CN112538596A - Carbon nano tube-metal composite conductor and preparation method thereof - Google Patents

Carbon nano tube-metal composite conductor and preparation method thereof Download PDF

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CN112538596A
CN112538596A CN202010382234.2A CN202010382234A CN112538596A CN 112538596 A CN112538596 A CN 112538596A CN 202010382234 A CN202010382234 A CN 202010382234A CN 112538596 A CN112538596 A CN 112538596A
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metal
nano tube
carbon nanotube
carbon nano
composite conductor
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刘丹丹
王平
魏小典
赵静娜
李清文
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/006—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Abstract

The invention discloses a carbon nano tube-metal composite conductor and a preparation method thereof. The preparation method comprises the following steps: providing a carbon nanotube aggregate comprising a network structure formed by aggregation of carbon nanotubes; putting the carbon nano tube aggregate into an organic solution of metal salt for solvothermal reaction, so as to generate metal crystal grains at least in the network structure of the carbon nano tube aggregate, and then carrying out primary annealing and reduction treatment; and depositing metal on the surface and the interior of the carbon nano tube aggregate treated by the steps in an organic electrodeposition mode to obtain the carbon nano tube-metal composite conductor. The invention effectively constructs metal in a network structure in the carbon nano tube by means of solvothermal reaction and organic electrodeposition, nucleates in the carbon nano tube, promotes the growth of crystal nuclei by annealing, reduction treatment and hot pressing, reduces crystal boundary, reduces gaps between tubes and metal layers by hot pressing, and improves the conductivity and current-carrying capacity of the carbon nano tube-metal composite conductor.

Description

Carbon nano tube-metal composite conductor and preparation method thereof
Technical Field
The invention relates to a carbon nano tube-metal composite conductor and a preparation method thereof, belonging to the technical field of conductive materials.
Background
Light and large current-carrying conductors have great demands in the aspects of aerospace such as unmanned aerial vehicles, satellites, intelligent equipment and the like. Since all conductors in electric wires and cables are made of high-density metal materials, and the metal materials are used for providing reliable current-carrying performance, and the shortage of heavy weight is also needed, the light weight of the cables is still a leading-edge scientific problem which is highly regarded by western developed countries and is also a technical problem to be solved urgently. The light nano carbon material is used for replacing or partially replacing the existing metal material, and the light nano carbon material is an important research direction for conductor light weight. The carbon nanotube fiber has excellent performances of light weight, flexibility, high strength and the like, and the conductivity is 1-2 orders of magnitude higher than that of the carbon fiber, so that the carbon nanotube fiber is an ideal material for light weight of conductors. However, the carbon nanotube fiber is not as conductive as metal when used as a conductor in a cable. In view of these problems, in recent years, many researchers have used various methods to prepare carbon nanotube composite conductors, for example, patent No. CN101948988A is to fill multi-wall carbon nanotube powder into uniformly drilled holes on an electrical aluminum block, press the mixture into a composite material through a friction pressure reduction process, and then draw out composite conductive fibers. For example, patent publication No. CN104616718A is a flexible high-strength conductive fiber formed by wrapping a carbon nanotube fiber layer with aramid fiber as a reinforcing core and adding a protective sheath on the outermost layer. But the fatal weakness of the invention is that only the fiber layer is used as a conductive medium, and the conductivity is not high; the method also has certain defects, the composite conductive fiber prepared by chemical plating has large internal stress and more defects, and the composite conductive fiber only depends on the metal on the surface of the fiber to carry out electron transmission, thereby not exerting the advantages of the carbon nanotube.
In summary, the prior art mainly has the following disadvantages: 1) the powder filling hot-drawing method has low strength of the hot-drawn composite wire due to the weak bonding force between the carbon nano tube and the aluminum; 2) the outer wrapping method using aramid fiber as a core wire has the advantages that the current carrying capacity of the composite conducting wire is limited due to low conductivity of the carbon nano tube, joule heat is generated due to overlarge resistance of the conducting wire in the electrifying process, and the strength of the aramid fiber of the inner core is obviously reduced due to the temperature rise, so that the effective reinforcing effect cannot be realized; 3) the high-strength carbon nanotube fiber is used as an inner core, copper is deposited on the surface by chemical plating and electroplating methods, so that the problems that the particles of a copper coating are uneven, the uniformity is poor, the number of defects is large, and the strength of the composite fiber is influenced cannot be avoided. And only rely on the surface metal of fibre to carry out electron transport, do not exert the advantage of carbon nanotube itself.
