and few-layer graphene produced by jet cavitation , 2011 .

[5]  Yue Zhang,et al.  Transparent and flexible tactile sensors based on graphene films designed for smart panels , 2018, Journal of Materials Science.

[6]  J. Tascón,et al.  High-throughput production of pristine graphene in an aqueous dispersion assisted by non-ionic surfactants , 2011 .

[7]  Kian Ping Loh,et al.  Synthesis and reduction of large sized graphene oxide sheets. , 2017, Chemical Society reviews.

[8]  K. Yusoh,et al.  Black tea assisted exfoliation using a kitchen mixer allowing one-step production of graphene , 2017 .

[9]  Mustafa Lotya,et al.  The importance of repulsive potential barriers for the dispersion of graphene using surfactants , 2010 .

[10]  Min Yi,et al.  Preparation of graphene by jet cavitation , 2011, Nanotechnology.

[11]  T. Maloney,et al.  High-concentration shear-exfoliated colloidal dispersion of surfactant–polymer-stabilized few-layer graphene sheets , 2017, Journal of Materials Science.

[12]  Zhiyong Gu,et al.  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 , 2013 .

[13]  Christelle Monat,et al.  Liquid-phase exfoliation of flaky graphite , 2014 .

[14]  Xiaoping Dong,et al.  Graphene quantum dots-assisted exfoliation of graphitic carbon nitride to prepare metal-free zero-dimensional/two-dimensional composite photocatalysts , 2018, Journal of Materials Science.

[15]  W. Schuhmann,et al.  High-concentration graphene dispersions with minimal stabilizer: a scaffold for enzyme immobilization for glucose oxidation. , 2014, Chemistry.

[16]  Min Yi,et al.  Fluid dynamics: an emerging route for the scalable production of graphene in the last five years , 2016, 1603.03188.

[17]  F. Liu,et al.  Amine-based solvents for exfoliating graphite to graphene outperform the dispersing capacity of N-methyl-pyrrolidone and surfactants. , 2014, Chemical communications.

[18]  D. A. Brownson,et al.  A decade of graphene research: Production, applications and outlook , 2014 .

[19]  Puspendu Bhunia,et al.  Ultrasonic pretreatment of sludge: a review. , 2011, Ultrasonics sonochemistry.

[20]  Xiaoqing Jiang,et al.  Organic salt-assisted liquid-phase exfoliation of graphite to produce high-quality graphene , 2013 .

[21]  J. Coleman,et al.  Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions , 2008, 0809.2690.

[22]  Micah J. Green,et al.  Challenges in Liquid‐Phase Exfoliation, Processing, and Assembly of Pristine Graphene , 2016, Advanced materials.

[23]  J. Coleman,et al.  Production of Two-Dimensional Nanomaterials via Liquid-Based Direct Exfoliation. , 2016, Small.

[24]  Jonathan N. Coleman,et al.  Graphene Dispersion and Exfoliation in Low Boiling Point Solvents , 2011 .

[25]  M. Hersam,et al.  Highly concentrated graphene solutions via polymer enhanced solvent exfoliation and iterative solvent exchange. , 2010, Journal of the American Chemical Society.

[26]  C. Chia,et al.  Simplified production of graphene oxide assisted by high shear exfoliation of graphite with controlled oxidation , 2018 .

[27]  W. Peukert,et al.  Delamination of graphite in a high pressure homogenizer , 2015 .

[28]  N. Murthy,et al.  Self-Assembly and Critical Aggregation Concentration Measurements of ABA Triblock Copolymers with Varying B Block Types: Model Development, Prediction, and Validation. , 2016, The journal of physical chemistry. B.

[29]  Hongjun Gao,et al.  Solvothermal-assisted exfoliation process to produce graphene with high yield and high quality , 2009 .

[30]  B. Scrosati,et al.  The role of graphene for electrochemical energy storage. , 2015, Nature materials.

[31]  A. Bourlinos,et al.  Liquid-phase exfoliation of graphite towards solubilized graphenes. , 2009, Small.

[32]  J. Coleman,et al.  Towards Solutions of Single‐Walled Carbon Nanotubes in Common Solvents , 2008 .

[33]  R. Ruoff,et al.  Chemical methods for the production of graphenes. , 2009, Nature nanotechnology.

[34]  Lei Liu,et al.  Direct exfoliation of graphite in water with addition of ammonia solution. , 2017, Journal of colloid and interface science.

[35]  Lei Liu,et al.  Water can stably disperse liquid-exfoliated graphene. , 2013, Chemical communications.

