Hierarchical composite structures based on graphene foam or graphene-like foam

Patent metadata

Field	Value
Publication number	US-2017237075-A1
Application number	US-201515523337-A
Country	US
Kind code	A1
Filing date	Oct 30, 2015
Priority date	Oct 31, 2014
Publication date	Aug 17, 2017
Grant date	—

Abstract

The present invention relates to a hierarchical composite structure comprising an open cell graphene foam or graphene-like foam, wherein the graphene foam or graphene-like foam is coated with a conductive nanoporous spongy structure and wherein at least 10 % v/v of the hollow of the pores of the graphene foam or graphene-like foam is filled with the conductive nanoporous spongy structure. The invention also relates to a process for preparing a hierarchical composite structure wherein a conductive nanoporous spongy structure is electrodeposited so as to coat the open-cell graphene foam or graphene-like foam and to partially fill the hollow of the pores of the graphene foam or graphene-like foam.

First claim

1 . A hierarchical composite structure comprising an open-cell graphene foam or graphene-like foam, wherein the graphene foam or graphene-like foam is coated with a conductive nanoporous spongy structure and wherein at least 10% v/v of the hollow of the pores of the graphene foam or graphene-like foam is filled with the conductive nanoporous spongy structure.

2 . The hierarchical composite structure according to claim 1 , wherein from 10% to 90% v/v of the hollow of the pores of the graphene foam or graphene-like foam is filled with the conductive nanoporous spongy structure.

3 . The hierarchical composite structure according to claim 1 , wherein from 10% to 50% v/v of the hollow of the pores of the graphene foam or graphene-like foam is filled with the conductive nanoporous spongy structure.

4 . The hierarchical composite structure according to claims 1 - 3 , wherein the graphene in the open-cell graphene foam is single-layer, bilayer or multi-layer having from 3 to 20 layers of single atomic graphene.

5 . The hierarchical composite structure according to claims 1 - 3 , wherein the open-cell graphene-like material in the graphene-like foam is ultra-thin graphite having from 21 to 300 layers of single atomic graphene, or reduced graphene oxide.

6 . The hierarchical composite structure according to any preceding claims, wherein the structure of the graphene foam or graphene-like foam has pores of a mean diameter ranging from 5 to 500 μm.

7 . The hierarchical composite structure according to any preceding claims, wherein the nanopores of the conductive nanoporous spongy structure have a mean diameter ranging from 5 to 500 nm.

8 . The hierarchical composite structure according to claim 7 , wherein the conductive nanoporous spongy structure comprises a framework of nanofibers of a conductive polymer.

9 . The hierarchical composite structure according to claim 8 , wherein the conductive polymer is selected from the group consisting of polyaniline, polypyrrole, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), polyphenylene sulfide, polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphtalene, polyacetylene, polyphenylene vinylene and derivatives thereof.

10 . The hierarchical composite structure according to claim 9 , wherein the conductive polymer is polyaniline.

11 . A process for preparing a hierarchical composite structure, said process comprising:
a) providing a graphene foam or graphene-like foam having an open-cell structure; b) immersing the graphene foam or graphene-like foam in a electrolyte solution, wherein the electrolyte solution comprises a conductive material or a precursor thereof; c) removing the air trapped in the graphene foam or graphene-like foam immersed in the electrolyte solution; d) electrodepositing the conductive material, or the conductive material formed from the precursor thereof, on the graphene foam or graphene-like foam in the electrolyte solution, so as a conductive nanoporous spongy structure is formed coating the graphene foam or graphene-like foam and partially filling the hollow of the pores of the graphene foam or graphene-like foam.

12 . The process according to claim 11 , wherein the precursor of the conductive material is a precursor monomer of a conductive polymer.

13 . The process according to claim 12 , wherein the precursor monomer is aniline.

14 . The process according to anyone of claims 10 to 13 , wherein the electrolyte solution further comprises an anti-agglomerating agent, and wherein said anti-agglomerating agent is added to the electrolyte solution where the graphene foam or graphene-like foam is immersed or after conducting step c).

15 . The process according to anyone of claims 11 to 14 , wherein the electrodeposition is carried out upon application of an electrical potential.

16 . The process according to claim 15 , wherein a continuous potential is applied between 0.65 and 0.85 V.

17 . A hierarchical composite structure obtainable by the process as defined in any of claims 11 to 16 .

18 . The hierarchical composite structure according to claim 17 , wherein at least 10% v/v of the hollow of the pores of the graphene foam or graphene-like foam is filled with the conductive nanoporous spongy structure.

19 . An electrode comprising the hierarchical composite structure according to claims 1 - 10 and 17 - 18 .

20 . An electrochemical-energy-storage device comprising at least one electrode as defined in claim 19 , separated from a second electrode by a separator and immersed in an electrolyte.

21 . The electrochemical-energy-storage device according to claim 20 , which is a supercapacitor.

Assignees

• Repsol Sa

Inventors

• Pedrós Jorge
• Boscá Alberto
• Martínez Javier
• CALLE Fernando
• Ruiz-Gómez Sandra
• Pérez Lucas
• Barranco Violeta
• Páez Dueñas Antonio
• García San Luis Jesús

Classifications

• H01G11/52

  Separators · CPC title

• H01G11/48

  Conductive polymers · CPC title

• H01G11/24

  characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor · CPC title

• H01M4/808

  Foamed, spongy materials · CPC title

• H01M4/0452

  from solutions · CPC title