Electrochemical production of graphene sheets directly from graphite mineral
11247906 · 2022-02-15
Assignee
Inventors
Cpc classification
C25B1/00
CHEMISTRY; METALLURGY
C01B2204/04
CHEMISTRY; METALLURGY
C25B9/40
CHEMISTRY; METALLURGY
International classification
C25B1/00
CHEMISTRY; METALLURGY
Abstract
A method of producing graphene sheets directly from graphite mineral (graphite rock) powder, comprising: (a) forming an intercalated graphite compound by an electrochemical intercalation procedure conducted in an intercalation reactor, containing (i) a liquid solution electrolyte comprising an intercalating agent and a graphene plane-wetting agent dissolved therein; (ii) a working electrode that contains the graphite material powder as an active material; and (iii) a counter-electrode, and wherein a current is imposed upon the working electrode and counter electrode at a current density sufficient for effecting electrochemical intercalation of the intercalating agent and/or wetting agent into interlayer spacing, wherein the wetting agent is selected from melamine, ammonium sulfate, sodium dodecyl sulfate, Na(ethylenediamine), tetraalkylammonium salts, ammonia, carbamide, hexamethylenetetramine, organic amine, poly(sodium-4-styrene sulfonate), or a combination thereof; and (b) exfoliating and separating the intercalated graphite compound using ultrasonication, thermal shock exposure, and/or a mechanical shearing treatment to produce graphene sheets.
Claims
1. A method of producing isolated graphene sheets directly from a supply of graphite mineral powder comprising therein graphene planes with an interlayer spacing, said method comprising: (a) forming an intercalated graphite compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor comprises (i) a liquid solution electrolyte comprising intercalating agents and a graphene plane-wetting agent dissolved therein, wherein the intercalating agents comprise lithium perchlorate and at least one of sodium perchlorate and potassium perchlorate; (ii) a working electrode that comprises said graphite mineral powder as an active material in ionic contact with said liquid solution electrolyte; and (iii) a counter electrode in ionic contact with said liquid solution electrolyte, and wherein a current is imposed upon said working electrode and said counter electrode at a current density for a duration of time sufficient for effecting electrochemical intercalation of said intercalating agents and/or said wetting agent into said interlayer spacing, wherein said wetting agent is melamine, sodium (ethylenediamine), hexamethylenetetramine, 1-pyrenamine, or a combination thereof; and (b) exfoliating and separating said graphene planes from said intercalated graphite compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets.
2. The method of claim 1, wherein said method is conducted intermittently or continuously and said supply of graphite mineral powder and said liquid solution electrolyte are provided into said reactor intermittently or continuously.
3. The method of claim 1, wherein said graphite mineral powder comprises a proportion of layered graphite material in the range from 20% to 97% by weight.
4. The method of claim 1, wherein said graphite mineral powder comprises a proportion of layered graphite material in the range from 30% to 90% by weight.
5. The method of claim 1, wherein said working electrode comprises no other graphite material than said graphite mineral powder as an electrode active material to be intercalated.
6. The method of claim 1, wherein said mechanical shearing treatment comprises operating air milling, air jet milling, ball milling, rotating-blade mechanical shearing, or a combination thereof.
7. The method of claim 1, wherein the imposing current provides a current density in the range of 0.1 to 600 A/m.sup.2.
8. The method of claim 1, wherein the imposing current provides a current density in the range of 1 to 500 A/m.sup.2.
9. The method of claim 1, wherein the imposing current provides a current density in the range of 10 to 300 A/m.sup.2.
10. The method of claim 1, wherein said thermal shock exposure comprises heating said intercalated graphite to a temperature in the range of 300-1,200° C. for a period of 15 seconds to 2 minutes.
11. The method of claim 1, wherein said isolated graphene sheets comprise single-layer graphene.
12. The method of claim 1, wherein said isolated graphene sheets comprise few-layer graphene having 2-10 graphene planes.
13. The method of claim 1, wherein said electrochemical intercalation comprises intercalation of both said intercalating agents and said wetting agent into the interlayer spacing.
14. The method of claim 1, wherein said intercalated graphite compound comprises Stage-1, Stage-2, or a combination of Stage-1 and Stage-2 graphite intercalation compounds.
15. The method of claim 1, further comprising a step of re-intercalating said isolated graphene sheets using an electrochemical or chemical intercalation method to obtain intercalated graphene sheets followed by a step of further exfoliating and separating said intercalated graphene sheets to produce single-layer graphene sheets using ultrasonication, thermal shock exposure, exposure to water solution, mechanical shearing treatment, or a combination thereof.