[36]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[37]  B. Z. Jang,et al.  Processing of nanographene platelets (NGPs) and NGP nanocomposites: a review , 2008, Journal of Materials Science.

[38]  Duncan N. Johnstone,et al.  Microfluidization of Graphite and Formulation of Graphene-Based Conductive Inks , 2016, ACS nano.

[39]  J. Texter,et al.  Aqueous graphene dispersions-optical properties and stimuli-responsive phase transfer. , 2014, ACS nano.

[40]  K. Novoselov,et al.  Graphene-based liquid crystal device. , 2008, Nano letters (Print).

[41]  Jianfei Che,et al.  Preparation of Polylactide/Graphene Composites From Liquid-Phase Exfoliated Graphite Sheets , 2014 .

[42]  Jose Maria Kenny,et al.  Graphene based composites prepared through exfoliation of graphite platelets in methyl methacrylate/poly(methyl methacrylate) , 2012 .

[43]  M. Piccinini,et al.  High concentration few-layer graphene sheets obtained by liquid phase exfoliation of graphite in ionic liquid , 2010, 1010.2859.

[44]  Hongran Zhao,et al.  Ultrahigh performance heat spreader based on gas-liquid exfoliation boron nitride nanosheets , 2017, Nanotechnology.

[45]  J. Coleman,et al.  High-concentration, surfactant-stabilized graphene dispersions. , 2010, ACS nano.

[46]  W. Schuhmann,et al.  Highly concentrated aqueous dispersions of graphene exfoliated by sodium taurodeoxycholate: dispersion behavior and potential application as a catalyst support for the oxygen-reduction reaction. , 2012, Chemistry.

[47]  K. R. Paton,et al.  Production of few-layer graphene by microfluidization , 2017 .

[48]  A. Bourlinos,et al.  Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes , 2009 .

[49]  A. Okotrub,et al.  Structure and supercapacitor properties of few-layer low-fluorinated graphene materials , 2018, Journal of Materials Science.

[50]  A. Ciesielski,et al.  Graphene via sonication assisted liquid-phase exfoliation. , 2014, Chemical Society reviews.

[51]  TaeYoung Kim,et al.  High shear-induced exfoliation of graphite into high quality graphene by Taylor–Couette flow , 2016 .

[52]  Min Yi,et al.  Experimental study on a designed jet cavitation device for producing two-dimensional nanosheets , 2012 .

[53]  Jin Suk Chung,et al.  Liquid-phase exfoliation of graphene in organic solvents with addition of naphthalene. , 2014, Journal of colloid and interface science.

[54]  Efrat Ruse,et al.  Top-Down, Scalable Graphene Sheets Production: It Is All about the Precipitate , 2017 .

[55]  Xiaohua Zhang,et al.  Direct exfoliation of graphite into graphene in aqueous solution using a novel surfactant obtained from used engine oil , 2018, Journal of Materials Science.

[56]  Xuehong Lu,et al.  Lignin-assisted direct exfoliation of graphite to graphene in aqueous media and its application in polymer composites , 2015 .

[57]  Joonwon Lim,et al.  Perylene tetracarboxylate surfactant assisted liquid phase exfoliation of graphite into graphene nanosheets with facile re-dispersibility in aqueous/organic polar solvents , 2017 .

[58]  K. Ariga,et al.  Defect-free exfoliation of graphene at ultra-high temperature , 2018 .

[59]  Xiaodong Zhu,et al.  Direct Exfoliation of High‐Quality, Atomically Thin MoSe2 Layers in Water , 2018 .

[60]  Min Yi,et al.  A review on mechanical exfoliation for the scalable production of graphene , 2015 .

[61]  K. Suslick,et al.  The Temperature of Cavitation , 1991, Science.

[62]  Xianglong Li,et al.  Graphene hybridization for energy storage applications. , 2018, Chemical Society reviews.

[63]  Mustafa Lotya,et al.  Measurement of multicomponent solubility parameters for graphene facilitates solvent discovery. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[64]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[65]  Hongran Zhao,et al.  A water-based green approach to large-scale production of aqueous compatible graphene nanoplatelets , 2018, Scientific Reports.

[66]  S. Magdassi,et al.  The formation of carbon nanotube dispersions by high pressure homogenization and their rapid characterization by analytical centrifuge , 2010 .

[67]  Thomas M. Higgins,et al.  Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids. , 2014, Nature materials.

[68]  A. Balandin,et al.  Graphene-multilayer graphene nanocomposites as highly efficient thermal interface materials. , 2012, Nano letters.

