CN113026351B - Preparation method of carbon nano tube metal composite conductive fiber, product and application thereof - Google Patents
Preparation method of carbon nano tube metal composite conductive fiber, product and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- 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
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- 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
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1277—Other organic compounds
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a preparation method and a product of carbon nano tube metal composite conductive fiber and application thereof, wherein the preparation method comprises the steps of preparing the carbon nano tube fiber; the carbon nano tube fiber is densified by acetone, wherein, the temperature is reduced by adopting ice bath, and the temperature range is 0-20 ℃; the carbon nano tube fiber electroplating treatment, wherein the electroplating is pulse electroplating, the electroplating current is 49 mA-70 mA, the current conduction time is 0.5-1S, the disconnection time is 2S, the circulation time is 100-120 times, and the current density range is 0.049-0.07A/cm 2 . The carbon nano tube metal composite wire with excellent performance prepared by the method has the characteristics of light weight, high strength, high conductivity and high current carrying capacity, can reduce the quality of a transformer, reduce the production cost of the transformer, prolong the service life of the transformer, and has large market demand and wide application range.
Description
Technical Field
The invention belongs to the field of novel nano composite materials, and particularly relates to a preparation method and a product of a carbon nano tube metal composite conductive fiber and application thereof.
Background
Since the discovery of Carbon Nanotubes (CNT) under high resolution electron microscopy by the japanese scientist rice island (lijima) in 1991, this novel material with unique one-dimensional nanostructures has become a hotspot for research by scientists worldwide. Because the carbon atoms in the carbon nanotubes adopt SP2 orbital hybridization and a unique one-dimensional spiral structure, the carbon nanotubes have a plurality of excellent performances such as extremely high strength/modulus, electrical conductivity, current-carrying capacity, thermal conductivity and low density, in order to obtain the preparation method with high yield, uniform pipe diameter, few structural defects, low impurity content, relatively low cost and convenient operation, a plurality of researches are carried out, and a plurality of preparation methods are discovered. In general, there are three main techniques for preparing CNTs, namely: arc discharge, laser evaporation, and Chemical Vapor Deposition (CVD).
At present, the most common synthesis method of carbon nanotube fibers is as follows: wet spinning, array spinning and chemical vapor deposition. In the three synthetic methods, the wet spinning method uses a surfactant and a coagulating bath containing a large amount of organic polymers, a large amount of organic impurities are doped in the fiber, and the prepared carbon nanotube fiber has poor electric conductivity and heat conductivity and is not suitable for being directly used as high-conductivity fiber or further processed as a matrix; the carbon nano tube fiber prepared by the array spinning method has excellent conductivity, but the preparation process is complex, the cost is high, the production efficiency is low, and the preparation cost is high, so that the method is not suitable for large-scale production and application; compared with the two methods, the CVD method has the advantages of simple synthesis method, high yield, mass production and lower cost, so the CVD method is the most widely used carbon nanotube fiber synthesis method at present.
With the continuous improvement of productivity level and the increasing demand for high-performance conductive materials, the conventional metal conductive materials are difficult to meet the demand, and have the defects of low strength, heavy weight, low current-carrying capacity, high-frequency signal transmission loss and the like, both of aluminum and copper.
Therefore, there is a need in the art to find a new material with light weight, high conductivity, high strength and high current-carrying capacity to replace the conventional metal conductive material, so as to meet the development requirements of electronic components of aerospace, optical fiber cables, automobile manufacturing and various mobile devices in the future.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the carbon nano tube metal composite conductive fiber.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of carbon nanotube metal composite conductive fiber comprises preparing carbon nanotube fiber; the carbon nano tube fiber is densified by acetone, wherein, the temperature is reduced by adopting ice bath, and the temperature range is 0-20 ℃; the carbon nano tube fiber electroplating treatment, wherein the electroplating is pulse electroplating, the electroplating current is 49 mA-70 mA, the current conduction time is 0.5-1S, the disconnection time is 2S, the circulation time is 100-120 times, and the current density range is 0.049-0.07A/cm 2 。
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the preparation of the carbon nanotube fiber comprises the steps of,
the method adopts an injection type vapor deposition growth mode without a substrate, after a carbon source and a catalyst precursor are directly injected into a reaction cavity, the series of reactions of catalyst particle generation, carbon source pyrolysis, carbon atom deposition and carbon nanotube crystallization growth can be realized in a high-temperature reaction zone, and the generated hollow cylindrical carbon nanotube aerogel can be directly converted into carbon nanotube fibers through solvent densification and twisting treatment after being blown out of the reaction zone by carrier gas.
