CN108221370B - Environment-stable high-conductivity graphene composite fiber and preparation method thereof - Google Patents

Environment-stable high-conductivity graphene composite fiber and preparation method thereof Download PDF

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CN108221370B
CN108221370B CN201810061944.8A CN201810061944A CN108221370B CN 108221370 B CN108221370 B CN 108221370B CN 201810061944 A CN201810061944 A CN 201810061944A CN 108221370 B CN108221370 B CN 108221370B
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graphene
fiber
conductivity
composite fiber
potassium
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CN108221370A (en
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高超
刘英军
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Changxin de Technology Co., Ltd.
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Changxing Dexi Technology Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Abstract

The invention discloses an environment-stable high-conductivity graphene composite fiber and a preparation method thereof. By adopting a wet spinning technology, firstly preparing graphene oxide fibers from graphene oxide, and then sequentially carrying out reduction treatment and chemical doping to prepare the high-conductivity graphene fibers. And further forming a molecular protective layer on the surface of the doped graphene fiber through in-situ grafting by surface grafting reaction. The preparation process is simple and controllable, and the obtained graphene fiber has excellent mechanical properties and conductivity. The graphene composite fiber with stable and high conductivity can be used as a lead and is applied to the fields of light electric motors, flexible wearable equipment, electromagnetic protective clothing and the like.

