Patent
US 10,435,797Electrochemical Production of Graphene Sheets from Coke or Coal
Aruna Zhamu, Bor Z. Jang
US
Copyright © 2026 Matter42. All rights reserved.
Patent
Atlas literature
Patent
US 10,435,797Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG.1 A flow chart showing an embodiment of the presently invented method of producing isolated graphene sheets.
FIG.2 Schematic drawing of an apparatus for electrochemical intercalation of coal or coke.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of producing isolated graphene sheets from a supply of coke or coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated coke or coal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coke or coal powder is selected from petroleum coke, coal- derived coke, meso-phase coke, synthetic coke, leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises an alkali metal or metal halide; wherein said liquid solution electrolyte further comprises a graphene plane- wetting agent selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1 -pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴-styrene sulfonate), and combinations thereof, and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coke or coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Previously presented
The method of claim 1, wherein multiple particles of said coke or coal 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 physical contact with said counter electrode. Previously presented
The method of claim 1, wherein said method is conducted intermittently or continuously and said supply of coke or coal powder and said liquid solution electrolyte are provided into said reactor intermittently or continuously. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 20% by weight. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 50% by weight. Original
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. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 0.1 to 600 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 1 to 500 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 10 to 300 A/m 2. Original
The method of claim 1, wherein said thermal shock exposure comprises heating said intercalated coke or coal compound to a temperature in the range of 300-1,200 ° C for a period of 15 seconds to 2 minutes. Original
The method of claim 1, wherein said isolated graphene sheets contain single- layer graphene. Original
The method of claim 1, wherein said isolated graphene sheets contain few-layer graphene having 2-10 hexagonal carbon atomic interlayers or graphene planes. Original
The method of claim 1, wherein said electrochemical intercalation includes intercalation of both said intercalating agent and said wetting agent into the interlayer spacing. Previously presented
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 and a step of 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. Original
The method of claim 1, wherein said intercalating agent includes a metal halide selected from the group consisting of MC l (M = Li, Na, K, Cs), M CI 2 (M = Zn, Ni, Cu, Mn), MC₁ 3 (M = Al, Fe, Ga), MC l 4 (M = Zr, Pt), MF 2 (M = Zn, Ni, Cu, Mn), MF 3 (M = Al, Fe, Ga), MF 4 (M = Zr, Pt), and combinations thereof. Original
The method of claim 1, wherein said intercalating agent comprises an alkali metal salt selected from the group consisting of sodium perchlorate (NaC lO 4), potassium perchlorate (KC 10 4), sodium hexafluorophosphate (NaPF 6), potassium hexafluorophosphate (KPF 6), sodium borofluoride (NaBF 4), potassium borofluoride (KBF 4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF 3 S O 3), potassium trifluoro-methanesulfonate (KCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2) 2), sodium trifluoromethanesulfonimide (NaTFS I), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2) 2), a sodium ionic liquid salt, lithium perchlorate (LiC lO 4), lithium hexafluorophosphate (LiPF 6), lithium borofluoride (LiBF 4), lithium hexafluoroarsenide (LiAsF 6), lithium trifluoro-methanesulfonate (LiCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2) 2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4), G 4 -) -lithium nitrate (LiNO 3), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3) 3), lithium bispe r fluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, and combinations thereof. Currently amended
The method of claim 1, wherein said intercalating agent comprises an organic solvent selected from the group consisting 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 (EE E), 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 (E A), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofloroether, and combinations thereof. Currently amended
Canceled
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A method of producing isolated graphene sheets from a supply of coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated oal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coal powder is selected from leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises dichloroacetic acid (C₁ 2 CH COO H), or an alkylsulfonic acid selected from methanesulfonic (MeS O 3 H), ethanesulfonic (EtS O 3 H), 1-propanesulfonic (n-PrSO 3 H), or a combination thereof and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Currently amended
The method of claim 24, wherein said reactor further comprises a graphene plane-wetting agent dissolved in said liquid solution electrolyte, wherein said graphene plane-wetting agent is selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴- styrene sulfonate), and combinations thereof. Previously presented
The method of claim 24, wherein said coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a Currently amended
The method of claim 24, wherein the imposing range of 0. 1 to 600 A/m 2. Previously presented concentration from 20% to 50% by weight. current provides a current density in the
Materials described outside the worked examples.
coke or coal powder
intercalated coke or coal compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 10–120 s | — |
Temperature |
Patent
Atlas literature
Patent
US 10,435,797Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG.1 A flow chart showing an embodiment of the presently invented method of producing isolated graphene sheets.
