CN111218814A - Graphene-metal wire composite fiber and preparation method thereof - Google Patents

Graphene-metal wire composite fiber and preparation method thereof Download PDF

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CN111218814A
CN111218814A CN201811417029.4A CN201811417029A CN111218814A CN 111218814 A CN111218814 A CN 111218814A CN 201811417029 A CN201811417029 A CN 201811417029A CN 111218814 A CN111218814 A CN 111218814A
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wire
graphene
sub
fiber
metal wire
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陈永胜
赵恺
张腾飞
任爱
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Nankai University
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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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • 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

Abstract

The invention relates to a graphene-metal wire composite fiber, wherein the composite fiber has an n-level super-spiral multistage structure composed of sub-fibers, a 1 st-level sub-fiber is formed by spirally winding s metal wires coated with graphene, an m-level sub-fiber is formed by spirally winding t m-1 th-level sub-fibers, continuous graphene with uniform thickness is arranged on the surfaces of the metal wires and among the metal wires, n is an integer not less than 6, m is an integer greater than 1 and less than or equal to n, and s and t are integers not less than 6 in each occurrence, and the volume percentage of the graphene is greater than or equal to 0.4% based on the volume of the metal wires coated with the graphene. The invention also relates to a method for preparing the graphene-metal wire composite material.

Description

Graphene-metal wire composite fiber and preparation method thereof
Technical Field
The invention belongs to the field of graphene reinforced composite materials, and particularly relates to a graphene-metal wire composite fiber with a multistage supercoiled structure and a preparation method thereof.
Background
Conventional metal conductors, such as copper (Cu) and aluminum (Al), are widely used in electrical applications such as wires and cables due to their excellent electrical conductivity. However, most metals are limited by electromigration, with a maximum current density of about 1010Am-2Typically, than carbon nanomaterials (about 10)12Am-2) The current density of (a) is two orders of magnitude lower. Furthermore, the lower melting point and thermal/chemical stability of metal conductors compared to conventional carbon-based materials (e.g., graphite conductors) prevents their use under heavy-duty and high-power conditions. In contrast, carbon nanomaterials, such as graphene and carbon nanotubes, have excellent current-carrying capability to maintain a high current density, and ultra-high thermal and chemical stability due to their strong C — C bonds. However, the low electrical conductivity of carbon nanomaterials and their macroscopic assemblies remains one of the obstacles in their use as electrical conductors. In general, high current carrying capacity and high conductivity are incompatible material properties because the former requires a strongly bonded chemical structural system, while the latter requires a weakly bonded system with a large number of free electrons. Therefore, achieving both high current carrying capacity and high conductivity in conventional materials is an urgent and important research task.
Graphene is a novel two-dimensional carbon nanomaterial and has excellent optical, electrical, thermal and mechanical properties. The composite material can be endowed with more excellent performance through the compounding of the nano graphene material and other traditional materials. The compounding of graphene with metals is one of the important parts in the research of graphene nanocomposites. The graphene has high current carrying capacity, melting point and thermal/chemical stability, and the composite material of the graphene and metal has obviously improved current carrying capacity and temperature/chemical stability.
Currently, the preparation method of graphene mainly includes a mechanical stripping method, a redox method, a Chemical Vapor Deposition (CVD) method, and the like, but compared with the former two methods, the CVD method can obtain high-quality graphene with controllable layer number by using methane, acetylene, and the like as carbon sources under the catalysis of a specific metal substrate. It is noted that high quality graphene can also be grown on polycrystalline metal substrates, which are less expensive than monocrystalline metal substrates. Thus, the chemical vapor deposition method is one of the effective methods expected to be applied to large-scale preparation of high-quality graphene.
For the preparation of graphene-metal composites, the incorporated graphene is typically obtained by mechanical exfoliation of graphite and reduction of graphene oxide. The graphene material is combined with metal powder or a metal precursor in a physical or chemical mode and further processed to obtain the graphene-metal composite material. However, as the volume fraction of graphene increases, problems of dispersion uniformity, orientation, and interfacial phase separation of the components arise, and the structural integrity of graphene is difficult to completely solve. Meanwhile, as the volume fraction of graphene increases, although the current carrying capacity increases, a significant decrease in conductivity is caused at the same time.