[69]  Brian P. Rook,et al.  Dispersion optimization of exfoliated graphene nanoplatelet in polyetherimide nanocomposites: Extrusion, precoating, and solid state ball milling , 2013 .

[70]  Lihua Zhu,et al.  From graphite to graphene: direct liquid-phase exfoliation of graphite to produce single- and few-layered pristine graphene , 2013 .

[71]  F. G. Calvo-Flores,et al.  Lignin as renewable raw material. , 2010, ChemSusChem.

[72]  R. Ruoff,et al.  From conception to realization: an historial account of graphene and some perspectives for its future. , 2010, Angewandte Chemie.

[73]  Seid Mahdi Jafari,et al.  Production of sub-micron emulsions by ultrasound and microfluidization techniques , 2007 .

[74]  Lei Liu,et al.  A green, rapid and size-controlled production of high-quality graphene sheets by hydrodynamic forces , 2014 .

[75]  O. Regev,et al.  Graphene Quantum Dots Produced by Microfluidization , 2016 .

[76]  Shannon M. Notley,et al.  Highly concentrated aqueous suspensions of graphene through ultrasonic exfoliation with continuous surfactant addition. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[77]  Chao Yan,et al.  Scalable exfoliation and dispersion of two-dimensional materials - an update. , 2017, Physical chemistry chemical physics : PCCP.

[78]  R. Lovrinčić,et al.  Critical parameters in exfoliating graphite into graphene. , 2013, Physical chemistry chemical physics : PCCP.

[79]  J. Dobson,et al.  Vortex fluidic exfoliation of graphite and boron nitride. , 2012, Chemical communications.

[80]  M. L. Cerrada,et al.  Polypropylene/graphene nanosheet nanocomposites by in situ polymerization: Synthesis, characterization and fundamental properties , 2013 .

[81]  D. Golberg,et al.  Rapid and direct conversion of graphite crystals into high-yielding, good-quality graphene by supercritical fluid exfoliation. , 2010, Chemistry.

[82]  Hao Sun,et al.  Developing Polymer Composite Materials: Carbon Nanotubes or Graphene? , 2013, Advanced materials.

[83]  O. Akhavan,et al.  Increasing the antioxidant activity of green tea polyphenols in the presence of iron for the reduction of graphene oxide , 2012 .

[84]  One-step green synthesis of graphene nanomesh by fluid-based method , 2014, 1611.00180.

[85]  Wei Wei Liu,et al.  Direct exfoliation of graphene in organic solvents with addition of NaOH. , 2011, Chemical communications.

[86]  Qingbiao Li,et al.  Production of graphene nanosheets by supercritical CO2 process coupled with micro-jet exfoliation , 2017 .

[87]  Ji-Beom Yoo,et al.  A facile approach to the fabrication of graphene/polystyrene nanocomposite by in situ microemulsion polymerization. , 2010, Journal of colloid and interface science.

[88]  M. Mazzotti,et al.  High pressure homogenization of pharmaceutical solids , 2012 .

[89]  Lei Liu,et al.  Low-temperature treatment for preservation and separation of graphene dispersions , 2018, Journal of Materials Science.

[90]  Kian Jon Chua,et al.  Simulation and development of a multi-leg homogeniser concentrating assembly for concentrated photovoltaic (CPV) system with electrical rating analysis , 2016 .

[91]  M. Burghard,et al.  Separation of carbon nanotubes by size exclusion chromatography , 1998 .

[92]  A. Ferrari,et al.  Light-enhanced liquid-phase exfoliation and current photoswitching in graphene–azobenzene composites , 2016, Nature Communications.

[93]  A. Green,et al.  Solution phase production of graphene with controlled thickness via density differentiation. , 2009, Nano letters.

[94]  Hyungdong Lee,et al.  Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control , 2015, Nature Communications.

[95]  Xingxiang Zhang,et al.  Liquid phase exfoliation of graphite into few-layer graphene by sonication and microfluidization , 2017 .

[96]  Miaofang Chi,et al.  Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids. , 2010, Chemical communications.

[97]  J. Coleman,et al.  Turbulence-assisted shear exfoliation of graphene using household detergent and a kitchen blender. , 2014, Nanoscale.

[98]  Anthony C. Coleman,et al.  Dispersion of graphene in ethanol using a simple solvent exchange method. , 2010, Chemical communications.

[99]  Jie Yin,et al.  Facile synthesis of soluble graphene via a green reduction of graphene oxide in tea solution and its biocomposites. , 2011, ACS applied materials & interfaces.

[100]  J. Tour,et al.  Chemical Mass Production of Graphene Nanoplatelets in ∼100% Yield. , 2016, ACS nano.

