Electrochemical production of graphene sheets from coke or coal

Patent metadata

Field	Value
Publication number	US-11560631-B2
Application number	US-201916596244-A
Country	US
Kind code	B2
Filing date	Oct 8, 2019
Priority date	Jun 26, 2016
Publication date	Jan 24, 2023
Grant date	Jan 24, 2023

Abstract

A method of producing graphene sheets from coke or coal powder, comprising: (a) forming an intercalated coke or coal compound by electrochemical intercalation conducted in an intercalation reactor, which contains (i) a liquid solution electrolyte comprising an intercalating agent; (ii) a working electrode that contains the powder in ionic contact with the liquid electrolyte, wherein the coke or coal powder is selected from petroleum coke, coal-derived coke, meso-phase coke, synthetic coke, leonardite, lignite coal, or natural coal mineral powder; and (iii) a counter electrode in ionic contact with the electrolyte, and wherein a current is imposed upon the working electrode and the counter electrode for effecting electrochemical intercalation of the intercalating agent into the powder; and (b) exfoliating and separating graphene planes from the intercalated coke or coal compound using an ultrasonication, thermal shock exposure, mechanical shearing treatment, or a combination thereof to produce isolated graphene sheets.

First claim

The invention claimed is:

1. 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; 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;
wherein said intercalating agent includes a species selected from a Brønsted acid selected from dichloroacetic (Cl 2 CHCOOH), or an alkylsulfonic acid selected from methanesulfonic (MeSO 3 H), ethanesulfonic (EtSO 3 H), or 1-propanesulfonic (n-PrSO 3 H), or a combination thereof.

2. The method of claim 1 , wherein multiple particles of said coke or coal in a working electrode compartment is dispersed in the liquid solution electrolyte 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 in ionic contact with said counter electrode.

3. The method of claim 2 , wherein said multiple particles are clustered together to form a network of electron-conducting pathways.

4. The method of claim 1 , wherein said reactor further contains a graphene plane-wetting agent dissolved in said liquid solution electrolyte.

5. 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.

6. The method of claim 2 , 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 working electrode compartment intermittently or continuously.

7. The method of claim 2 , 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.

8. The method of claim 2 , 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.

9. 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.

10. The method of claim 1 , wherein the imposing current provides a current density in the range from 0.1 to 600 A/m 2 .

11. The method of claim 1 , wherein the imposing current provides a current density in the range from 1 to 500 A/m 2 .

12. The method of claim 1 , wherein the imposing current provides a current density in the range from 10 to 300 A/m 2 .

13. The method of claim 1 , wherein said thermal shock exposure comprises heating said intercalated coke or coal compound to a temperature in the range from 300-1,200° C. for a period of 15 seconds to 2 minutes.

14. The method of claim 1 , wherein said isolated graphene sheets contain single-layer graphene.

15. The method of claim 1 , wherein said isolated graphene sheets contain few-layer graphene having 2-10 hexagonal carbon atomic interlayers or graphene planes.

16. The method of claim 4 , wherein said electrochemical intercalation includes intercalation of both said intercalating agent and said wetting agent into the interlayer spacing.

17. 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.

Assignees

• Global Graphene Group Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• C01B32/19

  by exfoliation · CPC title

• C25B1/135 Primary

  Carbon · CPC title

• C25B11/044

  Impregnation of carbon · CPC title

• C25B1/00 Primary

  Electrolytic production of inorganic compounds or non-metals · CPC title

• C25B9/40

  Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof · CPC title