Porous interconnected corrugated carbon-based network (ICCN) composite

• US 10,734,167 B2
• Filed: 11/18/2015
• Issued: 08/04/2020
• Est. Priority Date: 11/18/2014
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: El-Kady, Maher F., Kaner, Richard B., Hwang, Jee Youn
• Primary Examiner(s): Simone, Catherine A.
• Application Number:
  US14/945,232
• Publication Number:
  US 20160148759A1
• Time in Patent Office: 1,721 Days
• Field of Search: 428116, 428117, 428118, 428323, 428328, 428329, 428330, 428408
• CPC Class Codes: C01B 32/184 Preparation
• CPC Class Codes: C01B 32/194 After-treatment
• CPC Class Codes: C25D 9/08 by cathodic processes
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/36 Nanostructures, e.g. nanofibres, nanotubes or fullerenes
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/70 characterised by their structure
• CPC Class Codes: H01G 11/86 specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A porous interconnected corrugated carbon-based network (ICCN) composite and methods for making the same are disclosed. The porous ICCN composite is made up of a plurality of carbon layers that are interconnected and expanded apart from one another to form a plurality of pores. Metallic nanoparticles are disposed within the plurality of pores. In one embodiment, a light exposure only based method for producing the porous ICCN composite is disclosed. In another embodiment a light exposure plus an electrodeposition method for producing the porous ICCN composite is disclosed. In yet another exemplary embodiment, a capacitor having a first electrode and a second electrode separated from the first electrode by a dielectric wherein at least one of the first electrode and the second electrode is formed from the porous ICCN composite is disclosed.

Claims

1. A porous interconnected corrugated carbon-based network (ICCN) composite comprising:

a plurality of one atom thick two-dimensional carbon sheets that are interconnected in a layered structure, wherein consecutively layered carbon sheets are directly coupled and expanded apart from one another to form a plurality of pores; and

metallic nanoparticles disposed within the plurality of pores, wherein a percentage of surface area coverage of the metallic nanoparticles onto the plurality of one atom thick two-dimensional carbon sheets ranges from about 10% to about 95%.

2. The porous ICCN composite of claim 1 wherein an average minor axis diameter of the plurality of pores ranges (i) from about 2 nanometers to about 50 nanometers, or (ii) from about 50 nanometers to about 500 nanometers.

3. The porous ICCN composite of claim 1 wherein the metallic nanoparticles have a nanoflower shape.

4. The porous ICCN composite of claim 1 wherein the metallic nanoparticles are metal oxide particles.

5. The porous ICCN composite of claim 4 wherein the metallic nanoparticles are particles of manganese dioxide (MnO₂), ruthenium dioxide (RuO₂), cobalt oxide (CO₃O₄), nickel oxide (NiO), iron oxide (Fe₂O₃), copper oxide (CuO), molybdenum trioxide (MoO₃), vanadium pentoxide (V₂O₅), nickel hydroxide (Ni(OH)₂), or any combination thereof.

6. The porous ICCN composite of claim 1 wherein the porous ICCN composite (i) has an electrical conductivity that ranges from about 900 siemens/meter to about 1750 siemens/meter, or (ii) provides an energy density that ranges from about 2 Watt-hour/liter to about 41 Watt-hour/liter.

7. The porous ICCN composite of claim 1 wherein (i) an electrical conductivity of the plurality of one atom thick two-dimensional carbon sheets is greater than about 0.1 siemens/meter, (ii) a total surface area per unit mass of the plurality of one atom thick two-dimensional carbon sheets is at least about 1500 square meters per gram, or (iii) a total surface area per unit mass of the plurality of one atom thick two-dimensional carbon sheets ranges from about 1500 square meters per gram to about 1620 square meters per gram.