Furthermore, many of the copper-plated carbon nanotube structures reported in the literature at present are core-sheath structures, and the metal deposited by a common inorganic salt system only exists on the surface layer of the carbon nanotube, and the outer layer of the carbon nanotube is coated with a thin or thick copper layer, so that the electrical property and the current-carrying capacity of the conductor material are improved by increasing the thickness of the metal. The properties of the composite fiber depend on the thickness of the surface copper layer, the thicker the copper layer the higher the conductivity. Although the electrical properties are improved, the composite fiber of this structure has a limited degree of conductivity improvement due to poor surface bonding force between the copper layer and the carbon nanotube fiber and a copper layer with a large number of defects, mechanical properties are not ideal, and the carbon nanotube is not fully utilized, only the fiber surface is utilized.
Therefore, designing an effective carbon nanotube/copper composite structure is the key to realizing a light and large current-carrying wire, and has been the direction of researchers in the industry for a long time.
Disclosure of Invention
The invention mainly aims to provide a carbon nano tube-metal composite conductor and a preparation method thereof, thereby overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a carbon nano tube-metal composite conductor, which comprises the following steps:
(1) providing a carbon nanotube aggregate comprising a network structure formed by aggregation of carbon nanotubes;
(2) placing the carbon nano tube aggregate into an organic solution of metal salt, carrying out solvothermal reaction at the temperature of 20-30 ℃, so as to generate metal crystal grains at least in the network structure of the carbon nano tube aggregate, and then carrying out primary annealing and reduction treatment;
(3) and (3) depositing metal on the surface and the inside of the carbon nano tube aggregate treated in the step (2) in an organic electrodeposition mode to obtain the carbon nano tube-metal composite conductor.
In some embodiments, the method of making further comprises: (4) and (4) carrying out secondary annealing and reduction treatment on the carbon nano tube-metal composite conductor obtained in the step (3).
In some embodiments, the method of making further comprises: (5) and (4) carrying out hot-pressing treatment on the carbon nano tube-metal composite conductor treated in the step (4).
The embodiment of the invention also provides the carbon nano tube-metal composite conductor prepared by the method, wherein the metal crystals are uniformly distributed on the surface and in the carbon nano tube aggregate network structure.
Compared with the prior art, the invention has the beneficial effects that:
in order to utilize the carbon nano tube in the fiber to plate metal into the carbon nano tube aggregate to enable the metal and the carbon nano tube to fully act and maximally utilize the excellent performance of the carbon nano tube, the invention effectively constructs the metal into a network structure in the carbon nano tube aggregate by a solvothermal and organic system electrochemical controllable deposition method, nucleates in the carbon nano tube to effectively regulate and control the grain size and reduce the grain boundary, effectively reduces the resistance of the fiber in the carbon nano tube by reducing the metal consumption to fully exert the excellent performance of the carbon nano tube, promotes the crystal nucleus to grow, grows the metal grains and reduces the grain boundary by annealing, reduction treatment and hot pressing, reduces gaps between tubes and a metal layer by hot pressing, obtains a conductive film of a continuous metal-carbon structure, and fully utilizes the interaction between the carbon nano tube and the metal, the carbon nano tube has excellent heat conducting performance and low expansion coefficient, can quickly dissipate heat when a large current is applied, improves the conductivity and current-carrying capacity of the carbon nano tube-metal composite conductor, and further improves the mechanical and electrical properties of the composite conductor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1A is a schematic view of a process flow for preparing a carbon nanotube/metal composite conductor according to an exemplary embodiment of the present invention.
Fig. 1B is a schematic diagram illustrating the change of the internal structure of the carbon nanotube film during the preparation of the carbon nanotube/metal composite conductor according to the exemplary embodiment of the present invention.
Fig. 2A is a schematic diagram illustrating the comparison of copper content inside and on the surface of the carbon nanotube aggregate at different concentrations according to an exemplary embodiment of the present invention.
Fig. 2B is a graph showing a comparison of copper content inside and on the surface of the carbon nanotube aggregate at different current densities in accordance with an exemplary embodiment of the present invention.
Fig. 2C is a graph illustrating a comparison of copper content inside and on the surface of the carbon nanotube aggregate at different deposition times in accordance with an exemplary embodiment of the present invention.
Fig. 2D is a schematic cross-sectional structure of a carbon nanotube-metal composite conductor prepared in an exemplary embodiment of the present invention.
Fig. 2E is a schematic view of the internal structure of the carbon nanotube-metal composite conductor prepared in an exemplary embodiment of the present invention.