[101]  C. Dimitrakopoulos,et al.  Fast Production of High-Quality Graphene via Sequential Liquid Exfoliation. , 2015, ACS applied materials & interfaces.

[102]  Yong‐Young Noh,et al.  Production of graphene by exfoliation of graphite in a volatile organic solvent , 2011, Nanotechnology.

[103]  J. Coleman,et al.  High-concentration solvent exfoliation of graphene. , 2010, Small.

[104]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[105]  K. Novoselov,et al.  A roadmap for graphene , 2012, Nature.

[106]  Lei Liu,et al.  Hydrodynamics-assisted scalable production of boron nitride nanosheets and their application in improving oxygen-atom erosion resistance of polymeric composites. , 2013, Nanoscale.

[107]  J. Coleman Liquid exfoliation of defect-free graphene. , 2013, Accounts of chemical research.

[108]  W. Schuhmann,et al.  High-Yield Exfoliation of Graphite in Acrylate Polymers: A Stable Few-Layer Graphene Nanofluid with Enhanced Thermal Conductivity , 2013 .

[109]  C. Kumar,et al.  Kitchen Chemistry 101: Multigram Production of High Quality Biographene in a Blender with Edible Proteins , 2015 .

[110]  W. Meyer,et al.  Acrylate Functionalized Tetraalkylammonium Salts with Ionic Liquid Properties , 2012, Molecules.

[111]  Mehdi Shanbedi,et al.  Facile, environmentally friendly, cost effective and scalable production of few-layered graphene , 2017 .

[112]  Xingxiang Zhang,et al.  Low-temperature nanowelding ultrathin silver nanowire sandwiched between polydopamine-functionalized graphene and conjugated polymer for highly stable and flexible transparent electrodes , 2018, Chemical Engineering Journal.

[113]  Tae-Rin Lee Quantitative correlation between interlayer distance and shear rate in liquid-based exfoliation of graphene layers , 2018 .

[114]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[115]  Joong Tark Han,et al.  Extremely Efficient Liquid Exfoliation and Dispersion of Layered Materials by Unusual Acoustic Cavitation , 2014, Scientific Reports.

[116]  S. Kim,et al.  Surfactant mediated liquid phase exfoliation of graphene , 2015, Nano Convergence.

[117]  J. Tour,et al.  High-yield organic dispersions of unfunctionalized graphene. , 2009, Nano letters.

[118]  Jonathan N. Coleman,et al.  Correction to “Role of Solubility Parameters in Understanding the Steric Stabilization of Exfoliated Two-Dimensional Nanosheets by Adsorbed Polymers” , 2012 .

[119]  Jihong Yu,et al.  Preparation of Inorganic Materials Using Ionic Liquids , 2010, Advanced materials.

[120]  Zhenyu Sun,et al.  Liquid-phase exfoliation of graphite for mass production of pristine few-layer graphene , 2015 .

[121]  Micah J. Green,et al.  Polymer-stabilized graphene dispersions at high concentrations in organic solvents for nanocomposite production , 2011 .

[122]  Hongbing Lu,et al.  A non-dispersion strategy for large-scale production of ultra-high concentration graphene slurries in water , 2018, Nature Communications.

[123]  Steven M. L. Smith,et al.  Functional multi-layer graphene-algae hybrid material formed using vortex fluidics , 2013 .

[124]  G. Narsimhan,et al.  Drop Coalescence during Emulsion Formation in a High-Pressure Homogenizer for Tetradecane-in-Water Emulsion Stabilized by Sodium Dodecyl Sulfate. , 2001, Journal of colloid and interface science.

[125]  J. Coleman Liquid‐Phase Exfoliation of Nanotubes and Graphene , 2009 .

[126]  Balaji Sitharaman,et al.  Enzymatic Degradation of Oxidized and Reduced Graphene Nanoribbons by Lignin Peroxidase. , 2014, Journal of materials chemistry. B.

[127]  Nicole N. Hashemi,et al.  Graphene as a flexible electrode: review of fabrication approaches , 2017 .

[128]  V. Ramakrishnan,et al.  Synthesis of few layer graphene by direct exfoliation of graphite and a Raman spectroscopic study , 2014 .

[129]  Jonathan N. Coleman,et al.  Size selection of dispersed, exfoliated graphene flakes by controlled centrifugation , 2012 .

[130]  Y. Arao,et al.  Effect of graphite structures on the productivity and quality of few-layer graphene in liquid-phase exfoliation , 2018, Journal of Materials Science.