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the carbon source comprises a gas carbon source, a liquid carbon source and a solid carbon source, wherein the gas carbon source is one or more of methane, ethylene and acetylene, the liquid carbon source is one or more of ethanol, acetone and benzene, and the solid carbon source is one or more of charcoal, wood dust and plant ash.
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the carbon source is analytically pure ethanol.
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the catalyst is a double catalyst of ferrocene and copper acetate, wherein the molar ratio of copper to iron is 0.5-2.
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the carrier gas is a mixture of hydrogen and argon, and the mixing ratio is that the volume ratio of the hydrogen to the argon is 3:0.8-1.
As a preferable scheme of the preparation method of the carbon nano tube metal composite conductive fiber, the preparation method comprises the following steps: the carbon nanotube fiber is densified with acetone, including,
introducing the obtained carbon nanotube fiber into a container containing acetone through a Y-shaped glass tube, washing off organic matters and amorphous carbon remained on the surface of the carbon nanotube fiber by the acetone, and enabling the carbon nanotube fiber to shrink and become compact: wherein, acetone temperature: spinning speed at 0-20 deg.c: 0.8-3.2 m/min to obtain the filaments with the diameter of 25-30 mu m.
It is still another object of the present invention to overcome the deficiencies of the prior art and to provide a product made by the method for preparing a carbon nanotube metal composite conductive fiber.
The invention further aims to overcome the defects in the prior art and provide an application of the carbon nano tube metal composite conductive fiber in preparing the enameled wire with insulated appearance.
As a preferred embodiment of the application according to the invention, wherein: the surface of the obtained carbon nano tube metal composite wire is painted to form an enameled wire with insulated appearance, and the specific process comprises the following steps of: the speed is 13.5m/min; annealing; painting; baking; and (3) cooling: naturally cooling; and (3) wire winding: the wire winding speed is 13.5m/min; the tension is controlled during paying off, and the paying off tension is uniform and proper; the annealing is carried out continuously on a enamelling machine, the annealing temperature is controlled to be 500 ℃, and a two-stage temperature control mode is adopted; the longitudinal temperature of the baking furnace is changed from low to high to low during baking, the curing removal highest temperature is 550 ℃, the transverse temperature is linear, and heat preservation is well carried out; and uniformly winding the obtained enameled wire on an iron core of the transformer.
The invention has the beneficial effects that:
(1) The method combines the continuous preparation of the carbon nano tube fiber by the CVD method and the electroplating of metal by adopting the pulse current into a whole, thereby simplifying the production process and steps and having high production efficiency; the method can flexibly adjust the types of carbon nano tube fiber coating metal according to the performance requirements and the production cost of the carbon nano tube metal composite wire by specific application, control the cost and realize differentiated production.
(2) The carbon nano tube metal composite wire with excellent performance prepared by the method has the characteristics of light weight, high strength, high conductivity and high current carrying capacity, can reduce the quality of a transformer, reduce the production cost of the transformer, prolong the service life of the transformer, and has large market demand and wide application range.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a flow chart of a process for continuously preparing carbon nanotube fibers by CVD in-situ copper electroplating by pulse current in accordance with an embodiment of the present invention;
fig. 2 is a process flow chart of the method for preparing enamelled wires by painting the surface of the carbon nano tube copper composite wire in the embodiment of the invention;
FIG. 3 is a cross-sectional view of an enamel wire made of a carbon nanotube copper composite wire according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a carbon nanotube copper composite wire wound transformer coil in an embodiment of the present invention;
FIG. 5 is a schematic view of a CVD method for continuously producing carbon nanotube fibers in accordance with an embodiment of the present invention;
FIG. 6 is a schematic diagram of a densification process of carbon nanotube fiber with acetone in accordance with an embodiment of the present invention;
FIG. 7 is a schematic diagram of a carbon nanotube fiber electroplating apparatus in accordance with an embodiment of the present invention;
FIG. 8 is a graph showing the relationship between the strength of the carbon nanotube-copper composite fiber and the magnitude of the electroplating current in the embodiment of the invention;
FIG. 9 is a graph showing the relationship between the conductivity of the carbon nanotube-copper composite fiber and the electroplating current in the embodiment of the invention;
FIG. 10 is a schematic diagram of a carbon nanotube fiber in-situ continuous electroplating system in accordance with an embodiment of the present invention;