Fig. 2F is a schematic surface structure diagram of a carbon nanotube-metal composite conductor prepared in an exemplary embodiment of the present invention.
Fig. 3A and 3B are schematic views of the internal structure of the carbon nanotube-metal composite conductor prepared in comparative example 2.
Detailed Description
As mentioned above, the carbon nanotube film prepared by the floating method has the characteristics of compact structure, poor orientation, hydrophobic surface and the like, and the traditional electrochemical system (inorganic salt) deposition cannot reach the internal network of the film. In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to provide the technical solution of the present invention.
In summary, the technical scheme of the scheme is mainly that metal is effectively constructed in a network structure in the carbon nanotube by an organic system electrochemical controllable deposition method, the grain size is effectively regulated and controlled, the grain boundary is reduced, the resistance of fibers in the carbon nanotube is effectively reduced by reducing the metal consumption, and the excellent performance of the carbon nanotube is fully exerted. And then annealing, reducing and hot-pressing to grow metal grains, reduce grain boundary and further improve the mechanical and electrical properties of the composite conductor.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing a carbon nanotube-metal composite conductor, including:
(1) providing a carbon nanotube aggregate comprising a network structure formed by aggregation of carbon nanotubes;
(2) placing the carbon nano tube aggregate into an organic solution of metal salt, carrying out solvothermal reaction at the temperature of 20-30 ℃, so as to generate metal crystal grains at least in the network structure of the carbon nano tube aggregate, and then carrying out primary annealing and reduction treatment;
(3) and (3) depositing metal on the surface and the inside of the carbon nano tube aggregate treated in the step (2) in an organic electrodeposition mode to obtain the carbon nano tube-metal composite conductor.
The invention adopts the electrochemical deposition of an organic system to process the carbon nano tube-metal, and prepares the carbon nano tube-metal composite conductor with high conductivity and current carrying capacity, wherein metal crystals are uniformly distributed in the carbon nano tube aggregate.
In some preferred embodiments, the preparation method further comprises:
(4) and (4) carrying out secondary annealing and reduction treatment on the carbon nano tube-metal composite conductor obtained in the step (3).
In some preferred embodiments, the preparation method further comprises:
(5) and (4) carrying out hot-pressing treatment on the carbon nano tube-metal composite conductor treated in the step (4).
In some preferred embodiments, the carbon nanotube aggregate comprises a carbon nanotube film or a carbon nanotube fiber.
Further, the preparation method comprises the following steps: the carbon nano tube film is prepared by adopting a floating catalytic cracking method.
In some preferred embodiments, the organic solution comprises a metal salt and an organic solvent. The organic electrochemical deposition solution system is different from common electrochemical deposition, and the system adopts organic solution to construct metal in the network structure of the carbon nano tube aggregate, thereby fully exerting the advantages of the carbon nano tube.
Further, the metal salt includes copper acetate, nickel acetate, cobalt acetate, iron acetate, or the like, but is not limited thereto.
In some preferred embodiments, the concentration of the metal salt in the organic solution is 2 to 30mmol/L, preferably 5 to 30 mmol/L. Further, the organic solvent includes any one or a combination of two or more of acetonitrile, acetone, ethanol, and the like, but is not limited thereto.
In some preferred embodiments, in the step (2), the solvothermal reaction time is 0.5-1 h.
In some preferred embodiments, in the step (2), the metal grains have a grain size of 50 to 200nm, and the filling volume percentage of the metal grains in the network structure is more than 90%.
In some preferred embodiments, step (2) comprises: and carrying out primary annealing and reduction treatment on the carbon nanotube aggregate finally obtained by the solvothermal reaction at 200-300 ℃ in a reducing atmosphere for 2-3 h.
Further, the reducing atmosphere includes a mixed atmosphere formed of an inert gas and hydrogen gas.
Further, the flow ratio of the inert gas to the hydrogen is 100-200: 150 to 250.
In some preferred embodiments, in step (3), the process conditions of the organic electro-deposition mode are as follows: the current density is 0.1-5A/dm2The deposition time is 0.5-2.0 h.
In some preferred embodiments, in the step (4), the temperature of the secondary annealing and reduction treatment is 200-300 ℃ and the time is 2-3 h.
In some preferred embodiments, in the step (5), the pressure of the hot pressing treatment is 30 to 100Mpa, the temperature is 200 to 1000 ℃, and the time is 0.5 to 2 hours.