FIG.2 Schematic drawing of an apparatus for electrochemical intercalation of coal or coke.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of producing isolated graphene sheets from a supply of coke or coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated coke or coal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coke or coal powder is selected from petroleum coke, coal- derived coke, meso-phase coke, synthetic coke, leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises an alkali metal or metal halide; wherein said liquid solution electrolyte further comprises a graphene plane- wetting agent selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1 -pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴-styrene sulfonate), and combinations thereof, and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coke or coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Previously presented
The method of claim 1, wherein multiple particles of said coke or coal 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 physical contact with said counter electrode. Previously presented
The method of claim 1, wherein said method is conducted intermittently or continuously and said supply of coke or coal powder and said liquid solution electrolyte are provided into said reactor intermittently or continuously. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 20% by weight. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 50% by weight. Original
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. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 0.1 to 600 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 1 to 500 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 10 to 300 A/m 2. Original
The method of claim 1, wherein said thermal shock exposure comprises heating said intercalated coke or coal compound to a temperature in the range of 300-1,200 ° C for a period of 15 seconds to 2 minutes. Original
The method of claim 1, wherein said isolated graphene sheets contain single- layer graphene. Original
The method of claim 1, wherein said isolated graphene sheets contain few-layer graphene having 2-10 hexagonal carbon atomic interlayers or graphene planes. Original
The method of claim 1, wherein said electrochemical intercalation includes intercalation of both said intercalating agent and said wetting agent into the interlayer spacing. Previously presented
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 and a step of 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. Original
The method of claim 1, wherein said intercalating agent includes a metal halide selected from the group consisting of MC l (M = Li, Na, K, Cs), M CI 2 (M = Zn, Ni, Cu, Mn), MC₁ 3 (M = Al, Fe, Ga), MC l 4 (M = Zr, Pt), MF 2 (M = Zn, Ni, Cu, Mn), MF 3 (M = Al, Fe, Ga), MF 4 (M = Zr, Pt), and combinations thereof. Original
The method of claim 1, wherein said intercalating agent comprises an alkali metal salt selected from the group consisting of sodium perchlorate (NaC lO 4), potassium perchlorate (KC 10 4), sodium hexafluorophosphate (NaPF 6), potassium hexafluorophosphate (KPF 6), sodium borofluoride (NaBF 4), potassium borofluoride (KBF 4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF 3 S O 3), potassium trifluoro-methanesulfonate (KCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2) 2), sodium trifluoromethanesulfonimide (NaTFS I), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2) 2), a sodium ionic liquid salt, lithium perchlorate (LiC lO 4), lithium hexafluorophosphate (LiPF 6), lithium borofluoride (LiBF 4), lithium hexafluoroarsenide (LiAsF 6), lithium trifluoro-methanesulfonate (LiCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2) 2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4), G 4 -) -lithium nitrate (LiNO 3), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3) 3), lithium bispe r fluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, and combinations thereof. Currently amended
The method of claim 1, wherein said intercalating agent comprises an organic solvent selected from the group consisting 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 (EE E), 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 (E A), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofloroether, and combinations thereof. Currently amended
Canceled
Canceled
Canceled
Canceled
Canceled
A method of producing isolated graphene sheets from a supply of coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated oal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coal powder is selected from leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises dichloroacetic acid (C₁ 2 CH COO H), or an alkylsulfonic acid selected from methanesulfonic (MeS O 3 H), ethanesulfonic (EtS O 3 H), 1-propanesulfonic (n-PrSO 3 H), or a combination thereof and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Currently amended
The method of claim 24, wherein said reactor further comprises a graphene plane-wetting agent dissolved in said liquid solution electrolyte, wherein said graphene plane-wetting agent is selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴- styrene sulfonate), and combinations thereof. Previously presented
The method of claim 24, wherein said coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a Currently amended
The method of claim 24, wherein the imposing range of 0. 1 to 600 A/m 2. Previously presented concentration from 20% to 50% by weight. current provides a current density in the
Materials described outside the worked examples.
coke or coal powder
intercalated coke or coal compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 10–120 s | — |
Temperature |
Patent
Atlas literature
Patent
US 10,435,797Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG.1 A flow chart showing an embodiment of the presently invented method of producing isolated graphene sheets.