FIG. 11 shows a plot of the strength at break trend of filaments of different Cu-Fe ratios in an embodiment of the present invention;
FIG. 12 is a plot of filament strength trends for different Cu-Fe ratios in an embodiment of the present invention;
FIG. 13 is a graph showing the trend of the resistance of a 5cm wire with different Cu/Fe ratios in an embodiment of the present invention;
FIG. 14 is a plot of the conductivity trend of filaments of different Cu to Fe ratios in an embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Preparation of carbon nanotube fibers: weighing 7.696g of ferrocene, 5.13g of thiophene and 500g of analytically pure ethanol, carrying out ultrasonic treatment for 20min by using an ultrasonic cleaner, and uniformly mixing; the solution is pumped by a needle tube and then is injected into a tube furnace from an upper flange plate, and the injection speed is 12ml/h;
the carrier gas was set to be hydrogen and argon by a proton flowmeter, and the flow rate was 900sccm for hydrogen and 300sccm for argon. Carrier gas is injected from the upper end, carbon nano tube aerogel is generated after reaction in a high temperature area (1170 ℃), the carrier gas is driven to move downwards, and water is drawn out from a lower pipe orifice by using iron wires to form carbon nano tube fibers;
wherein, ferrocene powder (98%) is from the company of chemical reagent of Chinese medicine group, thiophene (99% +) is from the company of Siemens technology (China), analytically pure ethanol (99.7% +) is from the company of chemical reagent of Chinese medicine group, hydrogen (99.99% +) is from the company of Wu Jinhua yang gas of Changzhou, and argon (99.99% +) is from the company of Wu Jinhua yang gas of Changzhou;
the CVD method of fig. 5 is a schematic view of a structure for continuously producing carbon nanotube fibers, which includes a furnace 300, a furnace tube 301, an injection feed system 302, a box frame 303 and an air path system 304, wherein the furnace tube 301 is a tube type vertical furnace, and the box frame 303 is sealed with water.
(2) Densification of carbon nanotube fibers with acetone: introducing the carbon nanotube fiber obtained in the step (1) into one end of a glass container filled with acetone through a guide rod, immersing the carbon nanotube fiber in the acetone, and pulling out the carbon nanotube fiber from the other end of the container, wherein the pulling speed is 2.4m/min; because acetone is volatile, in order to reduce the evaporation rate of acetone, the size of the openings at the two ends of the container is reduced as much as possible, and the room temperature is kept below 25 ℃.
Fig. 6 is a schematic diagram of a densification treatment structure of carbon nanotube fibers by acetone, which comprises a guide rod 400, a glass container 401, an opening 402, an opening 403 and the guide rod 400, wherein the opening 402 and the opening 403 are rounded off to ensure that the carbon nanotube fibers are not hung up.
(3) Electroplating copper on the carbon nano tube fiber: introducing the carbon nanotube fiber densified by the acetone into a plating bath by using a copper rod, setting plating process parameters, turning on a power supply, starting pulse copper plating, and adjusting the spinning shaft speed to be 2.4m/min; electroplating parameters: the plating current is 70mA, the voltage is 5V, the current conduction time is 0.5S, the current disconnection time is 1S, and the circulation times are 120 times.
Fig. 7 is a schematic diagram of a carbon nanotube fiber electroplating apparatus comprising a guide bar 500, a copper bar 501, an electroplating bath 502, a metal sheet 503, a dc power supply 504, a collection roller 505, and carbon nanotube fibers 506.
The electroplating solution formula is copper sulfate pentahydrate, concentrated sulfuric acid and deionized water, the spinning speed of the collecting roller 505 is adjustable, and the metal sheet 503 can be replaced by different kinds of metals according to electroplating requirements.
(4) By repeating the steps (1), (2) and (3), continuous production of the carbon nanotube copper composite wire can be realized, and fig. 1 is a process flow chart of continuous preparation of carbon nanotube fibers by a CVD method and in-situ copper electroplating by pulse current.
Fig. 10 is a schematic diagram of an in-situ continuous electroplating system for carbon nanotube fibers, which includes a furnace 300, a furnace tube 301, an injection feeding system 302, a box frame 303 and an air path system 304, wherein the furnace tube 301 is a tubular vertical furnace, the box frame 303 is sealed by water, a guide rod 400, a glass container 401, an opening 402, an opening 403 and the guide rod 400, the opening 402 and the opening 403 are rounded, so that the carbon nanotube fibers are not hung up, and the guide rod 500, the copper rod 501, the electroplating bath 502, a metal sheet 503, a direct current power supply 504, a collecting roller 505 and the carbon nanotube fibers 506 are ensured. The method combines the continuous preparation of the carbon nano tube fiber by the CVD method and the electroplating of metal by adopting the pulse current into a whole, thereby simplifying the production process and steps and having high production efficiency; the method can flexibly adjust the types of carbon nano tube fiber coating metal according to the performance requirements and the production cost of the carbon nano tube metal composite wire by specific application, control the cost and realize differentiated production.