Description

Environment-stable high-conductivity graphene composite fiber and preparation method thereof
Technical Field
The invention relates to a high-conductivity graphene composite fiber, in particular to an environment-stable high-conductivity graphene composite fiber and a preparation method thereof.
Background
The graphene has the highest mechanical property, the modulus is 1.1TPa, and the strength is 180 GPa; the highest carrier transmission rate of up to 150000cm2Vs; highest conductivity (10)8S/m) and ultra-high current load density. The high-performance graphene fiber is prepared by adopting a graphene oxide liquid crystal wet spinning technology, and is expected to convert the excellent characteristics of graphene on the micro scale into the performances on the macro scale. Researches show that the graphene fiber has good development prospect as a light wire. However, the conductivity of the pure graphene fiber reported at present is 0.8MS/m at most, and the conductivity can be improved to 22MS/m after chemical doping, but the pure graphene fiber is unstable in air and is difficult to meet the actual application requirements (Advanced Materials 2016,28, 7941). Therefore, there is a need to search for new methods to improve the stability of doped graphene fibers.
Disclosure of Invention
The invention aims to overcome the defect of poor conductivity stability of the existing chemical-doped graphene fiber, and provides an environmentally-stable high-conductivity graphene composite fiber and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: the utility model provides a high electrically conductive graphite alkene composite fiber of environmental stability, includes graphite alkene inner core and molecule inoxidizing coating, the graphite alkene inner core is formed along axial orderly arrangement by graphite alkene, and about 0.3 ~ 0.4nm of graphite alkene interval, the doping has potassium ion between the graphite alkene lamina, the molecule inoxidizing coating comprises the halohydrocarbon molecule, and the halohydrocarbon molecule is covalence bonded with the graphite alkene on graphite alkene inner core top layer.
Further, in the graphene inner core, the content of potassium is 10-30 wt%; the orientation degree of the graphene fibers is 80-90%.
A preparation method of an environment-stable high-conductivity graphene composite fiber comprises the following steps:
(1) enabling 10mg/mL of graphene oxide spinning solution to pass through a spinning head with the aperture of 30-300 mu m at the extrusion speed of 1-100 mL/h, staying in a coagulation bath at 10-50 ℃ for 5-60 s, and collecting to obtain continuous graphene oxide fibers;
(2) and (2) placing the graphene oxide fiber obtained in the step (1) in a graphite furnace at the temperature of 1000-3000 ℃, and carrying out heat treatment in the atmosphere for 0.5-1.5 h to obtain the high-quality graphene fiber.
(3) And (3) treating the high-quality graphene fiber obtained in the step (2) in potassium steam for 1-24 hours to obtain the high-conductivity potassium-doped graphene fiber.
(4) And (3) placing the potassium-doped graphene fiber obtained in the step (2) in halogenated hydrocarbon, keeping for 12-24 hours, and taking out to obtain the graphene composite fiber with stable environment and high conductivity.
Further, in the step (4), the halogenated hydrocarbon is mainly formed by mixing one or more of chloro-n-hexane, iodo-n-hexane, fluoro-n-hexane, perfluorooctyl iodoalkane, perfluorodecyl iodoalkane, 1,2, 2-tetrahydroperfluorohexyl iodide and the like according to any proportion.
The invention has the following technical effects:
1. the graphene fiber is prepared by adopting a wet spinning technology, so that the operation is simple and convenient;
2. the conductivity of the graphene fiber is obviously improved through high-temperature heat treatment and chemical doping.
3. The surface in-situ grafting is used for forming a molecular protective layer, so that oxygen and water are prevented from entering the fiber, and the conductivity of the fiber can be kept stable for a long time.
Drawings
Fig. 1 is a schematic structural diagram of an environmentally stable highly conductive graphene composite fiber;
fig. 2 is a conductive performance evaluation curve of the graphene fiber before and after the grafting of the molecular protective layer.
Detailed Description
It should be noted that, in the present invention, the potassium-doped graphene fiber is only required to be soaked in the halogenated hydrocarbon solvent, and the halogenated hydrocarbon compound and the graphene with negative charges on the surface layer undergo a covalent grafting reaction to form a hydrophobic protective layer, so that the whole process is simple and controllable. After the reaction, the graphene composite fiber has good stability in the air, and the conductivity is obviously superior to that of potassium-doped graphene fiber without surface modification.
The invention is further described with reference to the following figures and examples. The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention, and the non-essential changes and modifications thereof by those skilled in the art can be made without departing from the spirit and scope of the invention.
Example 1:
(1) allowing 10mg/mL graphene oxide spinning solution to pass through a spinning head with the aperture of 30 mu m at the extrusion speed of 1mL/h, staying in a coagulating bath at 10 ℃ for about 60s, and collecting to obtain continuous graphene oxide fibers;
(2) and (2) placing the graphene oxide fiber obtained in the step (1) in a graphite furnace at 1000 ℃, and carrying out heat treatment for 0.5h in the atmosphere to obtain the high-quality graphene fiber.
(3) And (3) treating the graphene fiber obtained in the step (2) in potassium steam for 1h to obtain the high-conductivity potassium-doped graphene fiber.
(4) And (3) placing the potassium-doped graphene fiber obtained in the step (2) into perfluorooctyl iodoalkane, keeping for 12 hours, and taking out to obtain the graphene composite fiber with stable environment and high conductivity.
The environment-stable high-conductivity graphene composite fiber is obtained through the steps, the diameter of the fiber is 5-150 mu m, the fiber comprises a graphene inner core and a molecular protective layer, the graphene inner core is formed by orderly arranging graphene along the axial direction, and the orientation degree is 90%; the graphene layers have the spacing of about 0.3-0.4 nm, potassium ions are doped between the graphene layers, and the content of potassium is 10 wt%; the molecular protective layer is composed of halogenated hydrocarbon molecules. By Raman spectroscopy, at 1350cm-1A strong D peak appears, which indicates that halogenated hydrocarbon molecules are grafted on the surface of the fiber. Similarly, the covalent grafting reaction of the halogenated hydrocarbon molecules and the fiber surface layer graphene can be analyzed from the X-ray photoelectron spectrum. The test shows that the elongation at break is 2-8%, the tensile strength is 200-800 MPa, and the electric conductivity in the air can be maintained at 1000000S/m for a long time.
Example 2:
(1) allowing 10mg/mL graphene oxide spinning solution to pass through a spinning head with the aperture of 300 mu m at the extrusion speed of 100mL/h, staying in a coagulating bath at 50 ℃ for about 5s, and collecting to obtain continuous graphene oxide fibers;
(2) and (2) placing the graphene oxide fiber obtained in the step (1) in a graphite furnace at 2000 ℃, and carrying out heat treatment for 1h in the atmosphere to obtain the high-quality graphene fiber.
(3) And (3) treating the graphene fibers obtained in the step (2) in potassium steam for 16 hours to obtain the high-conductivity potassium-doped graphene fibers.
(4) And (3) placing the potassium-doped graphene fiber obtained in the step (2) into perfluorodecyl iodoalkane, keeping for 18h, and taking out to obtain the graphene composite fiber with stable environment and high conductivity.
The environment-stable high-conductivity graphene composite fiber is obtained through the steps, the diameter of the fiber is 5-150 mu m, the fiber comprises a graphene inner core and a molecular protective layer, the graphene inner core is formed by orderly arranging graphene along the axial direction, the orientation degree is 90%, the distance between graphene layers is about 0.3-0.4 nm, potassium ions are doped between graphene layers, and the content of potassium is 24 wt%; the molecular protective layer is composed of halogenated hydrocarbon molecules. Through Raman spectrum analysis, a stronger D peak appears at 1350cm < -1 >, which indicates that halogenated hydrocarbon molecules are grafted on the surface of the fiber. Similarly, the covalent grafting reaction of the halogenated hydrocarbon molecules and the fiber surface layer graphene can be analyzed from the X-ray photoelectron spectrum. The test shows that the elongation at break is 1-6%, the tensile strength is 200-800 MPa, and the electric conductivity in the air can be maintained at 4000000S/m for a long time.
Example 3
(1) Enabling 10mg/mL graphene oxide spinning solution to pass through a spinning head with the aperture of 100 mu m at the extrusion speed of 80mL/h, staying in a coagulating bath at 40 ℃ for about 30s, and collecting to obtain continuous graphene oxide fibers;
(2) and (2) placing the graphene oxide fiber obtained in the step (1) in a graphite furnace at 3000 ℃, and carrying out heat treatment for 1.5h in the atmosphere to obtain the high-quality graphene fiber.
(3) And (3) treating the graphene fibers obtained in the step (2) in potassium steam for 24 hours to obtain the high-conductivity potassium-doped graphene fibers.
(4) And (3) placing the potassium-doped graphene fiber obtained in the step (2) into 1,1,2, 2-tetrahydroperfluorohexyl iodide, keeping for 24 hours, and taking out to obtain the graphene composite fiber with stable environment and high conductivity.
The environment-stable high-conductivity graphene composite fiber is obtained through the steps, the diameter of the fiber is 5-150 mu m, the fiber comprises a graphene inner core and a molecular protective layer, the graphene inner core is formed by orderly arranging graphene along the axial direction, and the orientation degree is 86%; the graphene layers have the spacing of about 0.3-0.4 nm, potassium ions are doped between the graphene layers, and the content of potassium is 30 wt%; the molecular protective layer is composed of halogenated hydrocarbon molecules. Through Raman spectrum analysis, a stronger D peak appears at 1350cm < -1 >, which indicates that halogenated hydrocarbon molecules are grafted on the surface of the fiber. Similarly, the covalent grafting reaction of the halogenated hydrocarbon molecules and the fiber surface layer graphene can be analyzed from the X-ray photoelectron spectrum. The test shows that the elongation at break is 0.5-3%, the tensile strength is 600-1000 MPa, and the electric conductivity in air can be maintained above 15000000S/m for a long time, as shown in FIG. 2.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the claims.