The invention adopts the metal technologies of promoting copper plating inside the carbon nano tube aggregate by combining the solvent heat treatment reaction with the organic electrochemical deposition, and the like, fills metal crystal grains into the carbon nano tube aggregate through the organic solvent heat high-temperature high-pressure treatment, promotes the internal copper crystal grains to grow and fill the inside of the carbon nano tube aggregate through the organic electrochemical deposition, adjusts the current density, thereby obtaining the metal nano crystal grains with uniform sizes, and fills the metal crystal grains inside and outside the carbon nano tube aggregate after electroplating for a period of time.
As a more preferred embodiment of the present invention, please refer to fig. 1A, which illustrates an example of a carbon nanotube-copper composite conductor, and a method for manufacturing the carbon nanotube-metal composite conductor includes the following steps:
1) preparing an organic solution, wherein the metal salt comprises copper acetate, and the organic solvent comprises acetonitrile, acetone, ethanol and the like;
2) carrying out organic heat treatment, namely putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave for sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed copper grains in the carbon nano tube film in advance;
3) annealing and reducing the prepared composite conductor to reduce copper acetate in the carbon nano tube film into copper;
4) fixing the processed film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, putting the mold into an electrodeposition device, and preparing a carbon nanotube-copper composite conductor with superior performance and structure by adopting a three-electrode system and regulating and controlling current density and electroplating time;
5) because incomplete electroplating copper oxide may exist in the electroplating process, the copper oxide needs to be annealed again and reduced;
6) and (3) putting the annealed carbon nanotube-copper composite material into a hollow cylindrical die with the diameter of 5cm, and adjusting the hot pressing time and temperature to obtain the carbon nanotube-copper composite material with excellent performance.
Another aspect of an embodiment of the present invention also provides a carbon nanotube-metal composite conductor prepared by the foregoing method, in which metal crystals are uniformly distributed on the surface and inside of the network structure of the carbon nanotube aggregate.
Further, the content of metal in the carbon nanotube-metal composite conductor is 80-95 wt%.
Further, the thickness of the metal layer on the surface of the carbon nanotube aggregate is 0.2 to 1 μm.
Further, the conductivity of the carbon nanotube-metal composite conductor is 1-2.5 multiplied by 107s/m, carrying capacity of 2-8 x 105A/cm2The mechanical property strength is 300-1000 MPa.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
Example 1
The present embodiment relates to a method for preparing a carbon nanotube-copper composite conductor, and as shown in fig. 1A, the method may specifically include the following steps:
1) preparing an organic solution, wherein the metal salt adopts copper acetate, the concentration of the organic solution is 2mmol/L, and the organic solvent adopts acetonitrile.
2) Carrying out organic heat treatment at the temperature of 20 ℃, reacting for 0.5h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed copper grains into the carbon nano tube film in advance, wherein the grain size of the copper grains is 50-200 nm, and the filling volume percentage of the copper grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to ensure that B in the carbon nano tube filmReducing acid copper into copper under the conditions of Ar flow of 200sccm and H2The flow rate is 150sccm, the annealing time is 3h, and the annealing temperature is 250 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 0.1A/dm2And the electroplating time is 2 hours to prepare the carbon nano tube-copper composite conductor with excellent performance and structure.
5) Because incomplete plating of copper oxide may exist in the plating process, re-annealing and reduction are needed, and the temperature and time range are consistent with those in the step 3).
6) Placing the annealed carbon nanotube-copper composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 30Mpa, the time is 2h, and the temperature is 200 ℃, so that the carbon nanotube-copper composite material with excellent performance is obtained: tests show that the content of metal in the carbon nanotube-copper composite material obtained in the embodiment is 80-85%, the thickness of the metal layer is 0.2-0.4 μm, and the electrical conductivity of the carbon nanotube-copper composite material is 1-1.5 × 107s/m, carrying capacity of 2-2.5 × 105A/cm2The mechanical property strength is 300-500 MPa.
In this embodiment, a schematic diagram of the internal structure change of the carbon nanotube film during the preparation of the carbon nanotube-copper composite material can be seen in fig. 1B. Fig. 2D is a schematic cross-sectional view of the carbon nanotube-copper composite material prepared in this embodiment, fig. 2E is a schematic internal structure, and fig. 2F is a schematic surface structure.
In some exemplary embodiments of the present invention, the inventors further examined the carbon nanotube-copper composite material obtained under different concentrations, and please refer to fig. 2A for a comparison of the copper content inside and on the surface of the carbon nanotube. Fig. 2B is a schematic diagram showing the comparison of the copper content in the carbon nanotube and the copper content on the surface of the carbon nanotube-copper composite material obtained under different current densities. Fig. 2C is a schematic diagram showing the comparison of the copper content in the carbon nanotubes and on the surface of the carbon nanotubes obtained from the carbon nanotube-copper composite material at different deposition times.