16. The method of claim 1, wherein said intercalating agents comprise a dichloroacetic acid (Cl.sub.2CHCOOH); or an alkylsulfonic acid selected from the group consisting of methanesulfonic (MeSO.sub.3H), ethanesulfonic (EtSO.sub.3H), or 1-propanesulfonic (n-PrSO.sub.3H); and combinations thereof.
17. The method of claim 1, wherein said intercalating agents comprise a metal halide.
18. The method of claim 1, wherein said intercalating agents further comprise an alkali metal salt selected from the group consisting of sodium perchlorate (NaClO.sub.4), potassium perchlorate (KClO.sub.4), sodium hexafluorophosphate (NaPF.sub.6), potassium hexafluorophosphate (KPF.sub.6), sodium borofluoride (NaBF.sub.4), potassium borofluoride (KBF.sub.4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF.sub.3SO.sub.3), potassium trifluoro-methanesulfonate (KCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF.sub.3SO.sub.2).sub.2), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF.sub.3SO.sub.2).sub.2), a sodium ionic liquid salt, lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-methanesulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), Li-fluoroalkyl-phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, and combinations thereof.
19. The method of claim 1, wherein said intercalating agents comprise an organic solvent which is tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), or a combination thereof.
20. The method of claim 1, wherein multiple particles of said graphite mineral powder are dispersed in said liquid solution electrolyte, disposed in a working electrode compartment, and supported or confined by a current collector in electronic contact therewith, and wherein said working electrode compartment and said multiple particles supported thereon or confined therein are not in electronic contact with said counter electrode.
21. The method of claim 20, wherein said multiple particles are clustered together to form a network of electron-conducting pathways.
22. The method of claim 20, wherein said method is conducted intermittently or continuously and said supply of graphite mineral powder and said liquid solution electrolyte are provided into said working electrode compartment intermittently or continuously.
23. The method of claim 20, wherein said graphite mineral powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 20% by weight.
24. The method of claim 20, wherein said graphite mineral powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 40% by weight.
25. A method of producing isolated graphene sheets directly from a supply of graphite mineral powder comprising therein graphene planes with an interlayer spacing, said method comprising: (a) forming an intercalated graphite compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor comprises (i) a liquid solution electrolyte comprising intercalating agents dissolved therein, wherein said intercalating agents comprises mixed metal ions; (ii) a working electrode that comprises said graphite mineral powder as an active material in ionic contact with said liquid solution electrolyte; and (iii) a counter electrode in ionic contact with said liquid solution electrolyte, and wherein a current is imposed upon said working electrode and said counter electrode at a current density for a duration of time sufficient for effecting electrochemical intercalation of said intercalating agents into said interlayer spacing; and (b) exfoliating and separating said graphene planes from said intercalated graphite compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets Wherein during sub process a) said liquid solution consists essentially of 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol), dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, gamma-butyrolactone (y-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), hydrofloroether, or a combination thereof, wherein said intercalating agents comprise two or more alkali metal salts selected from the group consisting of sodium perchlorate (NaCLO.sub.4), potassium perchlorate (KCLO.sub.4), sodium hexafluorophosphate (NaPF.sub.6), potassium hexafluorophosphate (KPF.sub.6), sodium borofluoride (NaBF.sub.4), potassium borofluoride (KBF.sub.4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF.sub.3SO.sub.3), potassium trifluoro-methanesulfonate (KCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF.sub.3 SO.sub.2).sub.2), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF.sub.3SO.sub.2).sub.2), a sodium ionic liquid salt, lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-methanesulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), Li-fluoroalkyl-phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), and an ionic liquid lithium salt.