Patent CN108193065A discloses a preparation method of graphene reinforced copper-based composite material, which is characterized in that multilayer graphene is added between copper foils, and a discharge plasma sintering and cold rolling process is performed to obtain a layered multilayer graphene/copper composite material, wherein the resistivity of the obtained composite material is reduced by 11% -18% compared with that of pure copper. Patent CN105624445A discloses a preparation method of a graphene reinforced copper-based composite material, graphene is dispersed in copper powder by a physical method and ball-milled, and hot-pressed and sintered to obtain a block composite material, wherein the resistivity of the obtained composite material is reduced by 22% compared with that of pure copper. Obtaining higher current-carrying capacity enhancement by using lower volume fraction of graphene is one of the problems to be solved. In addition, the one-dimensional fiber material is difficult to obtain by the simple mixing and mechanical blending composite process widely reported at present.
In view of this, the present invention provides a graphene-metal wire composite fiber with high current-carrying capacity and high conductivity and a preparation method thereof to solve the problems in the prior art.
Disclosure of Invention
According to an aspect of the present invention, there is provided a graphene-metal wire composite fiber having an n-stage supercoiled multistage structure composed of sub-fibers, and a 1 st-stage sub-fiber is formed by spirally winding s metal wires coated with graphene, and an m-stage sub-fiber is formed by spirally winding t m-1 th-stage sub-fibers, wherein the metal wire surfaces and between the metal wires have continuous graphene having a uniform thickness, and n is an integer of not less than 6, m is an integer of more than 1 and not more than n, and s and t are each an integer of not less than 6 at each occurrence, and wherein the volume percentage of the graphene is not less than 0.4% by volume of the metal wires coated with graphene.
According to one embodiment, the diameter D of the composite fiber and the original diameter D of the metal wire are0Satisfies the following conditions: 0.8d0≤D≤1.5d0. According to another embodiment, the diameter D of the composite fiber and the original diameter D of the metal wire are0Satisfies the following conditions: 0.9d0≤D≤1.3d0. According to yet another embodiment, the diameter D of the composite fiber and the original diameter D of the metal wire are0Satisfies the following conditions: 0.9d0≤D≤1.2d0. According to yet another embodiment, the diameter D of the composite fiber and the original diameter D of the metal wire are0Satisfies the following conditions: d ═ D0。
According to one embodiment, the coverage of graphene on the surface of the metal wire is 99% or more. According to another embodiment, the coverage of graphene on the surface of the metal wire is 99.5-100%. According to one embodiment, the number of layers of graphene is 1-10. According to another embodiment, the volume percentage of the graphene is equal to or greater than 0.4% based on the volume of the metal wire coated with graphene. According to still another embodiment, the volume percentage of the graphene is 2.0% or less based on the volume of the metal wire coated with the graphene.
According to one embodiment, the diameter D of the composite fiber is 200 μm or less and the final diameter D of the 1 st stage sub-fiber1Is less than or equal toAt 1 μm. According to another embodiment, the metal wire is selected from the group consisting of copper wire, nickel wire, aluminum wire, gold wire, platinum wire, and any combination thereof. According to yet another embodiment, the metal wire is a copper wire or a nickel wire. According to a further embodiment, the metal wire is a copper wire.
According to another aspect of the present invention, there is provided a method of preparing a graphene-metal wire composite fiber, the method including: (1) growing graphene on the surfaces of the s metal wires by a chemical vapor deposition process; (2) twisting and compounding the wire coated with the graphene; (3) carrying out hot stretching treatment on the twisted and compounded wire; (4) performing multi-die cold drawing treatment on the wire subjected to hot drawing treatment to enable the total elongation of the wire to be 450-500% after passing through all dies; (5) subjecting the cold-drawn wire to a chemical vapor deposition process, thereby obtaining sub-fibers, (6) taking t sub-fibers to replace the wire in step (2) and repeating steps (2) - (5), wherein step (6) is repeated n-1 times, thereby obtaining the graphene-metal wire composite fiber, wherein t in each cycle may be the same or different.
According to one embodiment, the metal wire is washed before the step (1), the washing including washing the metal wire using one or more solvents selected from the group consisting of deionized water, ethanol, acetone, isopropanol, chloroform, and the like, repeated 2 to 3 times. According to another embodiment, the method comprises an optional step (3') between step (3) and step (4): the wire or sub-fiber is subjected to a chemical vapor deposition process to grow graphene on its surface. According to yet another embodiment, the chemical vapor deposition process used in step (5) and optionally step (3') is the same as the chemical vapor deposition process used in step (1). According to a further embodiment, the twisting composite treatment of step (2) is carried out under an atmosphere of air, argon, helium, with a degree of twisting of 5 to 40 revolutions/cm.
