CN108573763B - Preparation method of wire and cable conductor, graphene-coated metal powder and conductor - Google Patents
Preparation method of wire and cable conductor, graphene-coated metal powder and conductor Download PDFInfo
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H01B7/00—Insulated conductors or cables characterised by their form
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- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
Abstract
The invention discloses a metal-based-graphene wire and cable conductor, a preparation method thereof and a preparation method of graphene-coated metal powder, wherein the metal-based-graphene wire and cable conductor consists of graphene-coated metal powder and graphene powder, and the content of the graphene-coated metal powder is 80-100 wt%. The preparation method of the graphene-coated metal powder is sequentially carried out according to the sequence of the metal-anti-sintering agent first mixed powder, the metal-anti-sintering agent second mixed powder, the metal/graphene and anti-sintering agent mixed powder and the graphene-coated metal powder. The preparation method of the metal matrix-graphene wire and cable conductor is sequentially carried out according to the sequence of the graphene slurry and the prepared graphene-coated metal powder, metal matrix-graphene composite powder, metal matrix-graphene wire and cable conductor. The preparation method of the invention has simple process, economy and environmental protection. The conductor prepared by the invention has excellent electrical property, high oxidation resistance and strong corrosion resistance.
Description
Technical Field
The invention relates to the technical field of wire and cable materials and preparation, in particular to a metal-based graphene wire and cable conductor and a preparation method thereof as well as a preparation method of graphene-coated metal powder.
Background
The wire and cable industry is an important matching industry for economic construction and is widely applied to various fields of national economy. The conductors of the electric wire and the electric cable are mostly made of copper and aluminum, or silver or a superconducting material in a special field. The copper conductor has excellent conductivity, corrosion resistance and mechanical property, and the dosage of the copper conductor far exceeds that of the aluminum conductor, so the copper conductor becomes the preferred material of the cable conductor. Copper and copper alloy are the most commonly applied materials in wires and cables, and have low price, excellent electric and heat conduction performance and good plastic and corrosion resistance. However, the pure copper wire has low strength, is easy to break, and has high power grid failure; the pure copper contact line has low softening temperature resistance and poor heat resistance. In addition, the main disadvantage of the exposed pure copper contact wire is poor wear resistance, and the electrical wear increases with the increase of the power of the traction electric locomotive on high-speed and heavy-load lines, so that the service life of the traction electric locomotive is greatly shortened. Therefore, the copper powder is processed, and a second phase with special excellent performance is introduced to form a copper composite powder material, so that the application performance of the copper alloy is effectively improved, and the copper composite powder material has become a technical trend for modern industrial development. The introduced second phase can be fiber or particle, and can be nitride, oxide or even carbon material, wherein the carbon material can be classified into carbon nano tube, carbon fiber and graphene.
Graphene is the thinnest material known in the world nowadays, and is a two-dimensional monoatomic layer crystal connected by sp2 hybrid orbitals, and the special structure determines that the graphene has many special properties, such as a forbidden bandwidth close to zero, very high carrier mobility, large specific surface area, excellent electrical properties and heat conductivity, excellent mechanical properties, and indexes of young modulus, breaking strength and the like which are equivalent to those of carbon nanotubes. These unique properties make graphene an ideal reinforcement or filler in composite materials.
The existing experiment proves that the heat conduction, the electric conduction, the mechanical property and the like of the copper metal material mixed with the graphene sheet are obviously improved, but the graphene sheet is extremely easy to agglomerate in the copper powder and is unevenly dispersed, so that the compounding difficulty of copper and the graphene sheet is increased, and the further improvement of the property of the copper/graphene alloy material is limited. In order to obtain good conductivity, the prior art discloses a graphene wire, which is formed by winding a two-dimensional graphene film material into a graphene wire having one-dimensional conductivity characteristics by a winding technique. However, the mechanism of growing graphene on different substrates is different, and the quality, size and growth speed of graphene are also different; if the electroplating technology is adopted to press the graphene sheets into the graphene film, the excellent electric and heat conducting properties of the graphene are inevitably obviously reduced. In addition, graphene in the graphene wire is a main component, the process requirement of electroplating and growing large sheets of high-quality graphene is extremely high, and the winding and packaging processes are added, so that the preparation cost of the graphene wire is increased. The prior art also discloses a graphene wire and cable conductor, which is formed by a conductor electric core and a graphene film through directly growing graphene on the surface of the conductor electric core. However, the treatment of the conductor core with the high-temperature graphene growth in this patent may cause the growth of the crystal grains of the conductor core material and produce a work hardening effect, which directly affects the mechanical properties of the conductor core, and needs to perform subsequent processing heat treatment after the graphene growth, which affects the properties of the finally obtained graphene wire and cable conductor. In addition, the production efficiency is low due to the limitation of graphene growth equipment, and the difficulty of graphene electroplating and growth processes of large wires and cables is high. The prior art also discloses a preparation method of the graphene wire, which is to grow graphene on the surface of copper and then reduce the graphene into graphene to prepare the graphene wire. However, the copper wire surface needs to be cleaned by acid in the preparation process, so that the method is not environment-friendly, and a plasma generator needs to be loaded, so that the cost is high. The prior art discloses a wire and cable with copper or aluminum as a core and a copper-graphene complex phase as a sheath, and also discloses a preparation method of a copper-graphene complex phase conductive wire core, however, the former wire and cable with the copper-graphene complex phase as the sheath needs to be cleaned on the surface of a copper wire by acid in the preparation process, and is also electroplated in an aqueous solution environment, so that the wire and cable is not environment-friendly, and the main function of the electroplated graphene is to improve the oxidation resistance and corrosion resistance of the wire. The preparation method of the copper-graphene complex phase conductive wire core of the latter is similar to that of the former, and the copper-graphene complex phase is electroplated on the surface of the wire core by adopting an electroplating method, which is only different in the structure and the forming process of the wire and has the same defects. The prior art also discloses a copper-graphene composite material, which is prepared by uniformly distributing flake graphene in a copper matrix by a ball milling method, then adopting hot-pressing sintering and extruding, wherein the quality of the flake graphene has obvious influence on the performance of the composite material, the addition amount of the flake graphene is less, and a conductive network of the graphene is difficult to form in the composite material.