(5) And (3) detecting the performance of the carbon nano tube copper composite wire: randomly shearing a section of prepared fixed-length carbon nanotube copper composite wire sample, clamping two ends of the fixed-length carbon nanotube copper composite wire sample by copper sheets respectively, connecting the fixed-length carbon nanotube copper composite wire sample to the positive electrode and the negative electrode of a universal meter, and measuring the resistance of the fixed-length carbon nanotube copper composite wire sample; measuring the cross-sectional area by using an ultra-focal depth microscope; and finally, measuring the breaking strength of the steel by using a carbon fiber strength tester.
The curves of the experimentally measured intensity and conductivity as a function of the magnitude of the plating current are shown in fig. 8 (the intensity can be calculated from the breaking strength measured by a carbon fiber stretcher and the cross-sectional area measured by an ultra-focal depth microscope) and fig. 9, respectively. With the increase of the electroplating current, the conductivity of the carbon nano tube copper composite wire gradually increases, but when the current exceeds 35mA, the strength of the carbon nano tube copper composite wire begins to decrease, and when the electroplating current is 70mA, the voltage is 5V, the current conduction time is 0.5S, the current disconnection time is 1S, and the cycle times are carried outWhen the number is 120 times, the prepared carbon nano tube copper composite wire has the best comprehensive performance and the conductivity of 5.56 multiplied by 10 7 S/m, reaching more than 95% of pure copper, and the strength is more than 1.3Gpa, and shows that the carbon nano tube copper composite wire has excellent mechanical and electrical properties.
(6) Carbon nano tube copper composite wire surface paint: the technological process comprises paying off, annealing, painting, baking, cooling and reeling, wherein the technological process for preparing the enameled wire by painting the surface of the carbon nano tube copper composite wire is shown in figure 2.
The vertical enamelled wire machine is adopted, the height of a baking oven is 8m, the paying-off speed is 13.5m/min, the annealing temperature is 645 ℃, the main component of the enamelled wire paint is polyether nitrile ketone resin (PPENK) with a naphthyridine biphenyl structure, the solid content is 20%, the baking temperature is 300 ℃, the natural cooling mode is adopted, and the paying-off speed is 13.5m/min as the wire collecting speed.
The section of the enameled wire made of the carbon nanotube copper composite wire is shown in fig. 3, wherein the enameled wire comprises a carbon nanotube 100, a copper layer 101 and a wire paint layer 102.
(7) An enameled wire wound transformer coil prepared from a carbon nanotube copper composite wire is shown in fig. 4, which is a schematic diagram of a carbon nanotube copper composite wire wound transformer coil, wherein the enameled wire wound transformer coil comprises a carbon nanotube copper composite wire 200 and an iron core 201.
The number of turns of the primary and secondary coils is determined based on the transformer requirements.
Example 2
The plating layer is not uniform and the performance is poor by adopting direct current constant voltage 5V plating, namely the experiment, the step and the result thereof are as follows:
(1) Preparing continuous carbon nano tube fibers by a CVD method, and twisting after acetone densification;
(2) Constructing an electroplating device, wherein the electroplating device comprises an electroplating bath, an electrode, electroplating liquid and a spinning shaft;
(3) Winding the carbon nano tube fiber through an output shaft, contacting with a conductive electrode (pure copper rod), and immersing in electroplating solution;
(4) The 2450/pulse power supply is used for outputting direct current to perform constant voltage electroplating, 5V is tentatively set, and the specific size is adjustable in experiments, so that the carbon nano tube composite wire is prepared and is collected by another spinning shaft.
(5) Results: after 120 times of circulation, the surface of the carbon tube fiber is hardly plated with copper, and the carbon tube fiber is not plated with copper until 360 times of circulation, so that the electroplating efficiency is too low and the effect is poor.
Example 3
(1) Preparing continuous carbon nano tube fibers by a CVD method, and twisting after acetone densification;
(2) Constructing an electroplating device, wherein the electroplating device comprises an electroplating bath, an electrode, electroplating liquid and a spinning shaft;
(3) Winding the carbon nano tube fiber through an output shaft, contacting with a conductive electrode (pure copper rod), and immersing in electroplating solution;
(4) The 2450/pulse power supply is used for outputting pulse current to perform constant voltage electroplating, 5V is tentatively set, and the specific size is adjustable in experiments, so that the carbon nano tube composite wire is prepared and collected by another set of spinning shafts.
