Method of producing graphene

Patent metadata

Field	Value
Publication number	US-10458026-B2
Application number	US-201515118968-A
Country	US
Kind code	B2
Filing date	Jan 28, 2015
Priority date	Feb 14, 2014
Publication date	Oct 29, 2019
Grant date	Oct 29, 2019

Abstract

A method of producing graphene sheets comprising the steps of, forming a carbonaceous powder by electrochemical erosion of a graphite electrode in a molten salt comprising hydrogen ions, recovering the resulting carbonaceous powder from the molten salt liquid, and thermally treating the carbonaceous powder by heating the carbonaceous powder in a non-oxidising atmosphere to produce a thermally treated powder comprising graphene sheets. The method allows high production rates of high purity graphene sheets.

First claim

The invention claimed is:

1. A method of producing graphene sheets comprising the steps of,
(a) forming a carbonaceous powder by electrochemical erosion of a graphite electrode in a molten salt comprising hydrogen ions,
(b) recovering the resulting carbonaceous powder from the molten salt liquid, and
(c) thermally treating the carbonaceous powder by heating the carbonaceous powder in a non-oxidising atmosphere to produce a thermally treated powder comprising graphene sheets,
in which the molten salt is in contact with a moist gas during the electrochemical erosion of the graphite electrode, water from the moist gas either dissolving in the molten salt or reacting with the molten salt to introduce hydrogen ions into the molten salt.

2. A method according to claim 1 in which the molten salt comprises lithium chloride.

3. A method according to claim 1 in which electrochemical erosion of the graphite electrode is performed under an atmosphere of moist gas, wherein the molten salt is shrouded under a flow of moist gas.

4. A method according to claim 1 in which the molten salt is sparged with the moist gas during electrochemical erosion of the graphite electrode.

5. A method according to claim 1 in which the moist gas is a moist inert gas, for example moist argon or moist nitrogen.

6. A method according to any of claim 1 in which the moist gas is produced by flowing a gas over, or through, a water source.

7. A method according to claim 1 in which the temperature of the molten salt during the electrochemical erosion of the graphite electrode is greater than 800° C.

8. A method according to claim 1 in which the molten salt and the carbonaceous powder is recovered from the molten salt by a process comprising steps of cooling and solidifying the molten salt, and washing the solidified salt from the carbonaceous powder.

9. A method according to claim 8 further comprising the step of vacuum filtration of the washed carbonaceous material.

10. A method according to claim 1 in which the carbonaceous powder comprises a metal hydride compound prior to the step of thermal treatment, for example lithium hydride, the metal species in the metal hydride being derived from the molten salt.

11. A method according to claim 1 in which the carbonaceous powder is thermally treated by heating to a temperature of greater than 1,000° C., for example to 1250° C.+/−50° C., in a reducing atmosphere, for example, in a reducing gas atmosphere comprising a mixture of nitrogen and hydrogen.

12. A method according to claim 1 in which the graphene sheets are graphene nanosheets having lateral dimensions of greater than 200 nanometers.

13. A method according to claim 1 in which the current at the graphite electrode during electrochemical erosion of the electrode is greater than 0.5 A/cm 2 .

14. A method according to claim 1 in which graphene sheets are produced at a rate of greater than 1 kg per hour, per square meter of graphite electrode immersed in the ionic liquid.

15. A method according to claim 1 in which the graphite electrode is cathodic in polarity during electrochemical erosion.

16. A method according to claim 1 comprising the step of;
(a) forming a carbonaceous powder by electrochemical erosion of two or more graphite electrodes in a molten salt comprising hydrogen ions, each of the two or more graphite electrodes alternately serving as a negative electrode in connection with a positive counter electrode for periods of time in order to effect the electrochemical erosion.

17. A method of producing graphene sheets comprising the steps of,
(a) forming a carbonaceous powder by electrochemical erosion of a graphite electrode in a molten salt comprising hydrogen ions,
(b) recovering the resulting carbonaceous powder from the molten salt liquid, and
(c) thermally treating the carbonaceous powder by heating the carbonaceous powder in a non-oxidising atmosphere to produce a thermally treated powder comprising graphene sheets,
in which the molten salt is in contact with a dry gas during the electrochemical erosion of the graphite electrode, the dry gas comprising an inert gas comprising argon or nitrogen, and hydrogen.

18. A method according to claim 17 in which the molten salt comprises lithium chloride.

19. A method according to claim 17 in which the molten salt and the carbonaceous powder is recovered from the molten salt by a process comprising steps of cooling and solidifying the molten salt, and washing the solidified salt from the carbonaceous powder.

20. A method according to claim 19 further comprising the step of vacuum filtration of the washed carbonaceous material.

21. A method according to claim 17 in which the carbonaceous powder comprises a metal hydride compound prior to the step of thermal treatment, for example lithium hydride, the metal species in the metal hydride being derived from the molten salt.

22. A method according to claim 17 in which the carbonaceous powder is thermally treated by heating to a temperature of greater than 1,000° C., for example to 1250° C., +/−50° C., in a reducing atmosphere, for example, in a reducing gas atmosphere comprising a mixture of nitrogen and hydrogen.

23. A method according to claim 17 in which the graphene sheets are graphene nanosheets having lateral dimensions of greater than 200 nanometers.

24. A method according to claim 17 in which the current at the graphite electrode during electrochemical erosion of the electrode is greater than 0.5 A/cm2.

25. A method according to claim 17 in which graphene sheets are produced at a rate of greater than 1 kg per hour, per square meter of graphite electrode immersed in the ionic liquid.

26. A method according to claim 17 in which the graphite electrode is cathodic in polarity during electrochemical erosion.

27. A method according to claim 17 comprising the step of;
(a) forming a carbonaceous powder by electrochemical erosion of two or more graphite electrodes in a molten salt comprising hydrogen ions, each of the two or more graphite electrodes alternately serving as a negative electrode in connection with a positive counter electrode for periods of time in order to effect the electrochemical erosion.

Assignees

• Cambridge Entpr Ltd

Inventors

• Fray Derek
• Kamali Ali

Classifications

• C01B32/19

  by exfoliation · CPC title

• C01B32/184

  Preparation · CPC title

• Y10S977/734

  Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc. · CPC title

• Y10S977/845

  Purification or separation of fullerenes or nanotubes · CPC title

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title