Graphene, method and apparatus for preparing graphene

Patent metadata

Field	Value
Publication number	US-9738528-B2
Application number	US-201414907858-A
Country	US
Kind code	B2
Filing date	Aug 20, 2014
Priority date	Aug 21, 2013
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

There are provided a graphene having an oxygen atom content in a predetermined range or less and a carbon/oxygen weight ratio in a specific range to show excellent electrical and thermal conductivity properties, and a barrier property, and a method and an apparatus for preparing the graphene having excellent electrical and thermal conductivity properties and a barrier property by using a subcritical-state fluid or a supercritical-state fluid. According to the method and the apparatus for preparing the graphene, impurities such as graphene oxide, and the like, may be effectively removed, such that uniformity of the graphene to be prepared may be increased, and therefore, the graphene which is highly applicable as materials throughout the industry may be mass-produced.

First claim

The invention claimed is:

1. A method for preparing a graphene comprising:
forming a mixed solution including a graphite oxide, a solvent, a first oxidizing agent; and a sulfur compound or a nitrogen compound;
forming the graphene by reacting the mixed solution under a subcritical condition or a supercritical condition of the solvent; and
recovering the graphene
wherein the sulfur compound is represented by the following Chemical Formula 1, and the nitrogen compound is represented by the following Chemical Formula 2:
HO-A 1 -Q-A 2 -OH  [Chemical Formula 1 ]

in Chemical Formula 1, A1 and A2 are each independently linear or branched C1-C10alkylene group or C6-C20 arylene group, and Q is a sulfur atom (—S—) or a sulfone group(—(O═S═O)—), and

in Chemical Formula 2, at least one of R1 to R4 is a nitro group (—NO2), and the remainder is hydrogen, linear or branched C1-C7 alkyl group or C6-C20 aryl group.

2. The method of claim 1 , wherein the solvent includes water, carbon dioxide, or mixtures thereof.

3. The method of claim 1 , wherein the graphite oxide is formed by treating a graphite oxide precursor with an acid and a second oxidizing agent.

4. The method of claim 3 , wherein the graphite oxide precursor is at least one kind selected from the group consisting of graphite, graphene, graphite nanoplatelet, graphene nanoplatelet, expanded graphite, diamond, fullerene, carbon black, activated carbon, charcoal, carbon nanoribbon, carbon nanowire, carbon nanoclay, carbon nanotube, pitch carbon fiber, carbon nanofiber, carbon glass fiber, and asphalt.

5. The method of claim 1 , wherein the first oxidizing agent is at least one kind selected from the group consisiting of oxygen, ozone, and hydrogen peroxide.

6. The method of claim 1 , wherein the graphite oxide is included in an amount of 0.0001 to 30 parts by weight based on 100 parts by weight of the solvent.

7. The method of claim 1 , wherein the nitrogen compound or the sulfur compound is included at 0.0001 to 1 molar ratio (M) with respect to the mixed solution.

8. The method of claim 1 , wherein the subcritical condition or the supercritical condition has a temperature of 50 to 600° C.

9. The method of claim 1 , wherein the subcritical condition or the supercritical condition has a pressure of 30 to 500 atm.

10. The method of claim 1 , wherein in the forming of the graphene, the mixed solution further including a reducing adjuvant is reacted under the subcritical condition or the supercritical condition.

11. The method of claim 10 , wherein the reducing adjuvant is at least one selected from the group consisting of an ammonia water, amine, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium hydrogen carbonate (NaHCO3), sodium hydride (NaH), sodium borohydride (NaBH4), lithium aluminum hydride (LiAIH4), hydroquinone (HO—Ph—OH), hydrogen sulfide (HS), urea (NH2-CO—NH2), urea sulfide (NH2-CS—NH2), and sulfide dioxide urea (NH2-C(NH)—SOOH).

12. The method of claim 1 , further comprising, after the forming of the mixed solution and before the forming of the graphene, pre-heating the mixed solution to 50 to 500° C.

13. The method of claim 1 , further comprising, after the forming of the graphene and before the recovering of the graphene, high-pressure-filtering the graphene.

14. The method of claim 1 , further comprising, after the forming of the graphene and before the recovering of the graphene, washing the formed graphene.

15. An apparatus for preparing a graphene comprising:
a mixing bath forming a pre-mixed solution by mixing a graphite oxide, a solvent, and a sulfur compound or a nitrogen compound;
a first oxidizing agent feeding pump supplying a first oxidizing agent;
a pre-heater pre-heating the pre-mixed solution and the first oxidizing agent supplied from the mixing bath and the first oxidizing agent feeding pump, respectively;
a reactor connected to a rear end of the pre-heater, and generating a reaction of a mixed solution including the pre-mixed solution and the first oxidizing agent under a subcritical condition or a supercritical condition of the solvent;
a cooler connected to a rear end of the reactor and cooling a product of the reaction;
recovering baths connected to a rear end of the cooler and recovering the graphene from the product; and
a reducing adjuvant feeding pump connected to the middle of the reactor and injecting a reducing adjuvant into the reactor,
wherein the reducing adjuvant feeding pump is connected to a point of 1/6 to ½ from an entrance of the reactor.

16. The apparatus of claim 15 , further comprising a circulating pump connected to the mixing bath, and circulating and mixing the graphite oxide, the solvent, and the sulfur compound or the nitrogen compound to form the pre-mixed solution.

17. The apparatus of claim 15 , further comprising a heat exchanger provided between the mixing bath and the pre-heater, and connected to the rear end of the reactor and a front end of the cooler.

18. The apparatus of claim 15 , further comprising a cooling and pressure-releasing bath provided between the cooler and the recovering bath, and cooling and pressure-releasing the product.

19. The apparatus of claim 15 , wherein the recovering bath further includes filters filtering the product delivered from the cooler.

Assignees

• Hanwha Chemical Corp

Inventors

• Lee Jin Seo
• Do Seung Hoe
• Jeon Seong Yun
• Kong Jung Ho

Classifications

• C01B32/198

  Graphene oxide · CPC title

• C01B2204/22

  Electronic properties · CPC title

• C01B32/23

  Oxidation · CPC title

• B01J19/24

  Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) · CPC title

• C01B32/196 Primary

  Purification · CPC title