Example 2
The present embodiment relates to a method for preparing a carbon nanotube-copper composite conductor, and as shown in fig. 1A, the method may specifically include the following steps:
1) preparing an organic solution, wherein the metal salt adopts copper acetate, the concentration of the organic solution is 30mmol/L, and the organic solvent adopts acetonitrile.
2) Carrying out organic heat treatment at the temperature of 30 ℃, reacting for 1h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed copper grains into the carbon nano tube film in advance, wherein the grain size of the copper grains is 50-200 nm, and the filling volume percentage of the copper grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the copper acetate in the carbon nano tube film into copper, wherein the annealing condition is that the Ar flow is 200sccm and H2The flow rate is 200sccm, the annealing time is 3h, and the annealing temperature is 300 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 5A/dm2And the electroplating time is 0.5h to prepare the carbon nano tube-copper composite conductor with excellent performance and structure.
5) Because incomplete plating of copper oxide may exist in the plating process, re-annealing and reduction are needed, and the temperature and time range are consistent with those in the step 3).
6) And putting the annealed carbon nanotube-copper composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 100Mpa, the time is 0.5h, and the temperature is 1000 ℃, so that the carbon nanotube-copper composite material with excellent performance is obtained. As a result of testing, the content of the metal in the carbon nanotube-copper composite material obtained in the present example is 90 to 95%, the thickness of the metal layer is 0.8 to 1 μm, and the electrical conductivity of the carbon nanotube-copper composite material is 2 to 2.5 × 107s/m, carrying capacity of 6-8 x 105A/cm2The mechanical property strength is 700-1000 MPa.
The carbon nanotube-copper composite obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Example 3
The present embodiment relates to a method for preparing a carbon nanotube-copper composite conductor, and as shown in fig. 1A, the method may specifically include the following steps:
1) preparing an organic solution, wherein the metal salt adopts copper acetate, the concentration of the organic solution is 16mmol/L, and the organic solvent adopts ethanol.
2) Carrying out organic heat treatment at the temperature of 25 ℃, reacting for 0.8h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed copper grains into the carbon nano tube film in advance, wherein the grain size of the copper grains is 50-200 nm, and the filling volume percentage of the copper grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the copper acetate in the carbon nano tube film into copper, wherein the annealing condition is that the Ar flow is 150sccm and H2The flow rate is 200sccm, the annealing time is 2.5h, and the annealing temperature is 250 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 2.5A/dm2And the electroplating time is 1.2h to prepare the carbon nano tube-copper composite conductor with excellent performance and structure.
5) Because incomplete plating of copper oxide may exist in the plating process, re-annealing and reduction are needed, and the temperature and time range are consistent with those in the step 3).
6) And putting the annealed carbon nanotube-copper composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 80Mpa, the time is 1h, and the temperature is 600 ℃, so that the carbon nanotube-copper composite material with excellent performance is obtained. As a result of testing, the content of the metal in the carbon nanotube-copper composite material obtained in the present example is 85 to 90%, the thickness of the metal layer is 0.6 to 0.8 μm, and the electrical conductivity of the carbon nanotube-copper composite material is 1.5 to 2 × 107s/m, carrying capacityIs 4 to 6 x 105A/cm2The mechanical property strength is 600-800 MPa.
The carbon nanotube-copper composite obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Example 4
The present embodiment relates to a method for preparing a carbon nanotube-copper composite conductor, and as shown in fig. 1A, the method may specifically include the following steps:
1) preparing an organic solution, wherein the metal salt adopts copper acetate, the concentration of the organic solution is 10mmol/L, and the organic solvent adopts acetone.
2) Carrying out organic heat treatment at the temperature of 25 ℃, reacting for 1h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed copper grains into the carbon nano tube film in advance, wherein the grain size of the copper grains is 50-200 nm, and the filling volume percentage of the copper grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the copper acetate in the carbon nano tube film into copper, wherein the annealing condition is that the Ar flow is 100sccm and H2The flow rate is 250sccm, the annealing time is 2h, and the annealing temperature is 200 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 1A/dm2And the electroplating time is 1h to prepare the carbon nano tube-copper composite conductor with excellent performance and structure.
5) Because incomplete plating of copper oxide may exist in the plating process, re-annealing and reduction are needed, and the temperature and time range are consistent with those in the step 3).