According to one embodiment, the chemical vapor deposition process of step (1) is an atmospheric pressure chemical vapor deposition process or a low pressure chemical vapor deposition process with a gas pressure of 1 to 300Pa, wherein the carrier gas is selected from argon, helium, hydrogen or any combination thereof; the carbon source is a gaseous carbon source selected from methane, ethane, ethylene or any combination thereof or a liquid carbon source selected from methanol, ethanol, toluene or any combination thereof. According to another embodiment, the chemical vapor deposition process of step (1) comprises bringing a wire or a sub-fiber to a temperature of 800-1100 ℃, holding for 30 to 100 minutes, thereby undergoing a heat treatment, and subsequently heating the wire or the sub-fiber to a growth temperature of 800-1100 ℃ and equal to or higher than the heat treatment temperature and contacting with a carrier gas carrying a carbon source, graphene is grown on the surface of the wire or the sub-fiber for 5 to 60 minutes, wherein the flow rate of the carrier gas is 1 to 500 ml/min.
According to one embodiment, the step (3) includes heat-treating the strands or sub-fibers at 600 to 1100 ℃ for 30 to 60 minutes, followed by drawing the strands or sub-fibers, and then maintaining the drawn state and cooling to 200 ℃ or less. According to another embodiment, step (3) is repeated 5-6 times in a single cycle, eventually resulting in an elongation of the wire of 20-28%. According to one embodiment, step (4) comprises subjecting the wire rod or sub-fiber obtained in step (3) or (3') to a cold multi-die drawing process at normal temperature and pressure, wherein the wire rod or sub-fiber undergoes 1-30 passes using a cold multi-die drawing die having an inner circular hole, and the diameter of the wire rod or sub-fiber decreases by 10-30 μm per pass, wherein the drawing rate of the wire rod or sub-fiber per pass is 80-150 mm/min. According to another embodiment, the diameter of the wire or sub-fiber finally obtained in step (4) may be different from or the same as the initial diameter of the metal wire in step (1).
According to another aspect of the present invention, there is provided a use of the graphene-metal wire composite fiber in a wire or cable.
Drawings
The drawings are only for purposes of illustrating one or more embodiments of the invention along with the description and are not intended to limit the scope of the invention.
FIG. 1 is a schematic view of one example of a composite fiber of the present invention (i.e., an n-level superhelical graphene-copper wire composite wire);
FIG. 2 is a Raman spectrum of graphene in example 1;
FIG. 3 is a comparison of current carrying capacity of the graphene-copper wire composite fiber in example 2;
FIG. 4 is a temperature resistivity comparison of the graphene-copper wire composite fiber in example 2;
fig. 5 is a comparison of rated currents of the graphene-copper wire composite fibers in example 3.
Detailed Description
In order that the present disclosure may be better understood, a number of specific embodiments are provided below. The skilled person will adapt the embodiments according to the actual situation and may also combine technical features of several embodiments.
In one embodiment, there is provided a graphene-metal wire composite fiber having an n-stage supercoiled multistage structure composed of sub-fibers, and a 1 st-stage sub-fiber is formed by spiraling s metal wires coated with graphene, and an m-stage sub-fiber is formed by spiraling t m-1 th-stage sub-fibers, wherein the metal wire surface and between the metal wires have continuous and uniform-thickness graphene, and n is an integer of not less than 6, m is an integer of more than 1 and not less than n, and s and t are each an integer of not less than 6 at each occurrence, and wherein the volume percentage of graphene is not less than 0.4% by volume of the metal wires coated with graphene.
In one embodiment, each occurrence of n, s, and t is independently an integer greater than or equal to 6 and less than or equal to 30, e.g., 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30. In another embodiment, the volume percent of the graphene is 0.4% or more based on the volume of the metal wire coated with graphene. In yet another embodiment, the volume percent of the graphene is less than or equal to 2.0% based on the volume of the metal wire coated with graphene. For example, the volume percentage of the graphene is 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2.0% based on the volume of the metal wire coated with the graphene.
In one embodiment, the diameter D of the composite fiber is the original diameter D of the metal wire0Satisfies the following conditions: 0.8d0≤D≤1.5d0. In another embodiment, the diameter D of the composite fiber is the original diameter D of the metal wire0Satisfies the following conditions: 0.9d0≤D≤1.3d0. In yet another embodiment, the diameter D of the composite fiber is related to the original diameter D of the metal wire0Satisfies the following conditions: 0.9d0≤D≤1.2d0. In a preferred embodiment, the diameter D of the composite fiber is the original diameter D of the metal wire0Same, i.e. D ═ D0。
In one embodiment, the coverage of graphene on the surface of the metal wire is 99% or more. In another embodiment, the coverage of graphene on the surface of the metal wire is 99.5-100%, such as 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 100%. According to one embodiment, the number of layers of graphene is 1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers. Herein, "uniform thickness" means that the maximum thickness and the minimum thickness of the graphene layer are both within a range of "average thickness ± 10%".
