Production process for highly conducting and oriented graphene film

Patent metadata

Field	Value
Publication number	US-10163540-B2
Application number	US-201514757194-A
Country	US
Kind code	B2
Filing date	Dec 3, 2015
Priority date	Dec 3, 2015
Publication date	Dec 25, 2018
Grant date	Dec 25, 2018

Abstract

A process for producing a highly conducting film of conductor-bonded graphene sheets that are highly oriented, comprising: (a) preparing a graphene dispersion or graphene oxide (GO) gel; (b) depositing the dispersion or gel onto a supporting solid substrate under a shear stress to form a wet layer; (c) drying the wet layer to form a dried layer having oriented graphene sheets or GO molecules with an inter-planar spacing d 002 of 0.4 nm to 1.2 nm; (d) heat treating the dried layer at a temperature from 55° C. to 3,200° C. for a desired length of time to produce a porous graphitic film having pores and constituent graphene sheets or a 3D network of graphene pore walls having an inter-planar spacing d 002 less than 0.4 nm; and (e) impregnating the porous graphitic film with a conductor material that bonds the constituent graphene sheets or graphene pore walls to form the conducting film.

First claim

We claim:

1. A process for producing a thermally conducting film of conductor-bonded graphene sheets that are oriented, said process comprising:
(a) preparing either a graphene dispersion having discrete graphene sheets dispersed in a fluid medium or a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium, wherein said graphene oxide molecules contain an oxygen content from 5% to 50% by weight;
(b) dispensing and depositing said graphene dispersion or graphene oxide gel onto a surface of supporting solid substrate under a shear stress to form a wet layer of graphene or graphene oxide, having oriented graphene sheets or graphene oxide molecules, on said supporting substrate;
(c) at least partially removing said fluid medium from the wet layer of graphene or graphene oxide to form a dried layer of graphene, or dried layer of graphene oxide having an inter-planar spacing d 002 from 0.4 nm to 1.2 nm as determined by X-ray diffraction;
(d) heat treating the dried layer of graphene or graphene oxide at a heat treatment temperature from 55° C. to 3,200° C. for a desired length of time to produce a porous graphitic film having pores and constituent graphene sheets or a 3D network of graphene pore walls having an inter-planar spacing d 002 from 0.3354 nm to 0.4 nm, wherein said porous graphitic film has chemically bonded graphene planes that are all essentially oriented parallel to one another; and
(e) impregnating said porous graphitic film with a liquid or vapor phase metal conductor material or liquid or vapor phase metal conductor material precursor that bonds said constituent graphene sheets or 3D network of graphene pore walls to form said conducting film having a continuous network of electron-conducting and phonon-conducting pathways wherein said conductor material bridge gaps or interruptions in graphene planes, enabling barrier-free transport of electrons and phonons between graphene planes.

2. The process of claim 1 , further comprising a step (f) of mechanically compressing or consolidating said conducting film.

3. A process for producing a thermally conducting film of conductor-bonded graphene sheets that are oriented, said process comprising:
(a) preparing either a graphene dispersion having discrete graphene sheets dispersed in a fluid medium or a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium, wherein said graphene oxide molecules contain an oxygen content from 5% to 50% by weight;
(b) dispensing and depositing said graphene dispersion or graphene oxide gel onto a surface of supporting solid substrate under a shear stress to form a wet layer of graphene or graphene oxide, having oriented graphene sheets or graphene oxide molecules, on said supporting substrate;
(c) at least partially removing said fluid medium from the wet layer of graphene or graphene oxide to form a dried layer of graphene, or dried layer of graphene oxide having an inter-planar spacing d 002 from 0.4 nm to 1.2 nm as determined by X-ray diffraction;
(d) heat treating the dried layer of graphene or graphene oxide at a heat treatment temperature from 55° C. to 3,200° C. for a desired length of time to produce a porous graphitic film having pores and constituent graphene sheets or a 3D network of graphene pore walls having an inter-planar spacing d 002 from 0.3354 nm to 0.4 nm, wherein said porous graphitic film has chemically bonded graphene planes that are all essentially oriented parallel to one another;
(e) impregnating said porous graphitic film with a conductor material or conductor material precursor that bonds said constituent graphene sheets or 3D network of graphene pore walls to form said conducting film having a continuous network of electron-conducting and phonon-conducting pathways wherein said conductor material bridge gaps or interruptions in graphene planes, enabling barrier-free transport of electrons and phonons between graphene planes and wherein said conductor material or conductor material precursor is selected from an intrinsically conductive polymer, a conductive organic compound, or a combination thereof, wherein said intrinsically conductive polymer is selected from poly(fluorene), polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepine, poly(3,4-ethylenedioxythiophene) (PEDOT), poly(p-phenylene sulfide) (PPS), poly(acetylene) (PAC), or poly(p-phenylene vinylene) (PPV).