FIG.2 Schematic drawing of an apparatus for electrochemical intercalation of coal or coke.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of producing isolated graphene sheets from a supply of coke or coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated coke or coal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coke or coal powder is selected from petroleum coke, coal- derived coke, meso-phase coke, synthetic coke, leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises an alkali metal or metal halide; wherein said liquid solution electrolyte further comprises a graphene plane- wetting agent selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1 -pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴-styrene sulfonate), and combinations thereof, and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coke or coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Previously presented
The method of claim 1, wherein multiple particles of said coke or coal 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 physical contact with said counter electrode. Previously presented
The method of claim 1, wherein said method is conducted intermittently or continuously and said supply of coke or coal powder and said liquid solution electrolyte are provided into said reactor intermittently or continuously. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 20% by weight. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 50% by weight. Original
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. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 0.1 to 600 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 1 to 500 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 10 to 300 A/m 2. Original
The method of claim 1, wherein said thermal shock exposure comprises heating said intercalated coke or coal compound to a temperature in the range of 300-1,200 ° C for a period of 15 seconds to 2 minutes. Original
The method of claim 1, wherein said isolated graphene sheets contain single- layer graphene. Original
The method of claim 1, wherein said isolated graphene sheets contain few-layer graphene having 2-10 hexagonal carbon atomic interlayers or graphene planes. Original
The method of claim 1, wherein said electrochemical intercalation includes intercalation of both said intercalating agent and said wetting agent into the interlayer spacing. Previously presented
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 and a step of 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. Original
The method of claim 1, wherein said intercalating agent includes a metal halide selected from the group consisting of MC l (M = Li, Na, K, Cs), M CI 2 (M = Zn, Ni, Cu, Mn), MC₁ 3 (M = Al, Fe, Ga), MC l 4 (M = Zr, Pt), MF 2 (M = Zn, Ni, Cu, Mn), MF 3 (M = Al, Fe, Ga), MF 4 (M = Zr, Pt), and combinations thereof. Original
The method of claim 1, wherein said intercalating agent comprises an alkali metal salt selected from the group consisting of sodium perchlorate (NaC lO 4), potassium perchlorate (KC 10 4), sodium hexafluorophosphate (NaPF 6), potassium hexafluorophosphate (KPF 6), sodium borofluoride (NaBF 4), potassium borofluoride (KBF 4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF 3 S O 3), potassium trifluoro-methanesulfonate (KCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2) 2), sodium trifluoromethanesulfonimide (NaTFS I), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2) 2), a sodium ionic liquid salt, lithium perchlorate (LiC lO 4), lithium hexafluorophosphate (LiPF 6), lithium borofluoride (LiBF 4), lithium hexafluoroarsenide (LiAsF 6), lithium trifluoro-methanesulfonate (LiCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2) 2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4), G 4 -) -lithium nitrate (LiNO 3), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3) 3), lithium bispe r fluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, and combinations thereof. Currently amended
The method of claim 1, wherein said intercalating agent comprises an organic solvent selected from the group consisting 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 (EE E), 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 (E A), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofloroether, and combinations thereof. Currently amended
Canceled
Canceled
Canceled
Canceled
Canceled
A method of producing isolated graphene sheets from a supply of coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated oal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coal powder is selected from leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises dichloroacetic acid (C₁ 2 CH COO H), or an alkylsulfonic acid selected from methanesulfonic (MeS O 3 H), ethanesulfonic (EtS O 3 H), 1-propanesulfonic (n-PrSO 3 H), or a combination thereof and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Currently amended
The method of claim 24, wherein said reactor further comprises a graphene plane-wetting agent dissolved in said liquid solution electrolyte, wherein said graphene plane-wetting agent is selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴- styrene sulfonate), and combinations thereof. Previously presented
The method of claim 24, wherein said coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a Currently amended
The method of claim 24, wherein the imposing range of 0. 1 to 600 A/m 2. Previously presented concentration from 20% to 50% by weight. current provides a current density in the
Materials described outside the worked examples.