In one embodiment, the diameter D of the composite fiber is less than or equal to 200 μm, such as 180 μm, 150 μm, 130 μm, or 100 μm. In another embodiment, the final diameter d of the 1 st stage sub-fiber1Less than or equal to 1 μm, for example 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm or 0.5 μm. In one embodiment, the metal wire may be selected from the group consisting of copper wire, nickel wire, aluminum wire, gold wire, platinum wire, and any combination thereof. In another embodiment, the metal wire is a copper wire or a nickel wire. In yet another embodiment, the metal wire is a copper wire, such as a copper wire having a purity of 95 to 99.999% and a diameter of 0.05 to 0.2 mm.
In this embodiment, copper is used as a substrate, and since copper hardly forms a solid solution with carbon, copper mainly plays a catalytic role in the growth process of graphene, but once graphene covers the surface of the copper substrate, the catalytic role of copper at the graphene-covered position is largely suppressed, thereby preventing further deposition of carbon atoms and increase in the number of graphene layers. Therefore, the method described below can be used to effectively obtain a graphene thin film with a small number of layers or even a single layer by adjusting the process parameters.
In one embodiment, there is provided a method of making a graphene-metal wire composite fiber, the method comprising: (1) growing graphene on the surfaces of the s metal wires by a chemical vapor deposition process; (2) twisting and compounding the wire coated with the graphene; (3) carrying out hot stretching treatment on the twisted and compounded wire; (4) performing multi-die cold drawing treatment on the wire subjected to hot drawing treatment to enable the total elongation of the wire to be 450-500% after passing through all dies; (5) subjecting the cold-drawn wire to a chemical vapor deposition process, thereby obtaining sub-fibers, (6) taking t sub-fibers to replace the wire in step (2) and repeating steps (2) - (5), wherein step (6) is repeated n-1 times, thereby obtaining the graphene-metal wire composite fiber, wherein t in each cycle may be the same or different. In contrast, according to the step (1), graphene with high coverage rate, high quality and controllable number of layers can be grown in situ on the metal surface, thereby obtaining the graphene-coated metal wire. For example, according to the step (1), a commercial red copper wire can be used as a starting material to obtain the graphene-coated copper wire composite wire.
In one embodiment, the metal wire is washed before the step (1), the washing comprises washing the metal wire using one or more solvents selected from the group consisting of deionized water, ethanol, acetone, isopropanol, chloroform, and repeating 2-3 times. In another embodiment, the metal wire is washed with deionized water, ethanol, and acetone sequentially, and repeated 2-3 times.
In one embodiment, the chemical vapor deposition process of step (1) is an atmospheric pressure chemical vapor deposition process. In another embodiment, the chemical vapor deposition process of step (1) is a low pressure chemical vapor deposition process wherein the gas pressure is in the range of 1 to 300Pa, such as 50, 100, 150, 200, 250 Pa. In yet another embodiment, in step (1), the carrier gas is selected from argon, helium, hydrogen, or any combination thereof, for example the carrier gas is a combination gas of argon and hydrogen. In a further embodiment, in step (1), the carbon source is a gaseous carbon source selected from methane, ethane, ethylene or any combination thereof or a liquid carbon source selected from methanol, ethanol, toluene or any combination thereof. Preferably, a gaseous carbon source, such as methane or ethane, is employed.
In one embodiment, the chemical vapor deposition process of step (1) includes bringing a metal wire or sub-fiber to a temperature of 800-1100 ℃, holding for 30 to 100 minutes, thereby undergoing a heat treatment, and then heating the metal wire or sub-fiber to a growth temperature of 800-1100 ℃ and equal to or higher than the heat treatment temperature and contacting with a carrier gas carrying a carbon source or a liquid carbon source, the carrier gas having a flow rate of 1-500ml/min, to grow graphene on the surface of the metal wire for 5 to 60 minutes. In another embodiment, the heat treatment temperature is 800, 850, 900, 950, 1000 or 1050 ℃. In yet another embodiment, the growth temperature is 850, 900, 950, 1000, 1050, or 1100 ℃. In one embodiment, the growth time of the graphene is 5-60 minutes, preferably 10-40 minutes, e.g., 10, 15, 20, 25, 30, 35, 40 minutes.