26. A method of producing isolated graphene sheets directly from a supply of graphite mineral powder without purification comprising therein graphene planes with an interlayer spacing, said method comprising: (a) forming an intercalated graphite compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor comprises (i) a liquid solution electrolyte comprising intercalating agents and a graphene plane-wetting agent dissolved therein; (ii) a working electrode that comprises said graphite mineral powder as an active material in ionic contact with said liquid solution electrolyte; and (iii) a counter electrode in ionic contact with said liquid solution electrolyte, and wherein a current is imposed upon said working electrode and said counter electrode at a current density for a duration of time sufficient for effecting electrochemical intercalation of said intercalating agent and/or said wetting agent into said interlayer spacing, wherein said wetting agent is melamine, ammonium sulfate, sodium (ethylenediamine), carbamide, hexamethylenetetramine, organic amine, 1-pyrenamine, or a combination thereof; and wherein said intercalating agents comprise two or more salts selected from the group consisting of potassium perchlorate (KClO.sub.4), sodium hexafluorophosphate (NaPF.sub.6), potassium hexafluorophosphate (KPF.sub.6), sodium borofluoride (NaBF.sub.4), potassium borofluoride (KBF.sub.4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF.sub.3SO.sub.3), potassium trifluoro-methanesulfonate (KCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF.sub.3SO.sub.2).sub.2), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF.sub.3SO.sub.2).sub.2), a sodium ionic liquid salt, lithium hexafluoroarsenide (LiAsF.sub.6), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), Li-fluoroalkyl-phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), and an ionic liquid lithium salt; (b) exfoliating and separating said graphene planes from said intercalated graphite compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
(5) Carbon materials can assume an essentially amorphous structure (glassy carbon), a highly organized crystal (graphite), or a whole range of intermediate structures that are characterized in that various proportions and sizes of graphite crystallites and defects are dispersed in an amorphous matrix. Typically, a graphite crystallite is composed of a number of graphene sheets or basal planes that are bonded together through van der Waals forces in the c-axis direction, the direction perpendicular to the basal plane. These graphite crystallites are typically micron- or nanometer-sized. The graphite crystallites are dispersed in or connected by crystal defects or an amorphous phase in a graphite particle, which can be a graphite flake, carbon/graphite fiber segment, carbon/graphite whisker, or carbon/graphite nano-fiber. In the case of a carbon or graphite fiber segment, the graphene plates may be a part of a characteristic “turbostratic structure.”
(6) Basically, a graphite material is composed of many graphene planes (hexagonal carbon atomic interlayers) stacked together having inter-planar spacing. These graphene planes can be exfoliated and separated to obtain isolated graphene sheets that can each contain one graphene plane or several graphene planes of hexagonal carbon atoms. Further, natural graphite refers to a graphite material that is produced from purification of graphite mineral (mined graphite ore or graphite rock) typically by a series of flotation and acid treatments. Particles of natural graphite are then subjected to intercalation/oxidation, expansion/exfoliation, and separation/isolation treatments as discussed in the Background section. The instant invention obviates the need to go through the purification procedures that otherwise generate great amounts of polluting chemicals.
(7) One preferred specific embodiment of the present invention is a method of producing isolated graphene sheets, also called nano graphene platelets (NGPs), directly from graphite rock or graphite ore without purification. Each graphene sheet comprises one or multiple planes of two-dimensional hexagonal structure of carbon atoms. Each graphene sheet has a length and a width parallel to the graphene plane and a thickness orthogonal to the graphene plane. By definition, the thickness of an NGP is 100 nanometers (nm) or smaller (more typically <10 nm and most typically and desirably <3.4 nm), with a single-sheet NGP (single-layer graphene) being as thin as 0.34 nm. The length and width of a NGP are typically between 1 μm and 20 μm, but could be longer or shorter. For certain applications, both length and width are smaller than 1 μm.
(8) Generally speaking, as schematically shown in
(9) In this Step (b), thermal shock exposure may be conducted if some organic species have been intercalated into inter-graphene plane spaces to produce separated graphene sheets. If the anode contains Stage-1 graphite intercalation compounds, thermal shock alone can produce separated graphene sheets 16. Otherwise, thermal shock leads to the formation of exfoliated graphite 14 (also referred to as graphite worms), which is then subjected a mechanical shearing treatment or ultrasonication to produce the desired isolated graphene sheets 16. If the graphite intercalation compounds contain mainly alkali metal ions (Li, Na, and/or K) residing in inter-graphene plane spaces, the resulting alkali metal-intercalated graphite compounds may be immersed in water or water-alcohol solution (with or without sonication) to effect exfoliation and separation of graphene sheets.
(10) The exfoliation step preferably comprises heating the intercalated graphite to a temperature in the range of 300-1,200° C. for a duration of 10 seconds to 2 minutes, most preferably at a temperature in the range of 600-1,000° C. for a duration of 30-60 seconds. The exfoliation step in the instant invention does not involve the evolution of undesirable species, such as NO.sub.x and SO.sub.x, which are common by-products of exfoliating conventional sulfuric or nitric acid-intercalated graphite compounds.