6) And putting the annealed carbon nanotube-copper composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 50Mpa, the time is 1.5h, and the temperature is 400 ℃, so that the carbon nanotube-copper composite material with excellent performance is obtained. After testing, the inner metal of the carbon nanotube-copper composite material obtained in this exampleThe content of (A) is 80-90%, the thickness of the metal layer is 0.2-0.6 μm, and the conductivity of the carbon nanotube-copper composite material is 1-2 × 107s/m, carrying capacity of 2-6 x 105A/cm2The mechanical property strength is 300-700 MPa.
The carbon nanotube-copper composite obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Example 5
The embodiment relates to a preparation method of a carbon nanotube-nickel composite conductor, which can specifically comprise the following steps:
1) preparing an organic solution, wherein the metal salt adopts nickel acetate, the concentration of the organic solution is 15mmol/L, and the organic solvent adopts acetone.
2) Carrying out organic heat treatment at the temperature of 25 ℃, reacting for 1h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment, so that nickel grains are embedded in the carbon nano tube film in advance, wherein the grain size of the nickel grains is 50-200 nm, and the filling volume percentage of the nickel grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the nickel acetate in the carbon nano tube film into nickel under the conditions that the Ar flow is 100sccm and H flows2The flow rate is 250sccm, the annealing time is 3h, and the annealing temperature is 200 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 1A/dm2And the electroplating time is 1h to prepare the carbon nano tube-nickel composite conductor with excellent performance and structure.
5) Because incomplete plating of nickel oxide may exist in the plating process, re-annealing and reduction are needed, and the temperature and time range are consistent with those in the step 3).
6) Placing the annealed carbon nanotube-nickel composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 50Mpa, the time is 1.5h, and the temperature is 400 ℃, and obtaining the carbon nanotube-nickel composite materialCarbon nanotube-nickel composite material with excellent performance. Tests prove that the content of metal in the carbon nanotube-nickel composite material obtained in the embodiment is 80-90%, the thickness of the metal layer is 0.2-0.6 mu m, and the conductivity of the carbon nanotube-nickel composite material is 1-2 multiplied by 106s/m, carrying capacity of 1-2 x 105A/cm2The mechanical property strength is 500-700 MPa.
The carbon nanotube-nickel composite material obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Example 6
The embodiment relates to a preparation method of a carbon nanotube-cobalt composite conductor, which can specifically comprise the following steps:
1) preparing an organic solution, wherein the metal salt adopts cobalt acetate, the concentration of the organic solution is 30mmol/L, and the organic solvent adopts acetonitrile.
2) Carrying out organic heat treatment at the temperature of 30 ℃, reacting for 1h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed cobalt grains into the carbon nano tube film in advance, wherein the grain size of the cobalt grains is 50-200 nm, and the filling volume percentage of the cobalt grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the cobalt acetate in the carbon nano tube film into cobalt, wherein the annealing condition is that the Ar flow is 200sccm and the H flow is2The flow rate is 200sccm, the annealing time is 3h, and the annealing temperature is 300 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 5A/dm2And the electroplating time is 0.5h to prepare the carbon nano tube-cobalt composite conductor with excellent performance and structure.
5) Because the cobalt oxide which is not completely plated can exist in the electroplating process, the cobalt oxide needs to be annealed again and reduced, and the temperature and the time range are consistent with those in the step 3).
6) Putting the annealed carbon nano tube-cobalt composite material into a straight tubeAnd carrying out hot pressing treatment in a hollow cylindrical die with the diameter of 5cm, wherein the hot pressing pressure is 100Mpa, the time is 0.5h, and the temperature is 1000 ℃, so as to obtain the carbon nano tube-cobalt composite material with excellent performance. Tests prove that the content of metal in the carbon nanotube-cobalt composite material obtained in the embodiment is 90-95%, the thickness of the metal layer is 0.8-1 μm, and the conductivity of the carbon nanotube-cobalt composite material is 2-2.5 × 107s/m, carrying capacity of 6-8 x 105A/cm2The mechanical property strength is 700-1000 MPa.
The carbon nanotube-cobalt composite material obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Example 7
The embodiment relates to a preparation method of a carbon nanotube-iron composite conductor, which can specifically comprise the following steps:
preparing an organic solution, wherein the metal salt adopts ferric acetate, the concentration of the organic solution is 5mmol/L, and the organic solvent adopts ethanol.