Disclosure of Invention
The invention aims to reduce the cost of the traditional wire and cable, solve the problems of the existing metal-based graphene wire and cable conductor, and provide a metal-based graphene wire and cable conductor which has excellent electrical properties, high oxidation resistance and corrosion resistance and can be produced in a large scale.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal-based graphene wire and cable conductor is composed of graphene-coated metal powder and graphene powder, wherein the content of the graphene-coated metal powder is 80-100 wt%.
Preferably, the metal powder in the graphene-coated metal powder is one or more of copper, silver and aluminum.
The invention also aims to solve the problem of sintering and agglomeration of metal powder in the process of growing the graphene in situ at high temperature by the metal powder, and provides a preparation method of the graphene-coated metal powder prepared in situ with high efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of graphene-coated metal powder comprises the following steps:
step S1: uniformly mixing metal powder and an anti-sintering agent to obtain first mixed powder of the metal and the anti-sintering agent;
step S2: reacting the metal-anti-sintering agent first mixed powder with reducing gas in an oxygen-free high-temperature environment at 600-1050 ℃ to obtain metal-anti-sintering agent second mixed powder;
step S3: performing chemical vapor deposition on the metal-anti-sintering agent second mixed powder and methane gas at 600-1050 ℃, and cooling after the chemical vapor deposition process is finished to obtain metal/graphene and anti-sintering agent mixed powder;
step S4: and dispersing the mixed powder of the metal/graphene and the sintering inhibitor in a dispersing agent, carrying out ultrasonic layering, and separating out sintering inhibitor dispersion liquid and graphene-coated metal powder.
Preferably, in step S1, the metal powder is one or more of 100-1000 mesh copper, silver and aluminum.
Preferably, in the step S1, the anti-sintering agent is one or more powders of magnesium oxide, aluminum oxide or graphite with a particle size of 100nm to 10 μm, and the mass ratio of the metal powder to the anti-sintering agent is 10:3 to 5: 4.
Preferably, the steps S2 and S3 are performed in a CVD quartz tube chamber, and the CVD quartz tube chamber is evacuated to 10 in the step S2-3Introducing argon at the flow rate of 150-513 sccm below kPa to enable the pressure in the chemical vapor deposition vacuum device to reach a normal pressure state and an oxygen-free environment; in the step S2, introducing reducing gas hydrogen into a chemical vapor deposition quartz tube chamber at a flow rate of 10-20 sccm; in the step S3, methane gas is introduced into the chemical vapor deposition quartz tube chamber with a flow rate of 5-10 sccm.
Preferably, in the step S2, the temperature is increased at a speed of 10 to 20 ℃/min, so that the temperature inside the chemical vapor deposition quartz tube chamber reaches a high temperature environment of 600 to 1050 ℃.
Preferably, the dispersant in step S4 is water.
According to the preparation method of the graphene-coated metal powder, the metal powder and the anti-sintering agent are mixed and then subjected to chemical vapor deposition to grow the graphene in situ, so that sintering agglomeration of the metal powder in a high-temperature deposition process can be effectively avoided, the anti-sintering agent is removed in a post-treatment process, and the quality of the graphene-coated metal composite powder is not affected. The metal powder is coated with the graphene by a chemical in-situ growth method, so that the graphene has few structural defects and high quality.
The third purpose of the present invention is to provide a preparation method of a metal matrix-graphene wire and cable conductor.