(11) Schematically shown in
(12) Thus, in some embodiments, the invention provides a method of producing isolated graphene sheets having an average thickness smaller than 10 nm (mostly less than 2 nm) directly from a graphite mineral material having hexagonal carbon atomic interlayers with an interlayer spacing, the method comprising: (a) forming an intercalated graphite compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein the reactor contains (i) a liquid solution electrolyte comprising an intercalating agent and a graphene plane-wetting agent (briefly “wetting agent”) dissolved therein; (ii) a working electrode (e.g. anode) that contains the graphite mineral powder as an active material in ionic contact with the liquid solution electrolyte; and (iii) a counter electrode (e.g. cathode) in ionic contact with the liquid solution electrolyte, and wherein a current is imposed upon the working electrode and the counter electrode at a current density for a duration of time sufficient for effecting electrochemical intercalation of the intercalating agent and/or the wetting agent into the interlayer spacing, wherein the wetting agent is selected from melamine, ammonium sulfate, sodium dodecyl sulfate, sodium (ethylenediamine), tetraalkyammonium salts, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1-pyrenecarboxylic acid (PCA), 1-pyrenebutyric acid (PBA), 1-pyrenamine (PA), poly(sodium-4-styrene sulfonate), or a combination thereof; and (b) exfoliating and separating the hexagonal carbon atomic interlayers from the intercalated graphite compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce the isolated graphene sheets.
Preferably, the concentration of the milled graphite rock or graphite mineral in the liquid solution electrolyte is sufficiently high to achieve a network of electron-conducting pathways, which are in electronic contact with an anode (e.g. via an anode current collector), but not with a cathode.
(13) In an alternative electrochemical intercalation configuration, all the graphite materials to be intercalated and then exfoliated (e.g. milled powder of graphite rock) may be formed into a rod or plate that serves as an anode electrode. A metal or graphite rod or plate serves as a cathode. Both the anode and the cathode are in contact with or dispersed in a liquid solution electrolyte containing an intercalating agent and a wetting agent dissolved therein. In this alternative configuration, no graphite material to be intercalated (e.g. no graphite rock, graphite mineral or mined graphite ore) is dispersed in the liquid electrolyte. A current is then imposed to the anode and the cathode to allow for electrochemical intercalation of the intercalating agent and/or the graphene plane wetting agent into the anode active material (the graphite mineral material). Under favorable conditions (e.g. sufficiently high current density), exfoliation of graphite directly into graphene sheets occur. Alternatively and preferably, the electrochemical intercalation conditions are meticulously controlled to accomplish intercalation (for forming the intercalated graphite compound) without exfoliation. The intercalated compound is then exfoliated by using the procedures described in step (b). Such a two-step procedure is preferred over the direct exfoliation procedure because the latter often occurs in an uncontrollable manner and the electrode (e.g. anode) is broken or disrupted before intercalation into the entire rod can be completed.
(14) The mechanical shearing treatment, used to further separate graphite flakes and possibly reduce the flake size, preferably comprises using air milling (including air jet milling), ball milling, mechanical shearing (including rotating blade fluid grinding), any fluid energy based size-reduction process, ultrasonication, or a combination thereof.
(15) The intercalating agent may contain a Brønsted acid selected from phosphoric acid (H.sub.3PO.sub.4), dichloroacetic (Cl.sub.2CHCOOH), or an alkylsulfonic acid selected from methanesulfonic (MeSO.sub.3H), ethanesulfonic (EtSO.sub.3H), or 1-propanesulfonic (n-PrSO.sub.3H), or a combination thereof.
(16) In certain embodiments, the intercalating agent includes a metal halide. More specifically, the intercalating agent includes a metal halide selected from the group consisting of MCl (M=Li, Na, K, Cs), MCl.sub.2 (M=Zn, Ni, Cu, Mn), MCl.sub.3 (M=Al, Fe, Ga), MCl.sub.4 (M=Zr, Pt), MF.sub.2 (M=Zn, Ni, Cu, Mn), MF.sub.3 (M=Al, Fe, Ga), MF.sub.4 (M=Zr, Pt), and combinations thereof.
(17) Alternatively, the intercalating agent can include an alkali metal salt and this salt can be dispersed in an organic solvent or an ionic liquid. Preferably, the alkali metal salt is selected from sodium perchlorate (NaClO.sub.4), potassium perchlorate (KClO.sub.4), sodium hexafluorophosphate (NaPF.sub.6), potassium hexafluorophosphate (KPF.sub.6), sodium borofluoride (NaBF.sub.4), potassium borofluoride (KBF.sub.4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF.sub.3SO.sub.3), potassium trifluoro-metasulfonate (KCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF.sub.3SO.sub.2).sub.2), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF.sub.3SO.sub.2).sub.2), a sodium ionic liquid salt, lithium perchlorate (LiClO.sub.4), lithium hexafluorophosphate (LiPF.sub.6), lithium borofluoride (LiBF.sub.4), lithium hexafluoroarsenide (LiAsF.sub.6), lithium trifluoro-metasulfonate (LiCF.sub.3SO.sub.3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF.sub.3SO.sub.2).sub.2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium oxalyldifluoroborate (LiBF.sub.2C.sub.2O.sub.4), lithium nitrate (LiNO.sub.3), Li-Fluoroalkyl-Phosphates (LiPF.sub.3(CF.sub.2CF.sub.3).sub.3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, or a combination thereof.