In one embodiment, the twisting compounding treatment of step (2) is carried out under an atmosphere of air, argon, helium, and the degree of twisting is 5 to 40 rotations/cm, for example, 5, 10, 15, 16, 20, 25, 30, 35, 40 rotations/cm. In another embodiment, in the step (2), 6 to 30 graphene-coated metal wires may be subjected to twisting composite treatment, and 6 to 30 sub-fibers subjected to the previous circulation treatment may be subjected to twisting composite treatment, for example, 6, 7, 8, 9, 10, 12, 15, 18, 20, 25, or 30 metal wires or sub-fibers may be subjected to twisting composite treatment. Through twisting composite treatment, a part of graphene can be wrapped by other surrounding metal wires, and through the steps (3) and (4) described below, graphene can be uniformly distributed among the sub-fibers.
In one embodiment, step (3) comprises subjecting the strands or sub-fibers to a heat treatment at 600-1100 ℃ for 30-60 minutes, followed by stretching the strands or sub-fibers, and then maintaining the stretched state and reducing the temperature to 200 ℃ or lower. In another embodiment, the heat treatment temperature in step (3) is 600-1100 deg.C, 650-1050 deg.C, 700-1000 deg.C, 750-950 deg.C, 800-900 deg.C, and the heat treatment time is 30-60 minutes, 35-55 minutes, 40-50 minutes. In yet another embodiment, step (3) is repeated 5-6 times in a single cycle, ultimately resulting in a wire elongation of 20-28%, such as 20, 21, 22, 23, 24, 25, 26, 27 or 28%. In further embodiments, the heat treatment temperature, heat treatment time may be the same or different when repeating step (3). According to the invention, the stress generated by twisting and stretching can be eliminated in the step (3), the metal wires and the interfaces of the metal wires and the graphene are in good contact, and the whole structure is densified, namely, the structure densification is realized.
In one embodiment, an optional step (3') is provided between step (3) and step (4) according to actual needs, which comprises subjecting the wire or sub-fiber obtained in the previous step to a chemical vapor deposition process to grow graphene on its surface. In another embodiment, the chemical vapor deposition process used in step (3') is the same as the chemical vapor deposition process used in step (1). In yet another embodiment, the chemical vapor deposition process used in step (3') is different from the chemical vapor deposition process used in step (1). In one embodiment, step (3 ') may optionally be performed while repeating the recycling of steps (2) to (5), i.e., step (3') may be performed for each cycle, step (3 ') may not be performed, and step (3') may be performed as needed.
In one embodiment, step (4) comprises subjecting the wire or sub-fiber obtained in step (3) or (3') to a cold multi-die drawing process at ambient temperature and pressure, wherein the wire or sub-fiber undergoes 1-30 passes using a cold multi-die drawing die having an inner circular aperture, the diameter of the wire or sub-fiber decreasing by 10-30 μm (e.g., 10, 12, 15, 18, 20, 22, 25, 28, or 30 μm) per pass, wherein the wire or sub-fiber has a drawing rate of 80-150mm/min (e.g., 80, 100, 120, or 150mm/min) per pass. Here, the multimode cold drawing treatment is adopted, and compared with the single-mode multi-channel cold drawing treatment, the diameter of the sub-fiber is slowly reduced and changed, so that the stress and strain generated by deformation can be released, and the uniformity of the finally obtained composite wire is ensured.
In one embodiment, the diameter of the wire or sub-fiber finally obtained in step (4) may be different from or the same as the initial diameter of the metal wire in step (1). In another embodiment, the diameter of the wire or sub-fiber finally obtained in step (4) is the same as the initial diameter of the metal wire in step (1), i.e. graphene-metal wire sub-fibers are obtained which have the same diameter as the original metal wire, increased length and uniformly distributed graphene inside. In still another embodiment, the cold drawing die is a diamond high-precision drawing die, the section of the hole of the cold drawing die is circular, and drawing lubricating oil can be added or not added in the drawing process.
In one embodiment, the chemical vapor deposition process used in step (5) is the same as the chemical vapor deposition process used in step (1). In another embodiment, the chemical vapor deposition process used in step (5) is different from the chemical vapor deposition process used in step (1).
According to the method, firstly, graphene grows in situ on a metal wire, then twisting composite treatment, hot stretching treatment and multi-mode cold drawing treatment are sequentially combined, the steps are integrally combined together to be used as a circulating operation, and the composite fiber with the graphene uniformly distributed inside and good interface interaction between the graphene and a metal matrix on a microscopic scale is finally obtained through multiple circulating treatments (the structural schematic diagram of the composite fiber is shown in figure 1). The composite fiber has higher current-carrying performance than a pure copper wire, and simultaneously has excellent electric and heat conducting performance, effectively improved mechanical strength and excellent oxidation resistance and corrosion resistance. In addition, the method of the invention can realize continuous production.
