# US 10,479,690 B2 · Process for producing monolithic film of integrated highly oriented halogenated graphene sheets or molecules

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- Number: US 10,479,690 B2
- Document ID: US10479690B2
- Status: Granted
- Kind: B2
- Application number: 15/705,890
- Filed: 2017-09-15
- Published: 2018-01-18
- Granted: 2019-11-19
- Earliest claimed: 2015-09-23
- Assignees: Global Graphene Group, Inc.
- Applicants: Nanotek Instruments, Inc.
- Inventors: Aruna Zhamu; Bor Z. Jang
- Web page: https://patentgrep.com/patent/US10479690B2

## CPC

- C01B 32/194: After-treatment
- C23C 16/06: characterised by the deposition of metallic material
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

A process for producing an integrated layer (10 nm to 500 μm) of highly oriented halogenated graphene sheets, comprising: (a) preparing a graphene oxide (GO) dispersion having GO sheets dispersed in a fluid medium; (b) dispensing and depositing a layer of GO dispersion onto a surface of a supporting substrate under a shear stress condition that induces orientation of GO sheets to form a wet layer of GO on the supporting substrate; (c) introducing a halogenating agent into the wet layer of graphene oxide and effecting a chemical reaction between the halogenating agent and GO sheets to form a wet layer of halogenated graphene, C6ZxOy, wherein Z is a halogen element selected from F, Cl, Br, I, or a combination thereof, x=0.01 to 6.0, y=0 to 5.0, and x+y≤6.0; and (d) removing the fluid medium.

## Claims

### Claim 1

A process for producing an integrated layer of highly oriented halogenated graphene sheets or molecules, said process comprising:
(a) preparing either a graphene oxide dispersion having graphene oxide sheets dispersed in a fluid medium or a graphene oxide gel having graphene oxide molecules dissolved in a fluid medium, wherein said graphene oxide sheets or graphene oxide molecules contain an oxygen amount 5% by weight to 46% by weight;
(b) introducing a halogenating agent into said graphene oxide dispersion or gel and effecting a chemical reaction between said halogenating agent and said graphene oxide sheets or molecules to form a dispersion of halogenated graphene sheets or a gel of halogenated graphene molecules, wherein said halogenated graphene sheets or molecules have a chemical formula of C6ZxOy, wherein Z is a halogen element selected from F, Cl, Br, I, or a combination thereof, x=0.01 to 6.0, y=0 to 5.0, and x+y<6.0;
(c) dispensing and depositing a layer of said halogenated graphene dispersion or gel onto a surface of a supporting substrate under a shear stress condition, wherein said dispensing and depositing procedure includes shear-induced thinning of said halogenated graphene dispersion or gel and shear-induced orientation of halogenated graphene sheets or molecules, to form a wet layer of halogenated graphene on said supporting substrate; and
(d) removing said fluid medium from the wet layer of halogenated graphene to form said integrated layer of halogenated graphene having an inter-planar spacing d002 of 0.35 nm to 1.2 nm as determined by X-ray diffraction.

### Claim 2 (depends on 1)

The process of claim 1, wherein the graphene oxide sheets contain single-layer graphene oxide or few-layer graphene oxide sheets each having 2-10 oxidized graphene planes.

### Claim 3 (depends on 1)

The process of claim 1, wherein the dispensing and depositing step includes a reverse roll transfer coating procedure.

### Claim 4 (depends on 1)

The process of claim 1, wherein the dispensing and depositing step includes a slot die coating or comma coating procedure.

### Claim 5 (depends on 1)

The process of claim 1, further comprising a step (e) of heat treating the integrated layer of oriented halogenated graphene at a first heat treatment temperature higher than 100° C. but no greater than 3,200° C. for a desired length of time to produce a graphitic film having an inter-planar spacing d002 less than 0.4 nm and a combined oxygen/halogen content less than 1% by weight.

### Claim 6 (depends on 1)

The process of claim 1, wherein the fluid medium consists of water, an alcohol, a mixture of water and alcohol, or an organic solvent.

### Claim 7 (depends on 1)

The process of claim 1, further comprising a compression step, during or after removing the fluid medium, to reduce a thickness of said integrated layer.

### Claim 8 (depends on 1)

The process of claim 1, wherein the graphene oxide dispersion or gel has a graphene oxide content of 1% to 50% by weight prior to introducing the halogenating agent.

### Claim 9 (depends on 1)

The process of claim 1, wherein the graphene oxide dispersion or gel has a graphene oxide content of 3% to 50% by weight prior to introduction the halogenating agent, and the graphene oxide dispersion or gel possesses a liquid crystal phase.

### Claim 10 (depends on 1)

The process of claim 1, wherein the step of removing the fluid medium from the wet layer of halogenated graphene is carried out by heat treatment, vacuum, or a combination thereof.

### Claim 11 (depends on 1)

The process of claim 1, wherein the step of forming a dispersion of halogenated graphene sheets or a gel of halogenated graphene molecules comprises irradiation with UV light in a liquid medium containing chlorine or bromine.

### Claim 12 (depends on 1)

The process of claim 1, wherein the integrated layer of halogenated graphene has a thickness from 10 nm to 500 μm.