coke or coal powder
intercalated coke or coal compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 10–120 s | — |
Temperature |
Patent
Atlas literature
Patent
US 10,435,797Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG.1 A flow chart showing an embodiment of the presently invented method of producing isolated graphene sheets.
FIG.2 Schematic drawing of an apparatus for electrochemical intercalation of coal or coke.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of producing isolated graphene sheets from a supply of coke or coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated coke or coal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coke or coal powder is selected from petroleum coke, coal- derived coke, meso-phase coke, synthetic coke, leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises an alkali metal or metal halide; wherein said liquid solution electrolyte further comprises a graphene plane- wetting agent selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1 -pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴-styrene sulfonate), and combinations thereof, and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coke or coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Previously presented
The method of claim 1, wherein multiple particles of said coke or coal 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 physical contact with said counter electrode. Previously presented
The method of claim 1, wherein said method is conducted intermittently or continuously and said supply of coke or coal powder and said liquid solution electrolyte are provided into said reactor intermittently or continuously. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 20% by weight. Original
The method of claim 1, wherein said coke or coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a concentration higher than 50% by weight. Original
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. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 0.1 to 600 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 1 to 500 A/m 2. Original
The method of claim 1, wherein the imposing current provides a current density in the range of 10 to 300 A/m 2. Original
The method of claim 1, wherein said thermal shock exposure comprises heating said intercalated coke or coal compound to a temperature in the range of 300-1,200 ° C for a period of 15 seconds to 2 minutes. Original
The method of claim 1, wherein said isolated graphene sheets contain single- layer graphene. Original
The method of claim 1, wherein said isolated graphene sheets contain few-layer graphene having 2-10 hexagonal carbon atomic interlayers or graphene planes. Original
The method of claim 1, wherein said electrochemical intercalation includes intercalation of both said intercalating agent and said wetting agent into the interlayer spacing. Previously presented
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 and a step of 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. Original
The method of claim 1, wherein said intercalating agent includes a metal halide selected from the group consisting of MC l (M = Li, Na, K, Cs), M CI 2 (M = Zn, Ni, Cu, Mn), MC₁ 3 (M = Al, Fe, Ga), MC l 4 (M = Zr, Pt), MF 2 (M = Zn, Ni, Cu, Mn), MF 3 (M = Al, Fe, Ga), MF 4 (M = Zr, Pt), and combinations thereof. Original
The method of claim 1, wherein said intercalating agent comprises an alkali metal salt selected from the group consisting of sodium perchlorate (NaC lO 4), potassium perchlorate (KC 10 4), sodium hexafluorophosphate (NaPF 6), potassium hexafluorophosphate (KPF 6), sodium borofluoride (NaBF 4), potassium borofluoride (KBF 4), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-methanesulfonate (NaCF 3 S O 3), potassium trifluoro-methanesulfonate (KCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2) 2), sodium trifluoromethanesulfonimide (NaTFS I), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2) 2), a sodium ionic liquid salt, lithium perchlorate (LiC lO 4), lithium hexafluorophosphate (LiPF 6), lithium borofluoride (LiBF 4), lithium hexafluoroarsenide (LiAsF 6), lithium trifluoro-methanesulfonate (LiCF 3 S₀ 3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2) 2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 0 4), G 4 -) -lithium nitrate (LiNO 3), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3) 3), lithium bispe r fluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, and combinations thereof. Currently amended
