# US 9,040,013 B2 · Method of preparing functionalized graphene > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,013 B2 - Document ID: US9040013B2 - Status: Granted - Kind: B2 - Application number: 13/198,342 - Filed: 2011-08-04 - Published: 2013-02-07 - Granted: 2015-05-26 - Earliest claimed: 2011-08-04 - Assignees: Baker Hughes Incorporated - Applicants: Anil K. Sadana - Inventors: Anil K. Sadana - Web page: https://patentgrep.com/patent/US9040013B2 ## CPC - C07C 1/26: starting from organic compounds containing only halogen atoms as hetero-atoms - B82Y 40/00: Manufacture or treatment of nanostructures - C01B 32/194: After-treatment - Y10S 977/896: Chemical synthesis, e.g. chemical bonding or breaking - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A method of preparing functionalized graphene, comprises treating graphene with an alkali metal in the presence of an electron transfer agent and coordinating solvent, and adding a functionalizing compound. The method further includes quenching unreacted alkali metal by addition of a protic medium, and isolating the functionalized graphene. ## Claims ### Claim 1 A method of preparing functionalized graphene, comprising: treating graphene, with an alkali metal, in the presence of a coordinating solvent, and adding a functionalizing compound, wherein that the coordinating solvent comprises at least one of an ether or a tertiary amine; and wherein the coordinating solvent is free of ammonia. ### Claim 2 (depends on 1) The method of claim 1, wherein the graphene has an average particle size of less than about 1 micrometer. ### Claim 3 (depends on 1) The method of claim 1, wherein the graphene has an average particle size of greater than or equal to about 1 micrometer. ### Claim 4 (depends on 3) The method of claim 3, wherein the graphene has an average particle size of about 1 to about 10 micrometers. ### Claim 5 (depends on 1) The method of claim 1, wherein the graphene has a two-dimensional aspect ratio of greater than about 10. ### Claim 6 (depends on 1) The method of claim 1, wherein the graphene is exfoliated by fluorination, acid intercalation, acid intercalation followed by thermal shock treatment, or a combination comprising at least one of the foregoing. ### Claim 7 (depends on 1) The method of claim 1, wherein the alkali metal is lithium, sodium, or potassium. ### Claim 8 (depends on 1) The method of claim 1, wherein the ether is tetrahydrofuran, dioxane, diethyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, methyl-t-butyl ether, 1,2-dimethoxyethane, 1,2-dimethoxypropane, 1,3-dimethoxypropane, 1,2-diethoxyethane, 1,2-diethoxypropane, 1,3-diethoxypropane, or a combination comprising at least one of the foregoing. ### Claim 9 A method of preparing functionalized graphene, comprising: treating graphene, with an alkali metal, in the presence of a coordinating solvent, and adding a functionalizing compound, wherein the coordinating solvent comprises at least one of an ether; or an amine; and wherein the amine comprises a tertiary amine. ### Claim 10 (depends on 9) The method of claim 9, wherein the tertiary amine is n-methyl piperidine, n-methyl morpholine, N,N,N′,N′-tetramethyl-1,2-diaminoethane, or a combination comprising at least one of the foregoing. ### Claim 11 (depends on 1) The method of claim 1, further comprising a non-coordinating solvent. ### Claim 12 (depends on 11) The method of claim 11, wherein the non-coordinating solvent is a hydrocarbon solvent. ### Claim 13 (depends on 1) The method of claim 1, wherein treating is carried out at less than or equal to ambient temperature. ### Claim 14 (depends on 1) The method of claim 1, wherein the functionalizing compound comprises an alkyl halide, aralkyl halide, ester, amide, carbonate, aldehyde, unsaturated ester, or a combination comprising at least one of the foregoing. ### Claim 15 (depends on 1) The method of claim 1, wherein treating comprises dissolving the alkali metal in the coordinating solvent, followed by adding the graphene. ### Claim 16 (depends on 15) The method of claim 15, wherein treating further comprises adding an electron transfer agent to the coordinating solvent prior to dissolving the alkali metal. ### Claim 17 (depends on 1) The method of claim 1, wherein the alkali metal and the functionalizing compound are present in a molar ratio of about 1.2:1 to 1:1.2, respectively. ### Claim 18 (depends on 1) The method of claim 1, wherein treating is carried out for less than or equal to 1 hour. ### Claim 19 (depends on 1) The method of claim 1, further comprising: quenching unreacted alkali metal by addition of a protic medium, and isolating the functionalized graphene. ### Claim 20 (depends on 1) The method of claim 1, wherein the functionalized graphene has functional groups including carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, lactone, aryl, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the forgoing functional groups. ### Claim 21 A method of preparing functionalized graphene, comprising: dissolving an alkali metal, in a coordinating solvent, adding graphene, and adding a functionalizing compound, wherein that the coordinating solvent comprises an ether, a tertiary amine, or a combination comprising at least one of the foregoing; and wherein the coordinating solvent is free of ammonia. ### Claim 22 A method of preparing functionalized graphene, comprising: combining tetrahydrofuran, with naphthalene, dissolving an alkali metal, in the combination of tetrahydrofuran and naphthalene, adding graphene, and adding a functionalizing compound. ### Claim 23 (depends on 22) The method of claim 22, wherein the alkali metal comprises sodium. ### Claim 24 (depends on 1) The method of claim 1, wherein the ether is dioxane, diethyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, methyl-t-butyl ether, 1,2-dimethoxyethane, 1,2-dimethoxypropane, 1,3-dimethoxypropane, 1,2-diethoxyethane, 1,2-diethoxypropane, 1,3-diethoxypropane, or a combination comprising at least one of the foregoing.