(18) Preferably, the organic solvent used to dissolve the alkali metal salt is selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, propylene carbonate, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofloroether, or a combination thereof. Essentially all of these solvents can be used in the present electrochemical intercalation method to facilitate intercalation of alkali metal ions (e.g. Li.sup.+, Na.sup.+, or K.sup.+) into inter-graphene plane spaces. Under favorable electrochemical conditions, most of these organic solvents are capable of intercalating into these inter-planar spaces.
(19) The wetting agent is selected from melamine, ammonium sulfate, sodium dodecyl sulfate, sodium (ethylenediamine), tetraalkylammonium salts, ammonia, carbamide, hexamethylenetetramine, organic amine, poly(sodium-4-styrene sulfonate), or a combination thereof. We have surprisingly observed several advantages that can be achieved by adding a wetting agent in the electrolyte, in addition to an intercalating agent. . . Typically, the addition of a wetting agent to the liquid solution electrolyte leads to thinner graphene sheets as compared to the electrochemical intercalation electrolyte containing no wetting agent. This is reflected by the typically larger specific surface areas of the mass of graphene sheets produced after exfoliation as measured by the well-known BET method. It seems that the wetting agent can readily spread into inter-layer spaces, stick to a graphene plane, and prevent graphene sheets, once formed, from being re-stacked together. This is a particularly desirable feature considering the fact that graphene planes, when separated, have a great tendency to re-stack again. The presence of these graphene plane wetting agent serves to prevent re-stacking of graphene sheets.
(20) Some of the wetting agents (e.g. those containing an amine group) also serve to chemically functionalize the isolated graphene sheets, thereby improving the chemical or mechanical compatibility of the graphene sheets with a matrix resin (e.g. epoxy) in a composite material.
(21) It is quite surprising that sodium ions and potassium ions, albeit significantly larger than lithium ions in terms of ionic radii, can be intercalated into all kinds of graphite materials using the instant electrochemical configurations and method. Further unexpectedly, mixed ions (e.g. Li.sup.++Na.sup.+, or Li.sup.++K.sup.+) intercalated into inter-graphene plane spacing of a graphite material are more effective than single-ion species (e.g. Li.sup.+ only) in exfoliating graphite to form thinner graphene sheets.
(22) We have found that the invented electrochemical intercalation (with certain alkali metal salts and certain solvents and/or wetting agent) and thermal exfoliation can led to the formation of NGPs with an average thickness smaller than 5 nm. However, stage-2 and stage-3 graphite intercalation compounds can lead to graphene platelets thicker than 5 nm. In order to further reduce the platelet thickness, we have conducted further studies and found that repeated electrochemical intercalations/exfoliations are an effective method of producing ultra-thin, nano-scaled graphene platelets with an average thickness smaller than 2 nm or 5 graphene planes in each sheet or platelet and, in many cases, mostly single-layer graphene.
(23) It may be noted that, in a traditional graphite intercalation compound (GIC) obtained by intercalation of a laminar graphite material, the intercalant species may form a complete or partial layer in an inter-layer space or gallery. If there always exists one graphene layer between two neighboring intercalant layers, the resulting graphite is referred to as a Stage-1 GIC (i.e. on average, there is one intercalation layer per one graphene plane). If n graphene layers exist between two intercalant layers, we have a Stage-n GIC. Alkali metal-intercalated graphite compounds were found to be stage-2, stage-3, stage-4, or stage-5, depending on the type of carboxylic acid used. It is generally believed that a necessary condition for the formation of all single-layer graphene is to have a perfect Stage-1 GIC for exfoliation. Even with a Stage-1 GIC, not all of the graphene layers get exfoliated for reasons that remain unclear. Similarly, exfoliation of a Stage-n GIC (with n>5) tends to lead to a wide distribution of NGP thicknesses (mostly much greater than n layers). In other words, exfoliation of Stage-5 GICs often yields NGPs much thicker than 10 or 20 layers. Hence, a major challenge is to be able to consistently produce NGPs with well-controlled dimensions (preferably ultra-thin) from acid-intercalated graphite. In this context, it was surprising for us to discover that the instant method can consistently lead to the formation of few-layer graphene and/or single-layer graphene only. The production yield is typically higher than 70%, more typically higher than 80%, and most typically higher than 90%.
