Graphene macro-assembly-fullerene composite for electrical energy storage

• US 9,870,871 B1
• Filed: 09/08/2016
• Issued: 01/16/2018
• Est. Priority Date: 09/08/2016
• Status: Active Grant

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Inventors: Campbell, Patrick G., Baumann, Theodore F., Biener, Juergen, Merrill, Matthew, Montalvo, Elizabeth, Worsley, Marcus A., Biener, Monika M., Hernndez, Maira Raquel Cern
• Primary Examiner(s): McCracken, Daniel C
• Application Number:
  US15/260,197
• Time in Patent Office: 495 Days
• Field of Search: 423448
• 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 32/152 Fullerenes
• CPC Class Codes: C01B 32/194 After-treatment
• CPC Class Codes: C07C 2604/00 Fullerenes, e.g. C60 buckminsterfullerene or C70
• CPC Class Codes: H01G 11/32 Carbon-based
• CPC Class Codes: H01G 11/36 Nanostructures, e.g. nanofibres, nanotubes or fullerenes
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries
• CPC Class Codes: Y10S 977/738 Modified with biological, organic, or hydrocarbon material
• CPC Class Codes: Y10S 977/847 Surface modifications, e.g. functionalization, coating
• CPC Class Codes: Y10S 977/948 Energy storage/generating using nanostructure, e.g. fuel cell, battery

Abstract

Disclosed here is a method for producing a graphene macro-assembly (GMA)-fullerene composite, comprising providing a GMA comprising a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds, and incorporating at least 20 wt. % of at least one fullerene compound into the GMA based on the initial weight of the GMA to obtain a GMA-fullerene composite. Also described are a GMA-fullerene composite produced, an electrode comprising the GMA-fullerene composite, and a supercapacitor comprising the electrode and optionally an organic or ionic liquid electrolyte in contact with the electrode.

Claims

1. A method for producing a graphene macro-assembly (GMA)-fullerene composite, comprising providing a GMA comprising a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds, and incorporating at least 20 wt. % of at least one fullerene compound into the GMA based on the initial weight of the GMA to obtain the GMA-fullerene composite, wherein the fullerene compound is covalently bound to the graphene sheets.

2. The method of claim 1, wherein the incorporating step comprises reacting the GMA with least one diazonium functionlized fullerene.

3. The method of claim 2, wherein the diazonium functionlized fullerene is represented by:

F*—

(R¹)_n, wherein;

F* comprises a fullerene having a surface comprising six-membered and five-membered rings,

R¹ comprises a diazonium group and a conjugated linker covalently connecting the diazonium group to the fullerene, and

n is at least one.

4. The method of claim 3, wherein n is 1 or 2, F* is C₆₀ or C₇₀, and R¹ is selected from the group consisting of

5. The method of claim 1, wherein based on the initial weight of the GMA at least 50 wt. % of the fullerene compound are incorporated into the GMA.

6. The method of claim 1, wherein based on the initial weight of the GMA at least 100 wt. % of the fullerene compound are incorporated into the GMA.

10. A GMA-fullerene composite produced by the method of claim 1.

11. The GMA-fullerene composite of claim 10, wherein the GMA-fullerene composite is a monolith having a thickness of at least 1 mm.

12. The GMA-fullerene composite of claim 10, wherein the GMA-fullerene composite has an electrical conductivity of at least 10 S/m.

13. The GMA-fullerene composite of claim 10, wherein the GMA-fullerene composite has a mesopore volume of at least 0.5 cm³/g.

14. The GMA-fullerene composite of claim 10, wherein the GMA-fullerene composite has a BET surface area of at least 200 m²/g.

15. The GMA-fullerene composite of claim 10, wherein the GMA-fullerene composite has a Young'"'"'s modulus of at least 20 MPa.

16. A supercapacitor comprising an electrode comprising the GMA-fullerene composite of claim 10, and further comprising an organic or ionic liquid electrolyte in contact with the electrode.

7. A method for producing a graphene macro-assembly (GMA)-fullerene composite, comprising providing a GMA comprising a three-dimensional network of graphene sheets crosslinked by covalent carbon bonds, and incorporating at least 20 wt. % of at least one fullerene compound into the GMA based on the initial weight of the GMA to obtain the GMA-fullerene composite, wherein the fullerene compound is noncovalently attached to the graphene sheets, and wherein the incorporating step comprises incubating the GMA in a solution comprising at least one phenylamine functionlized fullerene.

8. The method of claim 7, wherein the phenylamine functionlized fullerene is represented by:

F*—

(R²)_n, wherein;

F* comprises a fullerene having a surface comprising six-membered and five-membered rings,

R² comprises a phenylamine group and a conjugated linker covalently connecting the phenylamine group to the fullerene, and

n is at least one.

9. The method of claim 8, wherein n is 1 or 2, F* is C₆₀ or C₇₀, and R² is selected from the group consisting of

17. A GMA-fullerene composite produced by the method of claim 7.

18. A supercapacitor comprising an electrode comprising the GMA-fullerene composite of claim 17, and further comprising an organic or ionic liquid electrolyte in contact with the electrode.