(5) Specific parameters are as follows:
the anode electrode is a high-purity copper plate with the purity of 99.999 percent, and the conductive electrode is a high-purity copper rod;
the plating solution comprises 99.9% of copper sulfate pentahydrate, sulfuric acid and deionized water; the concentration of the copper sulfate pentahydrate is 140g/L, and the concentration of the sulfuric acid is 0.1mol/L;
the carbon nano tube fiber is densified firstly and twisted, and the diameter is 30um;
the current density is 1A/cm < 2 >, the current on time range is 0.05S, the current off time range is 2S, and the actual parameters can be adjusted for comparison experiments;
during electroplating, the temperature of the electroplating solution is 20-30 ℃;
collecting the prepared carbon nano tube composite wire by a collecting shaft;
the collecting shaft and the output shaft are respectively arranged at two ends of the electroplating bath, and the conductive electrode is arranged between the output shaft and the electroplating bath;
the rotation speed of the output shaft and the collection shaft is the same and is 5r/min, and the rotation speed is actually regulated according to the diameter of the spinning shaft.
(6) The specific operation flow is as follows:
preparing electroplating solution according to the specific parameters, and then placing the electroplating solution into an electroplating bath;
the positive electrode and the negative electrode of the pulse power supply are respectively connected with a pure copper plate and a pure copper rod by crocodile clips;
setting a pulse power supply according to the specific parameters;
building a double spinning shaft mechanism;
winding the prepared wire on an output shaft, releasing one end, immersing the wire in electroplating solution after contacting a pure copper rod, and winding the wire on a collecting shaft;
the rotation speeds of the double spindles are the same, and the rotation speed can be driven by one motor by using a synchronous belt transmission;
and switching on a pulse power supply, switching on a spinning shaft motor, and starting electroplating wire collection.
(7) Principle and method and explanation of beneficial effects
The pulse power supply is adopted for electrochemical deposition, when the current is conducted, the pulse peak current is several times or even tens times higher than the common direct current, and the instantaneous high current density enables metal copper ions to be reduced under extremely high overpotential, so that grains of a copper deposition layer are thinned, the copper grains are quickly nucleated on the surface of carbon nano tube fibers, an acting point is provided for the deposition of the subsequent metal grains, the interface binding force between metals of the carbon nano tube is effectively improved, when the current is turned off, discharge ions near a cathode region are restored to the original concentration again, concentration polarization is eliminated, the next pulse period is facilitated to continue using the high pulse peak current density, and meanwhile, the phenomena of favorable recrystallization, adsorption and desorption and the like for the deposition layer are also accompanied in the turn-off period. Such a process periodically runs through the beginning and end of the plating process, with the mechanism involved constituting the most basic mechanism for pulse plating.
The method is characterized in that the method adopts a pulse electroplating method to directly and uniformly deposit copper nano crystal grains on the surfaces of the carbon nano tube fibers and in gaps among the carbon nano tube fibers, so that the interfacial bonding force between the carbon nano tube and a copper layer can be effectively improved, and the strength and the conductivity of the carbon nano tube composite wire can be effectively increased through the interaction among crystal boundaries. The synchronous wheel transmission is utilized, so that the internal stress of the fiber is effectively reduced, and the method has a good effect on improving the strength of the carbon nano tube composite wire.
(8) According to the previous preferred investigation of the electroplating process, the electroplating voltages were chosen to be 5V and 0V, the current types being pulsed currents:
the current is 49mA, the current on time is 1S, the current off time is 2S, and the cycle number is 120;
the current is 70mA, the current on time is 0.5S, the current off time is 1S, and the cycle number is 120.
The performance of the carbon nanotube copper plated fiber parameters is shown in Table 1.
TABLE 1
Parameter description: 1. sample number of the copper-plated precursor wire is CL320200615-2 times of copper acetate; 2. the measurement time was 20200722; 3. a measured value of resistance of 5cm of fixed length fiber; 4. the used instrument is 2450, a ruler, a universal meter and a super depth of field microscope; 5. the electroplating current adopts pulse current; 6. numbering illustrates, for example, pulses 7-0.5-2-500-20200321: the plating current type is pulse current, the plating current is 7mA, the current on time is 0.5S, the current off time is 2S, the cycle number is 500, and the plating date is 20200721.