The method of claim 1, wherein said intercalating agent comprises an organic solvent selected from the group consisting 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 (EE E), 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 (E A), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofloroether, and combinations thereof. Currently amended
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A method of producing isolated graphene sheets from a supply of coal powder containing therein domains of hexagonal carbon atoms and/or hexagonal carbon atomic interlayers with an interlayer spacing, said method comprising: (a) forming an intercalated oal compound by an electrochemical intercalation procedure which is conducted in an intercalation reactor, wherein said reactor contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains said coke or coal powder as an active material in ionic contact with said liquid solution electrolyte, wherein said coal powder is selected from leonardite, anthracite, lignite coal, bituminous coal, natural coal mineral powder, or a combination thereof; 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 into said interlayer spacing; wherein said intercalating agent comprises dichloroacetic acid (C₁ 2 CH COO H), or an alkylsulfonic acid selected from methanesulfonic (MeS O 3 H), ethanesulfonic (EtS O 3 H), 1-propanesulfonic (n-PrSO 3 H), or a combination thereof and (b) exfoliating and separating said hexagonal carbon atomic interlayers from said intercalated coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce said isolated graphene sheets. Currently amended
The method of claim 24, wherein said reactor further comprises a graphene plane-wetting agent dissolved in said liquid solution electrolyte, wherein said graphene plane-wetting agent is selected from the group consisting of melamine, sodium (ethylenediamine), tetraalkylammonium, ammonia, carbamide, hexamethylenetetramine, organic amine, pyrene, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenamine, poly(sodium⁻⁴- styrene sulfonate), and combinations thereof. Previously presented
The method of claim 24, wherein said coal powder in said working electrode compartment is dispersed in the liquid solution electrolyte at a Currently amended
The method of claim 24, wherein the imposing range of 0. 1 to 600 A/m 2. Previously presented concentration from 20% to 50% by weight. current provides a current density in the
Materials described outside the worked examples.
coke or coal powder
intercalated coke or coal compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 10–120 s | — |
Temperature |
graphene plane-wetting agent
isolated graphene sheets
single-layer graphene
few-layer graphene
metal halide intercalating agent
alkali metal salt intercalating agent
organic solvent intercalating agent
coal powder
alkylsulfonic acid/dichloroacetic acid intercalating agent
| 300–1200 °C |
| — |
Temperature | 600–1000 °C | — |
Duration | 30–60 seconds | — |
Thickness | 200–300 nm | — |
Thickness | 2.2–7.9 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 3.4 nm | — |
Thickness | ≤ 2 nm | — |
Duration | 15–120 s | — |
graphene plane-wetting agent
isolated graphene sheets
single-layer graphene
few-layer graphene
metal halide intercalating agent
alkali metal salt intercalating agent
organic solvent intercalating agent
coal powder
alkylsulfonic acid/dichloroacetic acid intercalating agent
| 300–1200 °C |
| — |
Temperature | 600–1000 °C | — |
Duration | 30–60 seconds | — |
Thickness | 200–300 nm | — |
Thickness | 2.2–7.9 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 3.4 nm | — |
Thickness | ≤ 2 nm | — |
Duration | 15–120 s | — |
graphene plane-wetting agent
isolated graphene sheets
single-layer graphene
few-layer graphene
metal halide intercalating agent
alkali metal salt intercalating agent
organic solvent intercalating agent
coal powder
alkylsulfonic acid/dichloroacetic acid intercalating agent
| 300–1200 °C |
| — |
Temperature | 600–1000 °C | — |
Duration | 30–60 seconds | — |
Thickness | 200–300 nm | — |
Thickness | 2.2–7.9 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 3.4 nm | — |
Thickness | ≤ 2 nm | — |
Duration | 15–120 s | — |
graphene plane-wetting agent
isolated graphene sheets
single-layer graphene
few-layer graphene
metal halide intercalating agent
alkali metal salt intercalating agent
organic solvent intercalating agent
coal powder
alkylsulfonic acid/dichloroacetic acid intercalating agent
| 300–1200 °C |
| — |
Temperature | 600–1000 °C | — |
Duration | 30–60 seconds | — |
Thickness | 200–300 nm | — |
Thickness | 2.2–7.9 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 3.4 nm | — |
Thickness | ≤ 2 nm | — |
Duration | 15–120 s | — |