(24) The following examples serve to provide the best modes of practice for the present invention and should not be construed as limiting the scope of the invention:
EXAMPLE 1
Production of Isolated Graphene Sheets from Milled Graphite Rock (Graphite Ore or Mineral)
(25) Graphite rock (graphite ore or mineral), milled to an average diameter<10 μm, was used as the anode material and 1,000 mL of a liquid solution electrolyte (typically 0.5-3 M of an alkali metal salt in an organic solvent). Ethylene carbonate (EC), propylene carbonate (PC), and diethyl carbonate (DEC) were used as the solvent. The alkali metal salts used in this example include lithium perchlorate (LiClO.sub.4), sodium perchlorate (NaClO.sub.4), potassium perchlorate (KClO.sub.4), and their mixtures. The graphene plane wetting agents selected include melamine, sodium (ethylenediamine), and hexamethylenetetramine.
(26) The anode supporting element is a stainless steel plate and the cathode is a graphite foam of approximately 4 cm in diameter and 0.2 cm in thickness, impregnated with lithium or sodium. The separator, a glass fiber fabric, was used to separate the cathode plate from the milled graphite rock particles and to compress these particles down against the anode supporting element to ensure that the particles are in electrical connection with the anode supporting element to serve as the anode. The electrodes, electrolyte, and separator are contained in a Buchner-type funnel to form an electrochemical cell. The anode supporting element, the cathode, and the separator are porous to permit intercalate (contained in the electrolyte) to saturate the graphite and to pass through the cell from top to bottom.
(27) The milled graphite rock particles were subjected to an electrochemical charging treatment (i.e. charging alkali metal ions into inter-graphene plane spaces in a graphitic structure at a current of 0.5 amps (current density of about 0.04 amps/cm.sup.2) and at a cell voltage of about 4-6 volts for 2-5 hours. These values may be varied with changes in cell configuration and makeup. Following electrochemical charging treatment, the resulting intercalated particles (beads) were washed with water and dried.
(28) Subsequently, some of the alkali metal ion-intercalated compound was transferred to a water bath. The compound, upon contact with water, was found to induce extremely rapid and high expansions of graphite crystallites. Subsequently, some portion of this expanded/exfoliated graphite solution was subjected to sonication. Various samples were collected with their morphology studied by SEM and TEM observations and their specific surface areas measured by the well-known BET method.
(29) TABLE-US-00001 TABLE 1 Results of varying types of liquid electrolytes (alkali metal salts, solvents, and wetting agents). Specific Sam- Intercalating Wetting surface area ple agents agent (m.sup.2/g) Comments P-1 LiClO.sub.4 in EC None 720 >65% single- layer P-1-w LiClO.sub.4 in EC Melamine 824 >80% single- layer P-2 NaClO.sub.4 in EC None 810 >80% single- layer P-2-w NaClO.sub.4 in EC Melamine 910 >90% single- layer P-3 KClO.sub.4 in EC None 625 >40% single- layer P-3-w KClO.sub.4 in EC Melamine 690 >60% single- layer P-4 (LiClO.sub.4 + NaClO.sub.4) None 885 >85% single- in EC layer P-4-w (LiClO.sub.4 + NaClO.sub.4) Sodium 915 >90% single- in EC (ethylene- layer diamine) P-5 (LiClO.sub.4 + KClO.sub.4) None 730 >70% single- in EC layer P-5-w (LiClO.sub.4 + KClO.sub.4) Sodium 823 >80% single- in EC (ethylene- layer diamine) P-6 NaClO.sub.4 + PC None 683 >60% single- layer P-6-w NaClO.sub.4 + PC Hexa- 810 >80% single- methylene layer tetramine P-7 LiClO.sub.4 + PC None 640 >50% single- layer P-7-w LiClO.sub.4 + PC Hexa- 756 >70% single- methylene layer tetramine
(30) Several important observations may be made from the data in this table: 1) The intercalating electrolyte containing a graphene plane wetting agent leads to thinner (mostly single-layer) graphene sheets as compared to the electrolyte containing no such wetting agent. 2) Larger alkali metal ions (Na.sup.+ and K.sup.+), relative to Li.sup.+, are also effective intercalant when it comes to the production of ultra-thin graphene sheets. Actually, Na.sup.+ ions are more effective than Li.sup.+ in this aspect. 3) A mixture of two alkali metal salts (e.g. LiClO.sub.4+NaClO.sub.4) is more effective than single components alone in producing single-layer graphene sheets. 4) EC appears to be more effective than PC. 5) Products containing a majority of graphene sheets being single-layer graphene can be readily produced using the presently invented electrochemical intercalation method.