(9) Conductivity analysis:
with the increase of electroplating time and current, the increase of the speed of coating the surface of the carbon tube fiber in the beaker by copper can be easily observed, the color is more similar to copper, the longer the electroplating time and the larger the current are compared with the specific performance parameter table obtained after calculation, the better the conductivity of the CNT/copper composite fiber obtained after electroplating is, the samples with the numbers of 7-0.5-2-1200-20200321, 49-1-2-120-20200321 and 70-0.5-2-120-20200321 are respectively, the conductivity of the samples is very similar to that of pure copper, and the highest conductivity is 5.75x10 7 S/m, about 96.47% of pure copper, almostLike pure copper, the copper-free alloy can save a lot of copper if being applied to mass production.
Intensity analysis:
according to the table, the breaking strength of the pulse 35-1-2-120-20200321 reaches 33.5CN, the strength of the pulse 35-1-2-120-20200321 reaches 1735.57MPa after the combination of the cross sectional area calculation, and the breaking strength is slightly lower than 1805.81MPa of a copper acetate precursor sample with sample number CL320200615-2 times; the sample strength of the sample with the sample number of 7-0.5-2-1200-20200321 is 670.69MPa, which is obviously lower than other samples, and the copper-plated fibers become brittle because of the large number of electroplating cycles and thicker plating layers; other samples all exceeded 1GPa, far exceeding pure copper, but all decreased to a different extent relative to the wire samples, indicating that the wire strength after copper plating was lower.
When the strength and conductivity are compared, the samples numbered pulse 49-1-2-120-20200321 and pulse 70-0.5-2-20200608 have the best performance, the strength exceeds 1GPa, and the conductivity reaches more than 95% of pure copper.
It can be seen that when the current is 7mA, the current on time is 0.5S and 1S, the off time is 2S, and the cycle number is 120, the electroplated copper is little, and no obvious change is observed; the current is 21mA, the current on time is 0.5S, the off time is 2S, and the circulation times are 120 times as above; the current is 21mA, the current conduction time is 1S, the disconnection time is 2S, the obvious electroplating of the copper layer can be seen when the circulation times are 120 times, the color is changed to be the same as that of copper, the electroplating of a part is not complete, and the strength and the conductivity are not high; when the current reaches 35mA and above, copper grains are observed to be deposited on the carbon tube fiber rapidly at a macroscopic speed, and the electroplating efficiency is high. The longer the electroplating time is, the larger the current is, the higher the conductivity of the carbon tube fiber copper composite wire obtained after electroplating is, the electroplating current is 49mA, the current conduction time is 1S, the disconnection time is 2S, and the conductivity of the prepared carbon tube fiber copper composite wire is the highest when the circulation time is 120 times, thereby achieving 5.75X10 7 S/m, electroplating current of 70mA, current on time of 1S, off time of 2S and circulation times of 120 timesConductivity of the fiber copper composite wire is 5.56×10 7 S/m, the strength is highest and reaches more than 96% of pure copper, and the strength reaches more than 1.3 Gpa. However, if the current is increased again, the plating speed is increased, and the plating layer is thicker, but the granularity of the copper crystal grains on the plating is also larger, so that the brittleness of the carbon tube fiber copper composite wire is increased, and the flexibility is deteriorated.
Example 4
The preparation process of the carbon nano tube fiber is as follows:
(1) Experimental Process and design
Instrument and equipment and raw materials: a middle ring single temperature zone tubular shaft furnace, ethanol, ferrocene, thiophene and copper acetate;
technological parameters: the temperature is 1170 ℃, the speed of H2900sccm, ar300sccm, the liquid injection speed is 12ml/H, the needle head is inserted into 10cm, and the rotating speed of a spinning shaft is 30r/min;
the raw materials are as follows: copper acetate is added on the basis of a liquid preparation with the experiment number of CL320200115, and different copper-iron ratios are selected for comparison experiments, wherein Cu/Fe=0.5, 1, 1.5 and 2 are adopted as 4 groups of samples, and the copper-iron ratio is the atomic ratio.
Remarks: 1. the specific formula of the preparation liquid of the sample with the experiment number of CL320200115 precursor is 7.696g of ferrocene, 5.13g of thiophene and 500g of analytically pure ethanol;
the test conditions and results are shown in Table 2.
TABLE 2
Remarks: 1. the resistance is a measured value of a fixed-length resistance of 5 cm; 2. sample formula No. CL320200115 was 1.5 times iron, 1.5 times sulfur, anhydrous; 3. the copper acetate in the liquid with the number of CL320200615-2 times of copper acetate is saturated; 4. the filaments at the time of measuring the resistance value have been twisted.