4. The process of claim 1 , wherein said liquid or vapor phase metal conductor material or liquid or vapor phase metal conductor material precursor comprises a metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Pd, Ag, Cd, Au, Pt, W, Al, Sn, In, Pb, Bi, an alloy thereof, or a mixture thereof.

5. The process of claim 1 , wherein said liquid or vapor phase metal conductor material or liquid or vapor phase metal conductor material precursor comprises a metal selected from Cu, Al, Ti, Sn, Ag, Au, Fe, or an alloy thereof.

6. A process for producing a thermally conducting film of conductor-bonded graphene sheets that are oriented, said process comprising:
(a) preparing either a graphene dispersion having discrete graphene sheets dispersed in a fluid medium or a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium, wherein said graphene oxide molecules contain an oxygen content from 5% to 50% by weight;
(b) dispensing and depositing said graphene dispersion or graphene oxide gel onto a surface of supporting solid substrate under a shear stress to form a wet layer of graphene or graphene oxide, having oriented graphene sheets or graphene oxide molecules, on said supporting substrate;
(c) at least partially removing said fluid medium from the wet layer of graphene or graphene oxide to form a dried layer of graphene, or dried layer of graphene oxide having an inter-planar spacing d 002 from 0.4 nm to 1.2 nm as determined by X-ray diffraction;
(d) heat treating the dried layer of graphene or graphene oxide at a heat treatment temperature from 55° C. to 3,200° C. for a desired length of time to produce a porous graphitic film having pores and constituent graphene sheets or a 3D network of graphene pore walls having an inter-planar spacing d 002 from 0.3354 nm to 0.4 nm, wherein said porous graphitic film has chemically bonded graphene planes that are all essentially oriented parallel to one another;
(e) impregnating said porous graphitic film with a conductor material or conductor material precursor that bonds said constituent graphene sheets or 3D network of graphene pore walls to form said conducting film having a continuous network of electron-conducting and phonon-conducting pathways wherein said conductor material bridges gaps or interruptions in graphene planes, enabling barrier-free transport of electrons and phonons between graphene planes and wherein said conductor material or conductor material precursor contains a conductive organic compound selected from isotropic pitch, mesophase pitch, a polycyclic aromatic compound, pentacene, anthracene, rubrene, or a combination thereof.

7. The process of claim 1 , wherein said conductor material occupies a weight fraction of 0.1%-50% based on the total weight of said conducting film.

8. The process of claim 1 , wherein said conductor material occupies a weight fraction of 1%-20% based on the total weight of said conducting film.

9. The process of claim 1 , wherein said conductor material bonds said constituent graphene sheets at least in an end-to-end manner, or said conductor material fills into pores of said porous graphitic film.

10. The process of claim 1 , wherein said dispensing and depositing step includes an operation of spraying, casting, printing, coating, or a combin

Assignees

• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• C25D3/22

  of zinc · CPC title

• C23C14/0605

  Carbon · CPC title

• C01B32/19

  by exfoliation · CPC title

• C23C18/1644

  porous substrates · CPC title

• C25D5/54

  Electroplating of non-metallic surfaces (C25D7/12 takes precedence) · CPC title