Certain amounts of the mostly multi-layer graphene sheets were then subjected to re-intercalation under comparable electrochemical intercalation conditions to obtain re-intercalated NGPs. Subsequently, these re-intercalated NGPs were transferred to an ultrasonication bath ultra-thin NGPs. Electron microscopic examinations of selected samples indicate that the majority of the resulting NGPs are single-layer graphene sheets.
COMPARATIVE EXAMPLE 1
Sulfuric-Nitric Acid-Intercalated Graphite Rock Particles
(31) One gram of milled graphite rock powder as used in Example 1 were intercalated with a mixture of sulfuric acid, nitric acid, and potassium permanganate at a weight ratio of 4:1:0.05 (graphite-to-intercalate ratio of 1:3) for four hours. Upon completion of the intercalation reaction, the mixture was poured into deionized water and filtered. The sample was then washed with 5% HCl solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 5. The dried sample was then exfoliated at 1,000° C. for 45 seconds. The resulting NGPs were examined using SEM and TEM and their length (largest lateral dimension) and thickness were measured. It was observed that the presently invented electrochemical intercalation method leads to graphene sheets of comparable thickness distribution, but much larger lateral dimensions (3-5 μm vs. 200-300 nm). Graphene sheets were made into graphene paper layer using a well-known vacuum-assisted filtration procedure. The graphene paper prepared from hydrazine-reduced graphene oxide (made from sulfuric-nitric acid-intercalated graphite) exhibits electrical conductivity values of 25-350 S/cm. The graphene paper prepared from the relatively oxidation-free graphene sheets made by the presently invented electrochemical intercalation exhibit conductivity values of 2,500-4,500 S/cm.
EXAMPLE 2
Graphene Sheets from Milled Graphite Rock (Graphite Ore or Mineral)
(32) Samples of two grams each of graphite rock containing 56% natural flake graphite were milled down to an average diameter of 18.3 μm. The powder samples were subjected to similar electrochemical intercalation conditions described in Example 1, but with different alkali metal salts and solvents. The graphite rock powder samples were subjected to an electrochemical intercalation treatment at a current of 0.5 amps (current density of about 0.04 amps/cm.sup.2) and at a cell voltage of about 6 volts for 3 hours. Following the electrochemical intercalation treatment, the resulting intercalated flake was removed from the electrochemical reactor and dried.
(33) Subsequently, the intercalated compound was transferred to a furnace pre-set at a temperature of 950° C. for 45 seconds. The compound was found to induce rapid and high expansions of graphite crystallites with an expansion ratio of greater than 100. After a mechanical shearing treatment in a high-shear rotating blade device for 15 minutes, the resulting NGPs exhibit a thickness ranging from single-layer graphene sheets to 8-layer graphene sheets based on SEM and TEM observations. Results are summarized in Table 2 below:
(34) TABLE-US-00002 TABLE 2 Results of varying types of intercalating agents and wetting agents. Specific Sam- Alkali metal Wetting surface area ple salt in solvent agent (m.sup.2/g) Comments R-1 LiPF.sub.6 + PC None 712 >65% single- layer R-1-w LiPF.sub.6 + PC Tetraalky- 785 >75% single- ammonium layer R-2 (LiPF.sub.6 + NaPF.sub.6) + None 780 >75% single- PC layer R-2-w (LiPF.sub.6 + NaPF.sub.6) + Tetraalky- 854 >85% single- PC ammonium layer R-3 LiBF.sub.4 + PC None 670 >60% single- layer R-3-w LiBF.sub.4 + PC Carbamide 740 >70% single- layer R-4 LiTFSI + (PC + None 675 >60% single- EC) layer R-4-w LiTFSI + (PC + Carbamide 766 >70% single- EC) layer R-5 LiPF.sub.6 + DOL None 630 >50% single- layer R-5-w LiPF.sub.6 + DOL Organic 722 >65% single- amine layer R-6 LiPF.sub.6 + DME None 665 >60% single- layer R-6-w LiPF.sub.6 + DME Organic 776 >75% single- amine layer
(35) It may be noted that the interstitial spaces between two hexagonal carbon atomic planes (graphene planes) are only approximately 0.28 nm (the plane-to-plane distance is 0.34 nm). A skilled person in the art would predict that larger molecules and/or ions (K.sup.+ vs. Li.sup.+) cannot intercalate into interstitial spaces of a layered graphite material. After intensive R&D efforts, we found that electrochemical methods with a proper combination of an alkali metal salt and solvent, and an adequate magnitude of the imposing current density could be used to open up the interstitial spaces to accommodate much larger molecules and/or ions. The presence of a graphene plane-wetting agent serves to prevent exfoliated graphene sheets from being re-stacked back to a graphite structure.
