# US 10,865,502 B2 · Continuous graphene fibers from functionalized graphene sheets

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- Number: US 10,865,502 B2
- Document ID: US10865502B2
- Status: Granted
- Kind: B2
- Application number: 15/978,712
- Filed: 2018-05-14
- Published: 2019-11-14
- Granted: 2020-12-15
- Earliest claimed: 2018-05-14
- Assignees: Global Graphene Group, Inc.
- Applicants: Nanotek Instruments, Inc.
- Inventors: Aruna Zhamu; Bor Z. Jang
- Web page: https://patentgrep.com/patent/US10865502B2

## CPC

- D01F 9/22: from polyacrylonitriles
- C09K 5/14: Solid materials, e.g. powdery or granular
- D01D 5/04: Dry spinning methods {(D01D5/0038 takes precedence)}
- D01F 9/08: of inorganic material (working or processing of metal wire B21F; from softened glass, minerals or slags C03B37/00)
- D01F 9/12: Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F 9/145: from pitch or distillation residues
- H01B 1/04: mainly consisting of carbon-silicon compounds, carbon or silicon
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- Y10S 977/734: Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S 977/847: Surface modifications, e.g. functionalization, coating
- Y10S 977/961: for textile or fabric treatment
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- D01D: MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K})
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Provided is a graphene-based long fiber comprising chemically functionalized graphene sheets that are chemically bonded with one another having an inter-planar spacing d002 from 0.36 nm to 1.5 nm as determined by X-ray diffraction and a non-carbon element content of 0.1% to 40% by weight, wherein the functionalized graphene sheets are substantially parallel to one another and parallel to the fiber axis direction and the fiber contains no core-shell structure, have no helically arranged graphene domains, and have a length no less than 0.5 cm and a physical density from 1.5 to 2.2 g/cm3. The graphene fiber typically has a thermal conductivity from 300 to 1,600 W/mK, an electrical conductivity from 600 to 15,000 S/cm, or a tensile strength higher than 1.0 GPa.

## Claims

### Claim 1

A graphene-based long fiber comprising chemically functionalized graphene sheets that are chemically bonded or interconnected with one another having an inter-planar spacing d002 from 0.36 nm to 1.5 nm as determined by X-ray diffraction and a non-carbon element content of 0.1% to 47% by weight, wherein said functionalized graphene sheets are substantially parallel to one another and parallel to a fiber axis direction and said fiber contains no core-shell structure, have no helically arranged graphene domains, and have a length no less than 0.5 cm and a physical density from 1.5 to 2.2 g/cm3, wherein said graphene sheets are chemically bonded between functional groups, wherein said functionalized graphene sheets are chemically bonded or interconnected with one another in a face-to-edge manner.

### Claim 2 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from the group consisting of alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, carboxylic group, amine group, sulfonate group (—SO3H), aldehydic group, quinoidal, fluorocarbon, derivatives thereof, and combinations thereof.

### Claim 3 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from a derivative of an azide compound selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropanoate, chlorocarbonate, azidocarbonate, dichlorocarbene, carbene, aryne, nitrene, (R-)-oxycarbonyl nitrenes, where R=any one of the following groups,
and combinations thereof.

### Claim 4 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from an oxygenated group consisting of hydroxyl, peroxide, ether, keto, aldehyde, and combinations thereof.

### Claim 5 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from the group consisting of —SO3H, —COOH, —NH2, —OH, —R′CHOH, —CHO, —CN, —COCl, halide, —COSH, —SH, —COOR′, —SW, —SiR′3, —Si(—OR′—)yR′3-y, —Si(—O—SiR′2—)OR′, —R″, Li, AlR′2, Hg—X, TlZ2 and Mg—X; wherein y is an integer equal to or less than 3, R′ is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R″ is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate, derivatives thereof, and combinations thereof.