Furthermore, the graphene grows in situ, so that metal crystal grains and the graphene have good interface interaction, and the problem that the graphene and metal materials are dispersed on a bulk phase is effectively solved by combining various processing technologies and circulating for many times, so that the defect that metal wires (such as copper wires) cannot prepare large-area high-quality graphene is overcome. Meanwhile, the method of the invention adopts simple and continuous operation, and is convenient for realizing large-scale production.
Examples
Examples are provided below to further illustrate embodiments of the invention. However, it will be understood by those skilled in the art that the examples are provided only for the purpose of more clearly illustrating the present invention, and are not intended to limit the scope of the present invention in any way.
Example 1:
(1) selecting a commercial copper wire with the diameter of 0.2mm and the purity of 99.5%, sequentially cleaning the copper wire by using deionized water, ethanol and acetone, and repeating the steps for 3 times. The method adopts a normal pressure chemical vapor deposition process, wherein argon and hydrogen are selected as carrier gas, the flow rate of the carrier gas is 200ml/min, ethane is selected as a carbon source, the heat treatment temperature is 900 ℃, the heat treatment time is 30 minutes, the growth temperature is 950 ℃, and the growth time is 20 minutes. And continuously growing graphene with high coverage rate, high quality and controllable layer number on the surface of the copper wire to obtain the graphene-coated copper wire with controllable length.
(2) And 6 obtained samples are selected for twisting composite treatment, and twisted wires are obtained. The degree of twisting was 15 revolutions/cm and the operation was carried out in air.
(3) The resulting twisted wire was heat-treated at 900 ℃ for 40min, then stretched until the wire was straightened but subjected to a tensile force of not more than 1N, then kept in the stretched state and cooled to 180 ℃, then again heated to 900 ℃, and the above operation of step (3) was repeated 5 times, with the final twisted wire having an elongation of 25%.
(4) The obtained sample was subjected to the same conditions and process as in step (1), and graphene was again grown on the surface thereof.
(5) And (3) carrying out multi-mode cold drawing treatment on the obtained sample, passing the sample through a diamond high-precision wire drawing die at normal temperature, and carrying out 15 passes at a drawing speed of 100mm/min to finally obtain the graphene-copper composite wire with the same diameter as the original copper wire.
(6) And (3) growing the graphene on the surface of the obtained sample by the chemical vapor deposition process again, wherein the process and the conditions are the same as those in the step (1).
Further, the steps (2) to (6) may be sequentially repeated for the sample obtained in the step (6), thereby realizing the cyclic operation. Specifically, a 0.2mm diameter copper wire material is subjected to step (1), and then 6 cycles are performed according to the above steps (2) - (6), wherein 6 wires obtained in step (1) are taken in the first cycle, and 6 sub-fibers obtained in the previous cycle are taken in each of the following 5 cycles, thereby finally obtaining a material equivalent to 66Stranded graphene-copper wire composite fibers.
And performing Raman spectrum measurement on the graphene-copper wire composite fiber, wherein the test result is shown in figure 2.
Example 2:
(1) selecting a commercial copper wire with the diameter of 0.2mm, washing the copper wire with the purity of 99% by using deionized water, ethanol and acetone in sequence, and repeating the steps for 3 times. The method adopts a normal pressure chemical vapor deposition process, wherein argon and hydrogen are selected as carrier gas, the flow rate of the carrier gas is 300ml/min, ethane is selected as a carbon source, the heat treatment temperature is 900 ℃, the heat treatment time is 40 minutes, the growth temperature is 950 ℃, and the growth time is 15 minutes. And continuously growing graphene with high coverage rate, high quality and controllable layer number on the surface of the copper wire to obtain the graphene-completely-coated copper wire with controllable length.
(2) And 7 obtained samples are selected for twisting composite treatment, and twisted wires are obtained. The degree of twisting was 20 revolutions/cm and the operation was carried out in air.
(3) The resulting twisted wire was heat treated at 900 ℃ for 40min, then stretched until the wire was straightened but subjected to a tension of not more than 1N, then held in the stretched state and cooled to 120 ℃, then again heated to 900 ℃, and the above operation of step (3) was repeated 6 times, with the final twisted wire elongation being 25%.
(4) The obtained sample was subjected to the same conditions and process as in step (1), and graphene was again grown on the surface thereof.
