Supercapacitor having highly conductive graphene foam electrode

Patent metadata

Field	Value
Publication number	US-2017200565-A1
Application number	US-201614998475-A
Country	US
Kind code	A1
Filing date	Jan 11, 2016
Priority date	Jan 11, 2016
Publication date	Jul 13, 2017
Grant date	—

Abstract

A supercapacitor electrode comprising a solid graphene foam impregnated with a liquid or gel electrolyte, wherein the solid graphene foam is composed of multiple pores and pore walls, wherein pore walls contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 5% by weight of non-carbon elements wherein non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof, and the solid graphene foam, when measured in a dried state without electrolyte, has a physical density from 0.01 to 1.7 g/cm 3 , a specific surface area from 50 to 3,200 m 2 /g, a thermal conductivity of at least 200 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 2,000 S/cm per unit of specific gravity.

First claim

We claim:

1 . A supercapacitor electrode comprising a solid graphene foam impregnated with a liquid or gel electrolyte, wherein said solid graphene foam is composed of multiple pores and pore walls, wherein said pore walls contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 5% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, or a combination thereof, and said solid graphene foam, when measured in a dried state without said electrolyte, has a physical density from 0.01 to 1.7 g/cm 3 , a specific surface area from 50 to 3,300 m 2 /g, a thermal conductivity of at least 200 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 2,000 S/cm per unit of specific gravity.

2 . The supercapacitor electrode of claim 1 , wherein said pore walls contain stacked graphene planes having an inter-plane spacing d 002 from 0.3354 nm to 0.40 nm as measured by X-ray diffraction.

3 . The supercapacitor electrode of claim 1 , wherein said pore walls contain a pristine graphene and said solid graphene foam has a density from 0.1 to 1.7 g/cm 3 or an average pore size from 0.5 nm to 50 nm.

4 . The supercapacitor electrode of claim 1 , wherein said pore walls contain a non-pristine graphene material selected from the group consisting of graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, doped graphene, and combinations thereof, and wherein said solid graphene foam contains a content of non-carbon elements in the range of 0.01% to 2.0% by weight.

5 . The supercapacitor electrode of claim 1 , wherein said solid graphene foam further contains a carbon or graphite material selected from carbon nanotubes, carbon nano-fibers, carbon fiber segments, graphite fiber segments, activated carbon, carbon black particles, carbon wires, natural graphite particles, needle coke particles, meso-carbon micro-beads, particles of a natural or artificial graphite, expanded graphite flakes, or a combination thereof.

6 . The supercapacitor electrode of claim 1 , wherein said solid graphene foam has a specific surface area from 200 to 3,000 m 2 /g or a density from 0.1 to 1.5 g/cm 3 .

7 . The supercapacitor electrode of claim 1 , wherein said non-carbon elements include an element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

8 . The supercapacitor electrode of claim 1 , wherein said multiple pores contain a redox pair partner selected from an intrinsically conductive polymer, a transition metal oxide, and/or an organic molecule, wherein said redox pair partner is in physical or electronic contact with said graphene material, forming a redox pair therewith.

9 . The supercapacitor electrode of claim 8 , wherein said intrinsically conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, sulfonated polyacetylene, or a combination thereof.

10 . The supercapacitor electrode of claim 1 , which is in a continuous-length roll sheet form having a thickness from 10 nm to 10 mm and a length of at least 2 meters and is produced by a roll-to-roll process.

11 . The supercapacitor electrode of claim 1 , wherein said solid graphene foam has an oxygen content or non-carbon content less than 1% by weight, and said pore walls have an inter-graphene spacing less than 0.35 nm, a thermal conductivity of at least 250 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 2,500 S/cm per unit of specific gravity.

12 . The supercapacitor electrode of claim 1 , wherein said graphene foam has an oxygen content or non-carbon content less than 0.01% by weight and said pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.34 nm, a thermal conductivity of at least 300 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 3,000 S/cm per unit of specific gravity.

13 . The supercapacitor electrode of claim 1 , wherein said graphene foam has an oxygen content or non-carbon content no greater than 0.1% by weight and said pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.336 nm, a mosaic spread value no greater than 0.7, a thermal conductivity of at least 350 W/mK per unit of specific gravity, and/or an electrical conductivity no less than 3,500 S/cm per unit of specific gravity.

14 . The supercapacitor electrode of claim 1 , wherein said graphene foam has pore walls containing stacked graphene planes having an inter-graphene spacing less than 0.336 nm, a mosaic spread value no greater than 0.4, a thermal conductivity greater than 400 W/mK per unit of specific gravity, and/or an electrical conductivity greater than 4,000 S/cm per unit of specific gravity.

15 . The supercapacitor electrode of claim 1 , wherein the pore walls contain stacked graphene planes having an inter-graphene spacing less than 0.337 nm and a mosaic spread value less than 1.0.

16 . The supercapacitor electrode of claim 1 , wherein the solid graphene foam exhibits a degree of graphitization no less than 80% and/or a mosaic spread value less than 0.4.

17 . The supercapacitor electrode of claim 1 , wherein said pore walls contain a 3D network of interconnected graphene planes.

18 . The supercapacitor electrode of claim 1 , wherein said solid graphene foam contains pores having a pore size from 0.5 nm to 100 nm, measured in a dried state without said electrolyte.

19 . The supercapacitor electrode of claim 1 , wherein said liquid electrolyte contains an aqueous electrolyte, organic electrolyte, ionic liquid electrolyte, or a mixture of an organic and an ionic liquid electrolyte.

20 . A supercapacitor comprising an anode, a porous separator-electrolyte layer or electrolyte-permeable membrane, and a cathode, wherein either or both of said anode and said cathode contains the electrode of claim 1 .

21 . The supercapacitor of claim 20 , which is a lithium-ion capacitor or sodium-ion capacitor having a cathode containing the electrode of claim 1 and an anode containing a pre-lithiated anode active material or a pre-sodiated anode active material.

Assignees

• Zhamu Aruna
• Jang Bor Z

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01G11/06

  with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC] · CPC title

• H01G11/26

  characterised by their structure, e.g. multi-layered, porosity or surface features · CPC title

• H01G11/58

  Liquid electrolytes · CPC title

• H01G11/32 Primary

  Carbon-based · CPC title

• H01G11/46

  Metal oxides · CPC title