Method of producing nano-scaled graphene and inorganic platelets and their nanocomposites

• US 8,114,373 B2
• Filed: 01/04/2011
• Issued: 02/14/2012
• Est. Priority Date: 02/22/2007
• Status: Active Grant

• Current Assignee: Global Graphene Group, Inc.
• Original Assignee: Nanotek Instruments, Inc.
• Inventors: Jang, Bor Z., Zhamu, Aruna
• Primary Examiner(s): Hendrickson, Stuart
• Assistant Examiner(s): Rump, Richard M
• Application Number:
  US12/983,947
• Publication Number:
  US 20110190435A1
• Time in Patent Office: 406 Days
• Field of Search: 423/415.1, 423/460, 423/509, 423/562, 423/447.1, 423/447.3, 423/445.B, 423/448, 423/439, 264/42, 252/378.R
• US Class Current: 423/415.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2204/04 Specific amount of layers or specific thickness
• CPC Class Codes: C01B 32/15 Nano-sized carbon materials
• CPC Class Codes: C01B 32/22 Intercalation
• CPC Class Codes: C01B 32/225 Expansion; Exfoliation
• CPC Class Codes: C01B 32/23 Oxidation
• CPC Class Codes: C01B 33/40 Clays
• CPC Class Codes: C01P 2004/24 Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
• CPC Class Codes: C09C 1/44 Carbon
• CPC Class Codes: C09C 1/46 Graphite C09C1/0015 takes precedence

Abstract

Disclosed is a method of exfoliating a layered material (e.g., graphite and graphite oxide) to produce nano-scaled platelets having a thickness smaller than 100 nm, typically smaller than 10 nm, and often between 0.34 nm and 1.02 nm. The method comprises: (a) subjecting the layered material in a powder form to a halogen vapor at a first temperature above the melting point or sublimation point of the halogen at a sufficient vapor pressure and for a duration of time sufficient to cause the halogen molecules to penetrate an interlayer space of the layered material, forming a stable halogen-intercalated compound; and (b) heating the halogen-intercalated compound at a second temperature above the boiling point of the halogen, allowing halogen atoms or molecules residing in the interlayer space to exfoliate the layered material to produce the platelets. Alternatively, rather than heating, step (a) is followed by a step of dispersing the halogen-intercalated compound in a liquid medium which is subjected to ultrasonication for exfoliating the halogen-intercalated compound to produce the platelets, which are dispersed in the liquid medium. The halogen can be readily captured and re-used, thereby significantly reducing the impact of halogen to the environment. The method can further include a step of dispersing the platelets in a polymer or monomer solution or suspension as a precursor step to nanocomposite fabrication.

Claims

1. A method of exfoliating a layered material to produce nano-scaled platelets having a thickness smaller than 100 nm, said method comprising:

a) subjecting said layered material to a halogen vapor at a first temperature between the melting point or sublimation point of said halogen with a halogen vapor pressure and for a duration of time sufficient to cause said halogen to penetrate an interlayer space of said layered material for forming a stable halogen-intercalated compound, wherein said layered material comprises a layered inorganic compound selected from the group consisting of (a) clay;

(b) bismuth selenide or telluride;

(c) transition metal dichalcogenide;

(d) sulfide, selenide, and telluride of niobium, molybdenum, hafnium, tantalum, tungsten, and rhenium;

(e) layered transition metal oxide;

(f) pre-intercalated compounds, and combinations thereof; and

wherein said halogen is selected from the group consisting of iodine bromide, bromine chloride, iodine pentafluoride, bromine trifluoride, chlorine trifluoride, phosphorus trichloride, phosphorus tetrachloride, phosphorus tribromide, phosphorus triiodide or a combination thereof, or in combinations with a diatomic halogen selected from the group consisting of bromine or iodine and

b) mixing said halogen-intercalated compound in a liquid medium which is subjected to ultrasonication for exfoliating said intercalated compound to produce the platelets and for dispersing said platelets in said liquid medium.

2. The method of claim 1 wherein said layered material comprises particles with a dimension smaller than 10 μ

m.

3. The method of claim 1 wherein said layered material comprises particles with a dimension smaller than 1 μ

m.

4. The method of claim 1 wherein said platelets have a thickness smaller than 10 nm.

5. The method of claim 1 wherein said platelets comprise single graphene or graphite oxide sheets.

6. The method of claim 1 wherein said stable halogen-intercalated compound comprises a compound of C₈Br or C₈β

.

7. The method of claim 1 further comprising a step of capturing at least portion of said halogen molecules after exfoliation.

8. The method of claim 1 wherein said step of intercalation comprises enclosing said layered material in a first chamber and said halogen in a second chamber which is in vapor communication with said first chamber and wherein said second chamber is at a lower temperature than said first chamber.

9. The method of claim 1 wherein said layered material comprises natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite oxide, graphite fluoride, pre-intercalated graphite, pre-intercalated graphite oxide, pre-intercalated graphite fluorite, graphite or carbon fiber, graphite nano-fiber, or a combination thereof.

10. The method of claim 1 further including a step of adding a monomer or polymer to said liquid medium to form a nanocomposite precursor suspension or solution.

11. The method of claim 10 further including a step of converting said suspension to a mat or paper, or converting said nanocomposite precursor suspension to a nanocomposite solid.

12. The method of claim 1 further including steps of mixing said platelets with a monomer or polymer to form a mixture and converting said mixture to obtain a nanocomposite solid.

13. The method of claim 10 wherein said platelets comprise graphite oxide or graphite fluoride platelets and said method further includes a step of partially or totally reducing said graphite oxide or graphite fluoride after the formation of said suspension.