(5) And (3) carrying out multi-mode cold drawing treatment on the obtained sample, passing the sample through a diamond high-precision wire drawing die at normal temperature, and carrying out 15 passes at a drawing speed of 100mm/min to finally obtain the graphene-copper composite wire with the same diameter as the original copper wire.
(6) And (3) growing the graphene on the surface of the obtained sample by the chemical vapor deposition process again, wherein the process and the conditions are the same as those in the step (1).
Further, the steps (2) to (6) may be sequentially repeated for the sample obtained in the step (6), thereby realizing the cyclic operation. Specifically, a 0.2mm diameter copper wire material is subjected to step (1), and then 6 cycles are performed according to the above steps (2) - (6), wherein 7 wires obtained in step (1) are taken in the first cycle, and 7 sub-fibers obtained in the previous cycle are taken in each of the following 5 cycles, thereby finally obtaining a material equivalent to 76Stranded graphene-copper wire composite fibers.
The current-carrying capacity of the composite fiber is improved to 5.8 multiplied by 10 by using a precise source meter to carry out current-carrying performance test on the composite fiber10Am-2As shown in fig. 3.
The composite copper wire is subjected to temperature resistivity test by using a precision source meter and a thermocouple, and the temperature resistivity is reduced to 2.2 multiplied by 10-3As shown in fig. 4.
Example 3:
(1) selecting a commercial copper wire with the diameter of 0.2mm, washing the copper wire with the purity of 99% by using deionized water, ethanol and acetone in sequence, and repeating the steps for 3 times. The method adopts a normal pressure chemical vapor deposition process, wherein argon and hydrogen are selected as carrier gas, the flow rate of the carrier gas is 250ml/min, ethane is selected as a carbon source, the heat treatment temperature is 900 ℃, the heat treatment time is 60 minutes, the growth temperature is 950 ℃, and the growth time is 15 minutes. And continuously growing graphene with high coverage rate, high quality and controllable layer number on the surface of the copper wire to obtain the graphene-completely-coated copper wire with controllable length.
(2) And 6 obtained samples are selected for twisting composite treatment, and twisted wires are obtained. The degree of twisting was 20 revolutions/cm and the operation was carried out in air.
(3) The resulting twisted wire was heat treated at 900 ℃ for 40min, then stretched until the wire was straightened but subjected to a tensile force of not more than 1N, then held in the stretched state and cooled to 150 ℃, then again heated to 900 ℃, and the above operation of step (3) was repeated 5 times, with the final twisted wire elongation being 28%.
(4) And (3) carrying out multi-mode cold drawing treatment on the obtained sample, passing the sample through a diamond high-precision wire drawing die at normal temperature, and carrying out 30 passes at a drawing speed of 100mm/min to finally obtain the graphene-copper composite copper wire with the same diameter as the original copper wire.
(5) And (3) growing the graphene on the surface of the obtained sample by the chemical vapor deposition process again, wherein the process and the conditions are the same as those in the step (1).
Further, the steps (2) to (5) may be sequentially repeated for the sample obtained in the step (5), thereby realizing a cyclic operation. Specifically, a 0.2mm diameter copper wire material is subjected to the step (1) and then circulated 8 times according to the steps (2) to (5), wherein 6 wires obtained in the step (1) are taken in the first circulation, and the sub-fibers obtained in the previous circulation are taken in the subsequent 7 circulations, so that 6 sub-fibers equivalent to 6 are finally obtained8Stranded graphene-copper wire composite fibers.
The rated current density of the composite fiber is improved to 2.78 multiplied by 10 under the temperature of 360K by using a precise source meter and a thermocouple to carry out the rated current density test10Am-2As shown in fig. 5.
It will be understood by those skilled in the art that appropriate modifications and variations can be made to the embodiments of the present invention without departing from the spirit or scope of the invention. It is intended that the scope of the invention be determined by the claims and their equivalents.

Claims (10)

1. The graphene-metal wire composite fiber is characterized in that the composite fiber has an n-level super-spiral multi-level structure formed by sub-fibers, the 1 st-level sub-fiber is formed by spirally winding s metal wires coated with graphene, the m-level sub-fiber is formed by spirally winding t m-1-level sub-fibers,
wherein the surface of the metal wire and between the metal wires are provided with continuous graphene with uniform thickness, n is an integer not less than 6, m is an integer greater than 1 and not less than n, and s and t are each an integer not less than 6 at each occurrence, and
wherein the volume percentage of the graphene is more than or equal to 0.4% by volume of the metal wire coated with the graphene.