From the data in the above table, it can be seen thatThe conductivity and the strength of the precursor after copper doping in the mixed solution are higher than those of the precursor without copper doping, and the conductivity and the strength of the prepared carbon nanotube fiber are improved along with the continuous increase of the copper-iron ratio, wherein the sample with the number of CL320200615-2 times of copper acetate has the best performance, the strength reaches about 1.8Mpa, and the conductivity is improved by several times compared with the sample with the number of CL 320200115; the conductivity reaches 8.20 multiplied by 10 5 S/m, although 2.86×10 with pure copper 7 S/m is still inferior by 2 orders of magnitude, but has been improved by more than 1 order of magnitude compared with the sample with the number of CL320200115, the performance is quite excellent, and the performance can be further improved by adopting post-treatment processes such as electroplating, annealing and the like.
(2) Mechanical property analysis:
the trend chart of the breaking strength of the precursor wires with different copper-iron ratios in fig. 11, and the trend chart of the strength of the precursor wires with different copper-iron ratios in fig. 12, can be seen from fig. 11 and 12 that the breaking strength of the carbon nanotube fiber gradually increases with the increase of the copper-iron ratio in the preparation liquid, and the strength of the carbon nanotube fiber can be calculated to increase with the increase of the copper-iron ratio in the preparation liquid by combining the sectional area measured by the previous super-depth microscope, wherein the sample strength of the 2-time copper acetate formula is the highest and reaches 1.8Gpa, which is the strongest precursor wire prepared in the laboratory at present; and also verifies the conjecture of high sample strength.
(3) Analysis of electrical properties:
fig. 13 is a graph showing the trend of the resistance of a 5cm wire with different copper-iron ratios, and fig. 14 is a graph showing the trend of the conductivity of a wire with different copper-iron ratios.
As can be seen from FIGS. 13 and 14, as the copper-doped proportion in the solution increases, the resistance value of the 5cm fixed-length precursor sample measured by a universal meter gradually decreases, and by combining the cross-sectional area measured by the former super-field-depth microscope, the conductivity of the carbon nanotube fiber can be calculated to increase along with the increase of the copper-iron ratio in the solution, wherein the conductivity of the sample of the 2-time copper acetate formula is highest and reaches 8.2X10 5 S/m, although 2.86×10 with pure copper 7 The conductivity of S/m was still less than 2 orders of magnitude, but was 6.33X10 of the sample of the copper-free precursor compared to the formulation with the number CL320200115 4 S/m phase comparison has already been carried outThe method obviously improves the conductivity by more than an order of magnitude, and then prepares the carbon nano tube copper composite fiber by adopting a pulse plating method, and the conductivity is presumed to be higher than that of a plating sample of a copper-free precursor of the preparation liquid.
By combining the graphs and the analysis, the mechanical property and the electrical property of the precursor sample of the 2 times copper acetate formula can be seen to be the best.
The inventor tries ferrocene and copper sulfate/copper chloride first, and as a result, the solubility of copper sulfate in ethanol is poor, the solubility of copper chloride is slightly better than that of copper sulfate, but the prepared carbon tube fiber is discontinuous, and finally, copper acetate is adopted, so that the relative solubility is better, and the continuity of the prepared carbon tube fiber is better.
The formula for preparing the carbon tube fiber by the CVD method adopts experiments of 4 groups of copper-iron ratios of 0.5, 1, 1.5 and 2 for comparison, the copper-iron ratio is the molar ratio, the conductivity and the strength of the carbon tube fiber are gradually improved along with the increase of the copper-iron ratio, the conductivity is highest when the copper-iron ratio is 2, and the conductivity reaches 8.2 multiplied by 10 5 S/m, the strength is close to 2Gpa, copper acetate can not be completely dissolved when the solubility of copper acetate in ethanol is limited, and the copper-iron ratio is 2 times that of saturated solution.
Aiming at the requirements of light weight, high strength, high conductivity and high current carrying capacity of a transformer coil, the invention provides a method for continuously preparing carbon nano tube fibers by a CVD method and adopting pulse current electroplating to prepare a high-performance carbon nano tube metal composite wire, which is applied to the transformer coil, and the type of carbon nano tube fiber plating metal can be flexibly adjusted according to the requirements of specific application on the performance of the carbon nano tube metal composite wire and the production cost.