8. A method of producing porous ICCN composite comprising:

providing a film comprising a mixture of a metallic precursor and a carbon-based oxide; and

exposing at least a portion of the film to light to form a porous interconnected corrugated carbon-based network (ICCN) composite comprising;

a plurality of one atom thick two-dimensional carbon sheets that are interconnected in a layered structure, wherein consecutively layered carbon sheets are directly coupled and expanded apart from one another to form a plurality of pores; and

metallic nanoparticles disposed within the plurality of pores, wherein a percentage of surface area coverage of the metallic nanoparticles onto the plurality of one atom thick two-dimensional carbon sheets ranges from about 10% to about 95%, and wherein the light converts the metallic precursor to metallic nanoparticles.

9. The method of producing porous ICCN composite of claim 8 wherein providing the film comprising the mixture of the metallic precursor and the carbon-based oxide comprises:

providing a solution comprising a liquid, the metallic precursor, and the carbon-based oxide;

disposing the solution with the liquid, the metallic precursor, and the carbon-based oxide onto a substrate; and

evaporating the liquid from the solution to form the film.

10. The method of producing the porous ICCN composite of claim 8 wherein the carbon-based oxide is graphite oxide.

11. The method of producing the porous ICCN composite of claim 8 wherein the metallic nanoparticles are particles of ruthenium oxide (RuO₂), cobalt oxide (CO₃O₄), nickel oxide (NiO), vanadium pentoxide (V₂O₅), iron oxide (Fe₂O₃), copper oxide (CuO), molybdenum trioxide (MoO₃), or any combination thereof.

12. The method of producing the porous ICCN composite of claim 8 wherein an electrical conductivity of the plurality of one atom thick two-dimensional carbon sheets is greater than about 0.1 siemens/meter.

13. The method of producing the porous ICCN composite of claim 8 wherein the porous ICCN composite has an electrical conductivity that ranges from about 900 siemens/meter to about 1750 siemens/meter.

14. A method of producing a porous interconnected corrugated carbon-based network (ICCN) composite comprising:

forming a porous ICCN composite comprising a plurality of one atom thick two-dimensional carbon sheets that are interconnected in a layered structure, wherein consecutively layered carbon sheets are directly coupled and expanded apart from one another to form a plurality of pores; and

electrodepositing metallic nanoparticles within the plurality of pores, wherein a percentage of surface area coverage of the metallic nanoparticles onto the plurality of one atom thick two-dimensional carbon sheets ranges from about 10% to about 95%.

15. The method of producing the porous ICCN composite of claim 14 wherein forming the porous ICCN composite comprises providing a film made of a mixture of a carbon-based oxide by:

providing a solution comprising a liquid and the carbon-based oxide;

disposing the solution with the liquid and the carbon-based oxide onto a substrate;

evaporating the liquid from the solution to form the film; and

exposing the film to light.

16. The method of producing the porous ICCN composite of claim 15 wherein the carbon-based oxide is graphite oxide.

17. The method of producing the porous ICCN composite of claim 14 wherein the metallic nanoparticles are particles of manganese dioxide (MnO2), ruthenium oxide (RuO₂), cobalt oxide (CO₃O₄), nickel oxide (NiO), vanadium pentoxide (V₂O₅), iron oxide (Fe₂O₃), copper oxide (CuO), molybdenum trioxide (MoO₃), nickel hydroxide (Ni(OH)₂), or any combination thereof.

18. The method of producing the porous ICCN composite of claim 14 wherein an electrical conductivity of the plurality of one atom thick two-dimensional carbon sheets is greater than about 0.1 siemens/meter.

19. The method of producing the porous ICCN composite of claim 15 wherein the porous ICCN composite has an electrical conductivity that ranges from about 900 siemens/meter to about 1750 siemens/meter.

20. The method of producing the porous ICCN composite of claim 14 wherein electrodepositing the metallic nanoparticles within the plurality of pores comprises:

submerging the porous ICCN composite into an aqueous solution having a metallic precursor; and

applying an electrical current through the porous ICCN composite to electrodeposit the metallic nanoparticles into the plurality of pores.

21. The method of producing the porous ICCN composite of claim 20 wherein the electrical current has a current density of at least about 250 microamperes per square centimeter.