2. The composite fiber according to claim 1, wherein the diameter D of the composite fiber and the original diameter D of the metal wire are0Satisfies the following conditions: 0.8d0≤D≤1.5d0Preferably, 0.9d0≤D≤1.3d0More preferably, 0.9d0≤D≤1.2d0Still more preferably, D ═ D0。
3. The composite fiber according to claim 1, wherein the coverage of graphene on the surface of the metal wire is 99% or more, preferably 99.5 to 100%; optionally wherein the number of layers of graphene is 1-10; optionally wherein the volume percentage of graphene is greater than or equal to 0.4% and less than or equal to 2.0% by volume of the metal wire coated with graphene.
4. The composite fiber according to claim 1, wherein the diameter D of the composite fiber is 200 μm or less, and the final diameter D of the 1 st stage sub-fiber1Less than or equal to 1 μm.
5. The composite fiber of claim 1, wherein said metal wire is selected from the group consisting of copper wire, nickel wire, aluminum wire, gold wire, platinum wire, and any combination thereof; preferably, the metal wire is a copper wire or a nickel wire.
6. A method of making the graphene-metal wire composite fiber of any one of claims 1-5, the method comprising:
(1) growing graphene on the surfaces of the s metal wires by a chemical vapor deposition process;
(2) twisting and compounding the wire coated with the graphene;
(3) carrying out hot stretching treatment on the twisted and compounded wire;
(4) performing multi-die cold drawing treatment on the wire subjected to hot drawing treatment to enable the total elongation of the wire to be 450-500% after passing through all dies;
(5) subjecting the cold-drawn wire to a chemical vapor deposition process to obtain sub-fibers,
(6) taking t pieces of sub-fibers to replace the wires in the step (2) and repeating the steps (2) to (5),
wherein step (6) is repeated n-1 times to obtain the graphene-metal wire composite fiber, wherein t in each cycle may be the same or different.
7. The method of claim 6, wherein the metal wire is washed before step (1), the washing comprising washing the metal wire with one or more solvents selected from the group consisting of deionized water, ethanol, acetone, isopropanol, chloroform, repeated 2-3 times; preferably wherein the method comprises an optional step (3') between step (3) and step (4): subjecting the wire or sub-fiber to a chemical vapor deposition process to grow graphene on its surface; preferably wherein the chemical vapour deposition process used in step (5) and optionally step (3') is the same as the chemical vapour deposition process used in step (1); preferably, the twisting composite treatment of the step (2) is carried out in the atmosphere of air, argon and helium, and the twisting degree is 5-40 r/cm.
8. The method of claim 6, wherein the chemical vapor deposition process of step (1) is an atmospheric pressure chemical vapor deposition process or a low pressure chemical vapor deposition process with a gas pressure of 1-300Pa, wherein the carrier gas is selected from argon, helium, hydrogen, or any combination thereof; the carbon source is a gaseous carbon source or a liquid carbon source, the gaseous carbon source is selected from methane, ethane, ethylene or any combination thereof, and the liquid carbon source is selected from methanol, ethanol, toluene or any combination thereof; preferably wherein the chemical vapour deposition process of step (1) comprises bringing the wire or sub-fibre to a temperature of 800-1100 ℃, holding for 30 to 100 minutes, thereby undergoing a heat treatment, and subsequently heating the wire or sub-fibre to a growth temperature of 800-1100 ℃ and equal to or higher than the heat treatment temperature and contacting with a carrier gas carrying a carbon source, graphene being grown on the surface of the wire or sub-fibre for 5 to 60 minutes, wherein the flow rate of the carrier gas is 1-500 ml/min.
9. The method of claim 6, wherein the step (3) comprises subjecting the strands or sub-fibers to a heat treatment at 600-1100 ℃ for 30-60 minutes, followed by drawing the strands or sub-fibers, and then maintaining the drawn state and reducing the temperature to 200 ℃ or lower; optionally, step (3) is repeated 5-6 times in a single cycle, whereby the elongation of the wire is 20-28%.
10. The method of claim 6, wherein step (4) comprises subjecting the wire rod or sub-fiber obtained in step (3) or (3') to cold drawing at normal temperature and pressure, wherein the wire rod is subjected to 1-30 passes using a cold drawing die having an inner circular hole, and the diameter of the wire rod or sub-fiber decreases by 10-30 μm in each pass, wherein the wire rod or sub-fiber has a drawing rate of 80-150mm/min in each pass; preferably, the diameter of the wire or sub-fiber finally obtained in step (4) may be different from or the same as the initial diameter of the metal wire in step (1).
CN201811417029.4A 2018-11-26 2018-11-26 Graphene-metal wire composite fiber and preparation method thereof Pending CN111218814A (en)

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