Synthesis of three-dimensional graphene foam: use as supercapacitors

Patent metadata

Field	Value
Publication number	US-9929287-B2
Application number	US-201314395985-A
Country	US
Kind code	B2
Filing date	Jun 3, 2013
Priority date	Jun 1, 2012
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

The invention relates to three-dimensional crystalline foams with high surface areas, high lithium capacity, and high conductivity for use as electrode materials and methods for their fabrication. In additional embodiments, the invention also relates to the use of three-dimensional crystalline foams as supercapacitors for improved charge and energy storage.

First claim

What is claimed is:

1. A graphene-based electrode, comprising:
a ferroelectric polymer; and
a graphene substrate, wherein the graphene substrate is coated with the ferroelectric polymer, wherein the graphene substrate is a graphene foam or a combination of a graphene foam and one or more of a graphene sheet, activated reduced graphene oxide, and a graphene composite, in which the graphene foam is a three-dimensional crystalline foam containing a group IV-B element and graphene formed from a carbon source, wherein the carbon source is carbon black, amorphous carbon, single-wall carbon nanotube, multi-wall nanotube, graphene oxide, graphite powder, or a combination thereof; the group IV-B element is silicon, germanium, tin, lead, or a combination thereof; and the three-dimensional crystalline foam is formed from a three-dimensional metal foam framework having a surface area of at least 500 m 2 /g.

2. The graphene-based electrode of claim 1 , wherein the graphene sheet is single-layer graphene or multi-layer graphene.

3. The graphene-based electrode of claim 1 , wherein the graphene composite comprises a graphene foam and a carbon nanotube.

4. The graphene-based electrode of claim 1 , wherein the ferroelectric polymer is a polymer or copolymer comprising vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,1-chlorofluoroethylene, or a combination thereof.

5. The graphene-based electrode of claim 1 , wherein the ferroelectric polymer is a blend comprising a ferroelectric polymer and a polar polymer.

6. The graphene-based electrode of claim 5 , wherein the polar polymer is poly(methyl methacrylate), polyvinyl alcohol, poly(ethylene oxide), polyvinyl chloride, polyacrylonitrile, poly(ethyl methacrylate), or a combination thereof.

7. The graphene-based electrode of claim 1 , wherein the ferroelectric polymer further comprises an electrolyte.

8. The graphene-based electrode of claim 1 , wherein the graphene substrate is made by chemical vapor deposition (CVD) on a metal template.

9. The graphene-based electrode of claim 8 , wherein the graphene substrate is coated with the ferroelectric polymer before the metal template is removed.

10. The graphene-based electrode of claim 1 , wherein the graphene foam contains single-layer or multi-layer graphene.

11. The graphene-based electrode of claim 1 , wherein the graphene composite is one of a polymer-graphene composite, a metal-graphene composite, a graphene-based composite, and a ceramic-based composite, or a combination thereof.

12. A supercapacitor for improved charge and energy storage, comprising:
a first graphene-based electrode containing a first graphene substrate and a first and a second surface, the first surface in contact with a first surface of a porous separator;
a second graphene-based electrode containing a second graphene substrate and a first and a second surface, the first surface in contact with a second surface of the porous separator;
wherein at least one of the first and the second graphene substrates is coated with a ferroelectric polymer;
a first metal electrode making contact with the second surface of the first graphene-based electrode; and
a second metal electrode making contact with the second surface of the second graphene-based electrode,

wherein the first graphene substrate and the second graphene substrate are the same graphene substrate or different graphene substrates, in which each graphene substrate is a graphene foam or a combination of a graphene foam and one or more of a graphene sheet, activated reduced graphene oxide, and a graphene composite; and each graphene substrate is a three-dimensional crystalline foam that contains a group IV-B element and graphene formed from a carbon source, wherein the carbon source is carbon black, amorphous carbon, single-wall carbon nanotube, multi-wall nanotube, graphene oxide, graphite powder, or a combination thereof; the group IV-B element is silicon, germanium, tin, lead, or a combination thereof; and the three-dimensional crystalline foam is formed from a three-dimensional metal foam framework having a surface area of at least 500 m 2 /g.

13. The supercapacitor of claim 12 , wherein the ferroelectric polymer is a polymer or copolymer comprising polyvinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, 1,1-chlorofluoroethylene, or a combination thereof.

14. The supercapacitor of claim 13 , wherein the ferroelectric polymer is a blend comprising a ferroelectric polymer and a polar polymer.

15. The supercapacitor of claim 14 , wherein the polar polymer is poly(methyl methacrylate), polyvinyl alcohol, poly(ethylene oxide), polyvinyl chloride, polyacrylonitrile, poly(ethyl methacrylate), or a combination thereof.

16. The supercapacitor of claim 13 , wherein the ferroelectric polymer further comprises an electrolyte.

17. A method of making a supercapacitor of claim 12 for improved charge and energy storage, the method comprising:
a) preparing a first and a second graphene substrate for a first and a second graphene-based electrode, respectively, wherein each graphene substrate is a graphene foam or a combination of the graphene foam and one or more of a graphene sheet, activated reduced graphene oxide, and a graphene composite, and wherein each graphene-based electrode includes a first and a second surface;
b) coating throughout at least one of the first and the second graphene substrates with a ferroelectric polymer;
c) contacting the first surface of the first graphene-based electrode with a first surface of a porous separator;
d) contacting the first surface of the second graphene-based electrode with a second surface of the porous separator;
e) contacting a first metal electrode with the second surface of the first graphene-based electrode; and
f) contacting a second metal electrode with the second surface of the second graphene-based electrode,

whereby the supercapacitor is obtained.

18. The method of claim 17 , wherein the graphene foam is prepared by:
mixing a carbon source and a skelet powder to obtain a uniform mixture,
applying pressure to the uniform mixture thus obtained to form a closed packed structure,
heating and applying pressure to the closed packed structure to form a graphene sheet layered around the skelet powder, and
dissolving the skelet powder in the closed packed structure in a chemical bath and removing the dissolved powder therefrom, thereby producing voids,

whereby the graphene foam is obtained.

19. The method of claim 18 , wherein the carbon source is coated on a group IV-B element.

20. The method of claim 17 , wherein the graphene composite contains the graphene foam and a carbon nanotube.

Assignees

• Nat Univ Singapore

Inventors

• Ozyilmaz Barbaros
• Kahya Orhan
• Lee Jonghak

Classifications

• H01G11/48 Primary

  Conductive polymers · CPC title

• C01B32/198

  Graphene oxide · CPC title

• H01G11/36

  Nanostructures, e.g. nanofibres, nanotubes or fullerenes · CPC title

• Y10T428/24997

  Of metal-containing material · CPC title

• C01B32/182

  Graphene · CPC title