2) Carrying out organic heat treatment at the temperature of 20 ℃, reacting for 0.8h, putting the prepared organic electrolyte into an autoclave, putting the packaged sample into the autoclave, sealing, and heating the autoclave to create a high-temperature and high-pressure environment so as to embed iron grains into the carbon nano tube film in advance, wherein the grain size of the iron grains is 50-200 nm, and the filling volume percentage of the iron grains in the network structure is more than 90%;
3) annealing and reducing the prepared composite conductor to reduce the ferric acetate in the carbon nano tube film into iron, wherein the annealing condition is that the Ar flow is 150sccm, H2The flow rate is 200sccm, the annealing time is 2.5h, and the annealing temperature is 250 ℃;
4) fixing the treated film on a self-made copper mold by using silver adhesive, packaging the mold by using hot melt adhesive, placing the mold into an electrodeposition device, adopting a three-electrode system, and regulating and controlling the current density to be 2.5A/dm2And the electroplating time is 1.2h to prepare the carbon nano tube-iron composite conductor with excellent performance and structure.
5) Because the incompletely electroplated iron oxide may exist in the electroplating process, the annealing and the reduction are needed again, and the temperature and the time range are consistent with those in the step 3).
6) And (3) putting the annealed carbon nanotube-iron composite material into a hollow cylindrical die with the diameter of 5cm for hot pressing treatment, wherein the hot pressing pressure is 80Mpa, the time is 1h, and the temperature is 600 ℃, so that the carbon nanotube-iron composite material with excellent performance is obtained. Tests prove that the content of metal in the carbon nanotube-iron composite material obtained in the embodiment is 85-90%, the thickness of the metal layer is 0.6-0.8 mu m, and the conductivity of the carbon nanotube-iron composite material is 1.5-2 multiplied by 107s/m, carrying capacity of 4-6 x 105A/cm2The mechanical property strength is 600-800 MPa.
The carbon nanotube-iron composite obtained in this example was tested for various properties, and the results were substantially the same as those of example 1.
Comparative example 1
The comparative example differs from example 1 in that: and (3) carrying out solvent heat treatment reaction by adopting an inorganic system.
In the comparison example, an inorganic system is adopted, so that metal is easier to deposit on the surface of the carbon tube, mainly the metal is used for transmitting electrons and is deposited on the surface of the fiber, and the uniformity is poor; the invention adopts organic system deposition to deposit among the internal networks of the fiber, thereby exerting more functions of the carbon nano tube.
Comparative example 2
In the comparison example, the SEM images of the carbon nanotube-metal composite conductor obtained by directly depositing metal on the carbon nanotube film or the carbon nanotube fiber by electroplating or chemical plating are shown in FIG. 3A and FIG. 3B, and the electrical conductivity is 0.5-1 × 107s/m, carrying capacity of 1-2 x 105A/cm2The mechanical strength is 300-700MPa, which is obviously not as excellent as the performances of the embodiment 1.
Comparative example 3
The comparative example differs from example 1 in that: introducing metal grains into the carbon nanotube film or the carbon nanotube fiber by a hydrothermal method, and depositing a metal layer by adopting an electroplating and chemical plating mode based on a water phase system.
The carbon nanotube-metal composite conductor obtained in the comparative example had an electrical conductivity of 0.5 to 1×107s/m, carrying capacity of 1-2 x 105A/cm2The mechanical strength is 300-700Mpa, and the performance is obviously not as excellent as that of the embodiment 1.
Comparative example 4
The comparative example differs from example 1 in that: the primary annealing and reduction steps are lacked.
The carbon nanotube-metal composite conductor obtained in the comparative example had an electrical conductivity of 0.1 to 0.5X 107s/m, carrying capacity of 0.1-0.2 x 105A/cm2The mechanical strength is 300-500 Mpa, which is obviously inferior to the performances of the embodiment 1.
Comparative example 5
The comparative example differs from example 1 in that: the secondary annealing and reduction steps are lacked.
The carbon nanotube-metal composite conductor obtained in the comparative example had an electrical conductivity of 0.5 to 1X 107s/m, carrying capacity of 1-2 x 105A/cm2The mechanical strength is 300-800 MPa, and is obviously inferior to the performances of the embodiment 1.
Comparative example 6
The comparative example differs from example 1 in that: the final hot pressing step is absent.
The carbon nanotube-metal composite conductor obtained in the comparative example had an electrical conductivity of 0.8 to 1.0X 107s/m, carrying capacity of 0.5-1 × 105A/cm2The mechanical property is 300-700MPa, which is obviously inferior to the properties of example 1.