Claims (4)

1. The environment-stable high-conductivity graphene composite fiber is characterized by comprising a graphene inner core and a molecular protective layer, wherein the graphene inner core is formed by orderly arranging graphene along the axial direction, the distance between graphene layers is 0.3-0.4 nm, potassium ions are doped between graphene layers, and the content of potassium is 10-30 wt%; the molecule protective layer is composed of halogenated hydrocarbon molecules, and the halogenated hydrocarbon molecules are covalently bonded with graphene on the surface layer of the graphene inner core.
2. The composite fiber according to claim 1, wherein the graphene core has a degree of orientation of 80-90% of graphene fibers.
3. The preparation method of the environmentally stable and highly conductive graphene composite fiber according to claim 1, comprising the following steps:
(1) enabling 10mg/mL of graphene oxide spinning solution to pass through a spinning head with the aperture of 30-300 mu m at the extrusion speed of 1-100 mL/h, staying in a coagulation bath at 10-50 ℃ for 5-60 s, and collecting to obtain continuous graphene oxide fibers;
(2) placing the graphene oxide fiber obtained in the step (1) in a graphite furnace at 1000-3000 ℃, and carrying out heat treatment in the atmosphere for 0.5-1.5 h to obtain a high-quality graphene fiber;
(3) treating the high-quality graphene fiber obtained in the step (2) in potassium steam for 1-24 hours to obtain a high-conductivity potassium-doped graphene fiber;
(4) and (3) placing the potassium-doped graphene fiber obtained in the step (2) in halogenated hydrocarbon, keeping for 12-24 hours, and taking out to obtain the graphene composite fiber with stable environment and high conductivity.
4. The method for preparing the environmentally stable and highly conductive graphene composite fiber according to claim 3, wherein the halogenated hydrocarbon in the step (4) is prepared by mixing one or more of chloro-n-hexane, iodo-n-hexane, fluoro-n-hexane, perfluorooctyl-iodoalkane, perfluorodecyl iodoalkane and 1,1,2, 2-tetrahydroperfluorohexyl iodide according to any ratio.
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Publication number Priority date Publication date Assignee Title
CN102586922A (en) * 2012-01-18 2012-07-18 浙江大学 Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene
CN102926020A (en) * 2012-11-14 2013-02-13 浙江大学 Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength
EP2687626A2 (en) * 2011-03-15 2014-01-22 IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) Graphene fiber and method for manufacturing same
CN104099687A (en) * 2013-04-10 2014-10-15 华为技术有限公司 Graphene fiber and preparation method thereof
CN105544017A (en) * 2016-01-27 2016-05-04 浙江大学 High-conductivity graphene fiber and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2687626A2 (en) * 2011-03-15 2014-01-22 IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) Graphene fiber and method for manufacturing same
CN102586922A (en) * 2012-01-18 2012-07-18 浙江大学 Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene
CN102926020A (en) * 2012-11-14 2013-02-13 浙江大学 Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength
CN104099687A (en) * 2013-04-10 2014-10-15 华为技术有限公司 Graphene fiber and preparation method thereof
CN105544017A (en) * 2016-01-27 2016-05-04 浙江大学 High-conductivity graphene fiber and preparation method thereof

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