(36) Re-intercalation of those multi-layer NGPs and subsequent exfoliation resulted in further reduction in platelet thickness, with an average thickness of approximately 0.75 nm (approximately 2 graphene planes on average).
EXAMPLE 3
Production of Isolated Graphene Sheets from Electrochemical Interaction, Exfoliation, and Separation of Milled Graphite Rock in an Aqueous Electrolyte Solution
(37) Samples of two grams each of graphite ore powder were milled down to an average size of 27 μm. The powder samples were subjected to electrochemical intercalation in aqueous electrolyte. A broad array of metal halide salts were dissolved in deionized water to form a liquid electrolyte. The wetting agents investigated include ammonia, ammonium sulfate, and sodium dodecyl sulfate. The graphite ore samples were subjected to an electrochemical intercalation treatment at a current of 0.5 amps (current density of about 0.04 amps/cm.sup.2) and at a cell voltage of about 1.8 volts for 3 hours. Following the electrochemical intercalation treatment, the resulting intercalated graphite (mostly Stage-1 GIC with some Stage-2) was removed from the electrochemical reactor and dried.
(38) Subsequently, the intercalated compound was transferred to a furnace pre-set at a temperature of 1,050° C. for 60 seconds. The compound was found to induce rapid and high expansions of graphite crystallites with an expansion ratio of greater than 200. After a mechanical shearing treatment in a high-shear rotating blade device for 15 minutes, the resulting NGPs exhibit a thickness ranging from single-layer graphene sheets to 5-layer graphene sheets based on SEM and TEM observations. Results are summarized in Table 3 below. It is clear that a wide variety of metal salts (MCl, MCl.sub.2, and MCl.sub.3, etc.; M=a metal) dissolved in a select solvent (e.g. water) can be utilized as an intercalating agent in the presently invented method, making this a versatile and environmentally benign approach (e.g. as opposed to the conventional method using strong sulfuric acid and oxidizing agents). It is also surprising to discover that a graphene plane wetting agent can be used to significantly improve the electrochemical intercalation and exfoliation process for the production of ultra-thin graphene sheets.
(39) TABLE-US-00003 TABLE 3 Results of varying types of intercalating and wetting agents. % of single Specific or few-layer Sam- Aqueous Wetting surface area graphene sheets ple electrolyte agent (m.sup.2/g) (1-10 layers) C-1 LiCl + water None 310 >35% C-1-w LiCl + watr Ammonium 425 >60% sulfate C-2 LiI + water None 225 >20% C-2-w LiI + water Ammonium 414 >60% sulfate C-3 NaCl + water None 210 >15% C-3-w NaCl + water Sodium do- 385 >50% decyl sulfate C-4 NaF + water None 224 >20% C-4-w NaF + water Sodium do- 345 >40% decyl sulfate C-5 NaCl + None 270 >30% LiCl + water C-5-w NaCl + Ammonium 356 >40% LiCl + water sulfate C-6 ZnCl.sub.2 + water None 202 >15% C-6-w ZnCl.sub.2 + water Ammonia 355 >40% C-7 FeCl.sub.3 + water None 330 >35% C-7-w FeCl.sub.3 + water Ammonia 450 >60%
COMPARATIVE EXAMPLE 3
Conventional Hummers Method
(40) Highly intercalated and oxidized graphite was prepared by oxidation of milled graphite particles (same as in Example 3) with sulfuric acid, nitrate, and potassium permanganate according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957]. Upon completion of the reaction (10 hours allowed), the mixture was poured into deionized water and filtered. The sample was then washed with 5% HCl solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 5. The intent was to remove all sulfuric and nitric acid residue out of graphite interstices. The slurry was spray-dried and stored in a vacuum oven at 65° C. for 24 hours. The interlayer spacing of the resulting powder was determined by the Debey-Scherrer X-ray technique to be approximately 0.75 nm (7.5 Å), indicating that graphite has been converted into graphite oxide (Stage-1 and Stage-2 GICs). The dried, intercalated compound was placed in a quartz tube and inserted into a horizontal tube furnace pre-set at 950° C. for 35 seconds. The exfoliated worms were mixed with water and then subjected to a mechanical shearing treatment using a high-shear dispersion machine for 20 minutes. The resulting graphene sheets were found to have a thickness of 2.1-7.7 nm (specific surface areas from 185 to 325 m.sup.2/g). These values are not nearly as good as what is achieved by the instant method, which is also more environmentally benign.