First demonstrated in 2008,[1]liquid-phase exfoliation (LPE) is a solution-processing method which is used to convert layered crystals into two-dimensional nanosheets in large quantities.[2] It is currently one of the pillar methods for producing 2D nanosheets.[3] According to IDTechEx, the family of exfoliation techniques which are directly or indirectly descended from LPE now make up over 60% of global graphene production capacity.[4]
This method involves adding powdered layered crystals, for example of graphite, to appropriate solvents and inserting energy, often by ultrasonication, although high-shear mixing[5] is often commonly used. The addition of energy causes a combination of fragmentation and exfoliation resulting in the removal of small nanosheets from the layered crystals.[6] In this way graphite can be converted into large quantities of graphene nanosheets.[7] In general, these nanosheets tend to be a few monolayers thick and of lateral sizes ranging from tens of nanometers to many microns.[8] These dispersed nanosheets form quasi stable suspensions so long as solvents used have surface energies similar to that of the nanosheets. Dispersed concentrations of order 1 gram per litre can be achieved. In addition to solvents, it is also possible to use molecular stabilizers, for example surfactants or polymers to coat the nanosheets and stabilise them against regaggregation.[9] This has the advantage that it allows nanosheets to be suspended in water.
Although this method was first applied to exfoliate graphite to yield graphene nanosheets, it has since been used to produce a wide range of 2D materials including molybdenum disulfide, tungsten diselenide, boron nitride, nickel(II) hydroxide, germanium monosulfide, SnP3, and black phosphorus. The liquid suspensions produced by liquid phase exfoliation can be used to create a range of functional structures. For example, they can be printed into thin films and networks using standard techniques such as inkjet printing.[10]
Printed structures have been used in a range of applications in areas included printed electronics, sensors and nanocomposites. Related methods include exfoliation by wet ball milling, homogenization, microfluidization and wet jet milling.[11] Liquid phase exfoliation is different from other liquid exfoliation methods, for example the production of graphene oxide, because it is much less destructive, leaving minimal defects in the basal planes of the nanosheets. It has recently emerged that LPE can also be used to convert non-layered crystals into quasi-2D nanoplatelets.[12]
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^Coleman, Jonathan N.; Lotya, Mustafa; O’Neill, Arlene; Bergin, Shane D.; King, Paul J.; Khan, Umar; Young, Karen; Gaucher, Alexandre; De, Sukanta; Smith, Ronan J.; Shvets, Igor V.; Arora, Sunil K.; Stanton, George; Kim, Hye-Young; Lee, Kangho; Kim, Gyu Tae; Duesberg, Georg S.; Hallam, Toby; Boland, John J.; Wang, Jing Jing; Donegan, John F.; Grunlan, Jaime C.; Moriarty, Gregory; Shmeliov, Aleksey; Nicholls, Rebecca J.; Perkins, James M.; Grieveson, Eleanor M.; Theuwissen, Koenraad; McComb, David W.; Nellist, Peter D.; Nicolosi, Valeria (4 February 2011). "Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials". Science. 331 (6017): 568–571. Bibcode:2011Sci...331..568C. doi:10.1126/science.1194975. hdl:2262/66458. PMID21292974. S2CID23576676.
^Ferrari, Andrea C.; Bonaccorso, Francesco; Fal'ko, Vladimir; Novoselov, Konstantin S.; Roche, Stephan; Bøggild, Peter; Borini, Stefano; Koppens, Frank H. L.; Palermo, Vincenzo; Pugno, Nicola; Garrido, José A.; Sordan, Roman; Bianco, Alberto; Ballerini, Laura; Prato, Maurizio; Lidorikis, Elefterios; Kivioja, Jani; Marinelli, Claudio; Ryhänen, Tapani; Morpurgo, Alberto; Coleman, Jonathan N.; Nicolosi, Valeria; Colombo, Luigi; Fert, Albert; Garcia-Hernandez, Mar; Bachtold, Adrian; Schneider, Grégory F.; Guinea, Francisco; Dekker, Cees; Barbone, Matteo; Sun, Zhipei; Galiotis, Costas; Grigorenko, Alexander N.; Konstantatos, Gerasimos; Kis, Andras; Katsnelson, Mikhail; Vandersypen, Lieven; Loiseau, Annick; Morandi, Vittorio; Neumaier, Daniel; Treossi, Emanuele; Pellegrini, Vittorio; Polini, Marco; Tredicucci, Alessandro; Williams, Gareth M.; Hee Hong, Byung; Ahn, Jong-Hyun; Min Kim, Jong; Zirath, Herbert; van Wees, Bart J.; van der Zant, Herre; Occhipinti, Luigi; Di Matteo, Andrea; Kinloch, Ian A.; Seyller, Thomas; Quesnel, Etienne; Feng, Xinliang; Teo, Ken; Rupesinghe, Nalin; Hakonen, Pertti; Neil, Simon R. T.; Tannock, Quentin; Löfwander, Tomas; Kinaret, Jari (2015). "Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems". Nanoscale. 7 (11): 4598–4810. Bibcode:2015Nanos...7.4598F. doi:10.1039/C4NR01600A. hdl:2117/27112. PMID25707682.
^Paton, Keith R.; Varrla, Eswaraiah; Backes, Claudia; Smith, Ronan J.; Khan, Umar; O’Neill, Arlene; Boland, Conor; Lotya, Mustafa; Istrate, Oana M.; King, Paul; Higgins, Tom; Barwich, Sebastian; May, Peter; Puczkarski, Pawel; Ahmed, Iftikhar; Moebius, Matthias; Pettersson, Henrik; Long, Edmund; Coelho, João; O’Brien, Sean E.; McGuire, Eva K.; Sanchez, Beatriz Mendoza; Duesberg, Georg S.; McEvoy, Niall; Pennycook, Timothy J.; Downing, Clive; Crossley, Alison; Nicolosi, Valeria; Coleman, Jonathan N. (June 2014). "Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids"(PDF). Nature Materials. 13 (6): 624–630. Bibcode:2014NatMa..13..624P. doi:10.1038/NMAT3944. PMID24747780. S2CID43256835.
^Li, Zheling; Young, Robert J.; Backes, Claudia; Zhao, Wen; Zhang, Xun; Zhukov, Alexander A.; Tillotson, Evan; Conlan, Aidan P.; Ding, Feng; Haigh, Sarah J.; Novoselov, Kostya S.; Coleman, Jonathan N. (22 September 2020). "Mechanisms of Liquid-Phase Exfoliation for the Production of Graphene". ACS Nano. 14 (9): 10976–10985. doi:10.1021/acsnano.0c03916. hdl:2262/93628. PMID32598132. S2CID220269811.