The whole system proposal solves the problems of continuous purification, densification and electroplating of the carbon nano tube fiber, stable process, simple device, high production efficiency and good mechanical and electrical properties of the carbon nano tube fiber; the carbon tube fiber copper composite wire has high strength, good toughness, light weight and strong current carrying capacity, is suitable for being used as a transformer coil, not only can reduce the whole volume and the mass of a transformer, but also can not be burnt out when overvoltage occurs, protects the transformer, prolongs the service life and ensures that the transformer can work safely and stably for a long time.
The liquid injection speed of the invention is in the range of 8-16ml/h, preferably about 12ml/h, the liquid injection speed is too slow to cause discontinuous filament outlet, the liquid injection speed is too fast to cause liquid dripping, and the furnace tube mouth is easy to be blocked. The carrier gas flow is about 800-1500sccm, preferably about 1200sccm, and if the flow is too low, the filaments cannot be hung on the furnace tube wall easily, and if the flow is too high, the air flow in the furnace tube is disturbed, and the filaments are easily blown off. The spinning shaft speed is 20-40r/min, preferably about 30r/min, the spinning speed is too high to break the filaments, the carbon nanotube aerogel is accumulated at the furnace tube mouth and blocks the furnace tube mouth, and if the liquid injection speed and the carrier gas flow are increased, the filament outlet speed is high, and the spinning speed is also properly regulated.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (7)
1. A preparation method of carbon nano tube metal composite conductive fiber is characterized in that: comprising the steps of (a) a step of,
preparing carbon nano tube fibers: after directly injecting a carbon source and a catalyst precursor into a reaction cavity, the generation of catalyst particles, the pyrolysis of the carbon source, the deposition of carbon atoms and the crystal growth series reaction of the carbon nanotubes can be realized in a high-temperature reaction zone, and the generated hollow cylindrical carbon nanotube aerogel can be directly converted into carbon nanotube fibers through solvent densification and twisting treatment after being blown out of the reaction zone by carrier gas; wherein the catalyst is a double catalyst of ferrocene and copper acetate, and the molar ratio of copper to iron is 2:1, a step of;
densification treatment of carbon nano tube fibers by acetone: introducing the obtained carbon nanotube fiber into a container containing acetone through a Y-shaped glass tube, washing away organic matters and amorphous carbon remained on the surface of the carbon nanotube fiber by the acetone, and enabling the carbon nanotube fiber to shrink and become compact; wherein, acetone temperature: spinning speed at 0-20 deg.c: 0.8-3.2 m/min to obtain filaments with diameters of 25-30 mu m;
the carbon nano tube fiber electroplating treatment, wherein the electroplating is pulse electroplating, the electroplating current is 70mA, the current on time is 0.5S, the off time is 1S, the cycle times are 120 times, and the voltage is 5V.
2. The method for preparing the carbon nanotube metal composite conductive fiber according to claim 1, wherein: the carbon source comprises a gas carbon source, a liquid carbon source and a solid carbon source, wherein the gas carbon source is one or more of methane, ethylene and acetylene, the liquid carbon source is one or more of ethanol, acetone and benzene, and the solid carbon source is one or more of charcoal, wood dust and plant ash.
3. The method for preparing the carbon nanotube metal composite conductive fiber according to claim 1, wherein: the carbon source is analytically pure ethanol.
4. The method for preparing the carbon nanotube metal composite conductive fiber according to claim 1, wherein: the carrier gas is a mixture of hydrogen and argon, and the mixing ratio is that the volume ratio of the hydrogen to the argon is 3:0.8-1.
5. The product of the carbon nanotube metal composite conductive fiber of any one of claims 1 to 4.
6. The use of the carbon nanotube metal composite conductive fiber of claim 5 in the preparation of an insulated enamel wire.
7. The use according to claim 6, wherein: the surface of the obtained carbon nano tube metal composite wire is painted to form an enameled wire with insulated appearance, the specific process comprises,
paying off: the speed is 13.5m/min;
annealing;
painting;
baking;
and (3) cooling: naturally cooling;
and (3) wire winding: the wire winding speed is 13.5m/min; wherein, the liquid crystal display device comprises a liquid crystal display device,
tension is controlled during paying off, and paying off tension is uniform and proper;
the annealing is carried out continuously on a enamelling machine, the annealing temperature is controlled at 500 ℃, and a two-stage temperature control mode is adopted;
the longitudinal temperature of the baking furnace is changed from low to high to low during baking, the highest temperature of the curing area is 550 ℃, the transverse temperature is linear, and heat preservation is well carried out;
and uniformly winding the obtained enameled wire on an iron core of the transformer.
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