### Claim 6 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, derivatives thereof, and combinations thereof.

### Claim 7 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from OY, NHY, O═C—OY, P═C—NR′Y, O═C—SY, O═C—Y, —CR′1-OY, N′Y or C′Y, a derivative thereof, or a combination thereof, and Y is a functional group of a protein, a peptide, an amino acid, an enzyme, an antibody, a nucleotide, an oligonucleotide, an antigen, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from R′—OH, R′—NR′2, R′SH, R′CHO, R′CN, R′X, R′N+(R′)3X−, R′SiR′3, R′Si(—OR′—)yR′3-y, R′Si(—O—SiR′2—)OR′, R′—R″, R′—N—CO, (C2H4O—)wH, (—C3H6O—)wH, (—C2H4O)w—R′, (C3H6O)w—R′, R′, and w is an integer greater than one and less than 200.

### Claim 8 (depends on 1)

The long fiber of claim 1, wherein said chemically functionalized graphene sheets contain a chemical functional group selected from the group consisting of 10,12-pentacosadiyn-1-ol, hydroiodic acid, 1-pyrenebutyric acid N-hydroxysuccinimide ester, 1-aminopyrene, derivatives thereof, and combinations thereof.

### Claim 9 (depends on 1)

The long fiber of claim 1, wherein said inter-plane spacing d002 is greater than 0.4 nm and said inter-plane spacing d002 is no greater than 1.2 nm, the non-carbon element content is from 1% to 20%, or physical density from 1.7 to 2.15 g/cm3.

### Claim 10 (depends on 1)

The long fiber of claim 1, having a cross-section that is circular, elliptical, rectangular, flat-shaped, or hollow.

### Claim 11 (depends on 1)

The long fiber of claim 1, having a cross-section that has a length from 1 cm to 10,000 meters, a width or second largest dimension from 1 μm to 5 mm, and a thickness or smallest dimension from 10 nm to 500 μm, and a width-to-thickness ratio from 1 to 10,000.

### Claim 12 (depends on 1)

The long fiber of claim 1, having a thickness from 100 nm to 100 μm.

### Claim 13 (depends on 1)

The long fiber of claim 1, having a thermal conductivity from 200 to 1,600 W/mK, or an electrical conductivity from 600 to 15,000 S/cm.

### Claim 14 (depends on 1)

The long fiber of claim 1, having a thermal conductivity of at least 350 W/mK, or an electrical conductivity no less than 1,000 S/cm.

### Claim 15 (depends on 1)

The long fiber of claim 1, having a thermal conductivity of at least 600 W/mK, or an electrical conductivity no less than 2,500 S/cm.

### Claim 16 (depends on 1)

The long fiber of claim 1, having a thermal conductivity of at least 1,000 W/mK, or an electrical conductivity no less than 5,000 S/cm.

### Claim 17 (depends on 1)

The long fiber of claim 1, having a thermal conductivity of at least 1,200 W/mK, or an electrical conductivity no less than 8,000 S/cm.

### Claim 18 (depends on 1)

The long fiber of claim 1, wherein said long fiber contains a first graphene domain containing bonded graphene planes parallel to one another and having a first crystallographic c-axis, and a second graphene domain containing bonded graphene planes parallel to one another and having a second crystallographic c-axis wherein the first crystallographic c-axis and the second crystallographic c-axis are inclined with respect to each other at an angle less than 10 degrees.

### Claim 19 (depends on 1)

The long fiber of claim 1, wherein said long fiber contains a combination of sp2 and spa electronic configurations.

### Claim 20 (depends on 1)

The long fiber of claim 1, wherein said long fiber has a Young's modulus from 20 GPa to 300 GPa or a tensile strength from 1.0 GPa to 5.0 GPa.

### Claim 21 (depends on 1)

The long fiber of claim 1, wherein said long fiber has a Young's modulus from 30 GPa to 150 GPa or a tensile strength from 1.2 GPa to 3.0 GPa.

### Claim 22 (depends on 1)

A fiber yarn or bundle comprising at least a long fiber of claim 1 and optionally comprising multiple PAN-derived or pitch-derived carbon fibers.

### Claim 23 (depends on 1)

A fiber yarn or bundle comprising multiple long fibers of claim 1.