Direct microwave production of graphene

Patent metadata

Field	Value
Publication number	US-10896784-B2
Application number	US-201715475451-A
Country	US
Kind code	B2
Filing date	Mar 31, 2017
Priority date	Mar 31, 2017
Publication date	Jan 19, 2021
Grant date	Jan 19, 2021

Abstract

Provided is a method of producing graphene directly from a non-intercalated and non-oxidized graphitic material, comprising: (a) dispersing the graphitic material in a liquid solution to form a suspension, wherein the graphitic material has never been previously exposed to chemical intercalation or oxidation; and (b) subjecting the suspension to microwave or radio frequency irradiation with a frequency and an intensity for a length of time sufficient for producing graphene; wherein the liquid solution contains a metal salt dissolved in water, organic solvent, ionic liquid solvent, or a combination thereof. The method is fast (minutes as opposed to hours or days of conventional processes), environmentally benign, and highly scalable.

First claim

The invention claimed is:

1. A method of producing graphene directly from a non-intercalated and non-oxidized graphitic material, said method comprising:
(a) dispersing said graphitic material in a liquid solution to form a suspension, wherein said graphitic material has never been previously exposed to chemical intercalation or oxidation; and
(b) subjecting said suspension to microwave or radio frequency irradiation with a frequency and an intensity for a length of time sufficient for producing said graphene;
wherein said liquid solution contains a metal salt dissolved in water, organic solvent, ionic liquid solvent, or a combination thereof, wherein said liquid solution has a salt concentration from 0.01 M to 10 M;
wherein said method does not include strong acids.

2. The method of claim 1 , wherein said metal salt is a metal halide selected from the group consisting of MCl (M=Li, Na, K, Cs), MCl 2 (M=Zn, Ni, Cu, Mn), MCl 3 (M=Al, Fe, Ga), MCl 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.

3. The method of claim 1 , wherein said metal salt includes an alkali metal salt selected from lithium perchlorate (LiClO 4 ), sodium perchlorate (NaClO 4 ), potassium perchlorate (KClO 4 ), sodium hexafluorophosphate (NaPF 6 ), potassium hexafluorophosphate (KPF 6 ), sodium borofluoride (NaBF 4 ), potassium borofluoride (KBF 4 ), sodium hexafluoroarsenide, potassium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF 3 SO 3 ), potassium trifluoro-metasulfonate (KCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide sodium (NaN(CF 3 SO 2 ) 2 ), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide potassium (KN(CF 3 SO 2 ) 2 ), a sodium ionic liquid salt, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3 ) 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.

4. The method of claim 3 , wherein said organic solvent 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, ethylene carbonate (EC), propylene carbonate (PC), 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 hydrofluoroether, or a combination thereof.

5. The method of claim 1 wherein said graphitic material is selected from natural graphite, synthetic graphite, amorphous graphite, highly oriented pyrolytic graphite, meso-carbon micro-bead, graphitized meso-phase carbon, needle coke, carbon fiber, graphite fiber, carbon nano-fiber, graphitic nano-fiber, graphite fluoride, chemically modified graphite, expanded graphite, or a combination thereof.

6. The method of claim 1 wherein said microwave or radio frequency irradiation time is from 1 minute to 60 minutes.

7. The method of claim 1 wherein said microwave or radio frequency irradiation time is less than 30 minutes.

8. The method of claim 1 wherein said microwave or radio frequency irradiation time is less than 10 minutes.

9. The method of claim 1 , wherein said microwave or radio frequency irradiation is followed by a mechanical shearing treatment to produce a thinner or smaller graphene material.

10. The method of claim 9 , wherein said mechanical shearing treatment comprises using air milling, air jet milling, ball milling, rotating-blade mechanical shearing, ultrasonication, cavitation, or a combination thereof.

11. The method of claim 1 , wherein said liquid solution further comprises a chemical functionalizing agent and said microwave or radio frequency irradiation activates a chemical reaction between said agent and said graphene to produce a chemically functionalized graphene material.

12. The method of claim 1 wherein said graphene contains single-layer graphene sheets.

13. The method of claim 1 wherein said graphene contains at least 80% single-layer graphene sheets.

14. The method of claim 1 wherein said graphene contains pristine graphene, oxidized graphene with less than 5% oxygen content by weight, graphene fluoride, graphene fluoride with less than 5% fluorine by weight, graphene with a carbon content no less than 95% by weight, or functionalized graphene.

15. A slurry containing said metal salt solution and graphene sheets created by the process of claim 1 .

16. A supercapacitor, sodium battery, or lithium battery containing the slurry of claim 15 .

17. A method of producing graphene directly from a non-intercalated and non-oxidized graphitic material, said method comprising:
(a) dispersing said graphitic material in a liquid solution to form a suspension, wherein said graphitic material has never been previously exposed to chemical intercalation or oxidation; and
(b) subjecting said suspension to microwave or radio frequency irradiation;
wherein said liquid solution contains a metal salt, excluding lithium salt, aluminum salt, iron salt, copper salt, sodium salt, or a combination thereof, dissolved in water, organic solvent, ionic liquid solvent, or a combination thereof wherein said microwave or radio frequency irradiation time is from 1 minute to 60 minutes.

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Lin Yi-Jun
• Zhamu Aruna
• Jang Bor Z

Classifications

• Y10S977/842

  for carbon nanotubes or fullerenes · CPC title

• H01G11/32

  Carbon-based · CPC title

• C01B32/192

  starting from graphitic oxides · CPC title

• B01J19/126

  Microwaves · CPC title

• H01M4/625

  Carbon or graphite · CPC title