In summary, in order to utilize the carbon nanotubes in the fiber to plate metal into the carbon nanotube aggregate, so that the metal and the carbon nanotubes fully act, and the excellent performance of the carbon nanotubes is utilized to the maximum extent, the metal is effectively constructed in the network structure in the carbon nanotube aggregate by the method of solvothermal reaction and electrochemical controllable deposition of an organic system, nucleation is performed in the carbon nanotubes, the growth of crystal nuclei is promoted by annealing and aqueous solution plating, the gaps between the tubes and the metal layer are reduced by hot pressing, the conductive film of the continuous metal-carbon structure is obtained, the interaction between the carbon nanotubes and the metal is fully utilized, the excellent heat conductivity and the low expansion coefficient of the carbon nanotubes are utilized, the heat dissipation can be rapidly realized when large current is applied, and the conductivity and the current-carrying capacity of the carbon nanotube-metal composite conductor are improved.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (18)

1. A method for preparing a carbon nanotube-metal composite conductor is characterized by comprising the following steps:
(1) providing a carbon nanotube aggregate comprising a network structure formed by aggregation of carbon nanotubes;
(2) placing the carbon nano tube aggregate into an organic solution of metal salt, carrying out solvothermal reaction at the temperature of 20-30 ℃, so as to generate metal crystal grains at least in the network structure of the carbon nano tube aggregate, and then carrying out primary annealing and reduction treatment;
(3) and (3) depositing metal on the surface and the inside of the carbon nano tube aggregate treated in the step (2) in an organic electrodeposition mode to obtain the carbon nano tube-metal composite conductor.
2. The method of claim 1, further comprising:
(4) and (4) carrying out secondary annealing and reduction treatment on the carbon nano tube-metal composite conductor obtained in the step (3).
3. The method of claim 1, further comprising:
(5) and (4) carrying out hot-pressing treatment on the carbon nano tube-metal composite conductor treated in the step (4).
4. The method of claim 1, wherein: the carbon nanotube aggregate includes a carbon nanotube film or a carbon nanotube fiber.
5. The method of claim 1, wherein: the organic solution includes a metal salt and an organic solvent.
6. The method of claim 5, wherein: the metal salt comprises copper acetate, nickel acetate, cobalt acetate or iron acetate.
7. The method of claim 5, wherein: the concentration of the metal salt in the organic solution is 2-30 mmol/L, preferably 5-30 mmol/L.
8. The method of claim 5, wherein: the organic solvent comprises any one or the combination of more than two of acetonitrile, acetone and ethanol.
9. The preparation method according to claim 1, wherein in the step (2), the solvothermal reaction time is 0.5-1 h.
10. The method according to claim 1, wherein in the step (2), the metal crystal grains have a grain size of 50 to 200nm, and a filling volume percentage of the metal crystal grains in the network structure is 90% or more.
11. The method according to claim 1, wherein the step (2) comprises: and carrying out primary annealing and reduction treatment on the carbon nanotube aggregate finally obtained by the solvothermal reaction at 200-300 ℃ in a reducing atmosphere for 2-3 h.
12. The method of claim 11, wherein: the reducing atmosphere comprises a mixed atmosphere formed by inert gas and hydrogen; preferably, the flow ratio of the inert gas to the hydrogen is 100-200: 150 to 250.
13. The method according to claim 1, wherein in the step (3), the process conditions of the organic electro-deposition mode are as follows: the current density is 0.1-5A/dm2At the time of depositionThe time is 0.5 to 2.0 hours.
14. The preparation method according to claim 1, wherein in the step (4), the temperature of the secondary annealing and the reduction treatment is 200-300 ℃ and the time is 2-3 h; and/or in the step (5), the pressure of the hot pressing treatment is 30-100 Mpa, the temperature is 200-1000 ℃, and the time is 0.5-2 h.
15. The production method according to claim 4, characterized by comprising: the carbon nano tube film is prepared by adopting a floating catalytic cracking method.
16. The carbon nanotube-metal composite conductor prepared by the method of any one of claims 1 to 15, wherein the metal crystals are uniformly distributed on the surface and inside of the network structure of the carbon nanotube aggregate.
17. The carbon nanotube-metal composite conductor of claim 16, wherein: the content of metal in the carbon nanotube-metal composite conductor is 80-95 wt%; and/or the thickness of the metal layer on the surface of the carbon nano tube aggregate is 0.2-1 mu m.
18. The carbon nanotube-metal composite conductor of claim 16, wherein: the conductivity of the carbon nanotube-metal composite conductor is 1-2.5 multiplied by 107s/m, carrying capacity of 2-8 x 105A/cm2The mechanical strength is 300-1000 MPa.
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