A preparation method of a metal matrix-graphene wire and cable conductor comprises the following steps:
step S5: dispersing graphene in a dispersing agent to prepare graphene slurry;
step S6: fully mixing the graphene slurry with the graphene-coated metal powder prepared by the preparation method of the graphene-coated metal powder according to any one of claims 3 to 8, and evaporating to dryness to obtain metal matrix-graphene composite powder;
step S7: preparing the metal-based graphene composite powder into a metal-based graphene wire and cable conductor, wherein the content of graphene-coated metal powder in the metal-based graphene wire and cable conductor is 80-100 wt%.
Preferably, the dispersant in the step S5 is one or more of N, N-dimethylacetamide, ethylene glycol carbonate, ethyl acetate and tetrahydrofuran, and the ratio of graphene to the dispersant in the graphene slurry is 1g:200 ml.
Preferably, the graphene-coated metal powder in step S6 is 100-1000 mesh graphene-coated electrolytic metal powder or spherical metal powder.
According to the metal matrix-graphene wire and cable conductor and the preparation method thereof, the performance of the metal matrix-graphene wire and cable conductor is further enhanced through a proper amount of additional graphene powder, and the metal matrix-graphene wire and cable conductor is obtained through a traditional wire and cable conductor preparation process. The graphene in the conductor is in a 3D network structure, the electrical conductivity, the thermal conductivity and the mechanical property of the conductor are superior to those of a pure metal conductor, and the metal-based-graphene wire and cable conductor prepared by the method is simple in process, low in cost and easy to realize industrial production. The novel copper-aluminum composite wire can gradually replace the market positions of the existing copper wire and aluminum wire in the wire and cable, and obtain great economic benefits on the premise of saving a large amount of resources.
Drawings
Fig. 1 is a raman spectrum of graphene-coated copper powder according to a first embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of field emission of graphene coated copper powder according to a first embodiment of the present invention;
fig. 3 is a micro-topography of a copper-graphene wire and cable conductor in a first embodiment of the invention.
Detailed Description
The following examples, taken in conjunction with fig. 1 to 3, further illustrate the embodiments of the metal matrix-graphene wire and cable conductor of the present invention. The metal matrix-graphene wire and cable conductor of the present invention is not limited to the description of the following embodiments.
The method comprises the following steps of:
step S1: and (3) uniformly mixing the metal powder and the anti-sintering agent to obtain first mixed powder of the metal and the anti-sintering agent.
The metal powder adopted in the step is one or more of 100-1000 meshes of copper, silver and aluminum powder; in the step, the adopted anti-sintering agent is one or more of magnesium oxide, aluminum oxide or graphite with the particle size of 100 nm-10 mu m; the mass ratio of the metal powder to the anti-sintering agent in the step is 10: 3-5: 4.
Step S2: and reacting the metal-anti-sintering agent first mixed powder with reducing gas in an oxygen-free high-temperature environment at 600-1050 ℃ to obtain metal-anti-sintering agent second mixed powder.
Specifically, the first mixed powder of the metal-anti-sintering agent obtained in the step S1 is placed in a chemical vapor deposition quartz tube chamber; the chemical vapor deposition quartz tube chamber is vacuumized to 10 DEG-3Introducing argon at a flow rate of 150-513 sccm below kPa to make the pressure in the chemical vapor deposition vacuum device reach a normal pressure state and an oxygen-free ringEnvironmental conditions; then, introducing reducing gas hydrogen into the chemical vapor deposition quartz tube chamber at the flow rate of 10-20 sccm; and then, after the gases are uniformly mixed, heating at the speed of 10-20 ℃/min to enable the temperature in the chemical vapor deposition quartz tube chamber to reach the high-temperature environment of 600-1050 ℃.
Step S3: and carrying out chemical vapor deposition on the metal-anti-sintering agent second mixed powder and methane gas at the temperature of 600-1050 ℃, and cooling after the chemical vapor deposition process is finished to obtain the metal/graphene and anti-sintering agent mixed powder.
Specifically, methane gas is introduced into a chemical vapor deposition quartz tube chamber at a flow rate of 5-10 sccm, the chemical vapor deposition quartz tube chamber is subjected to heat preservation at a temperature of 600-1050 ℃ for a period of time, after the chemical vapor deposition process is finished, methane and hydrogen are closed, and the temperature is reduced to room temperature, so that the metal/graphene and anti-sintering agent mixed powder is obtained.
Step S4: and dispersing the mixed powder of the metal/graphene and the sintering inhibitor in a dispersing agent, carrying out ultrasonic layering, and separating out sintering inhibitor dispersion liquid and graphene-coated metal powder.
Specifically, the dispersant adopted in the step is water, the mixed powder of the metal/graphene and the sintering inhibitor is uniformly dispersed in the water, and the upper sintering inhibitor dispersion liquid is removed through multiple times of ultrasonic layered cleaning, so that the lower graphene-coated metal powder material can be obtained.
According to the preparation method of the graphene-coated metal powder, the metal powder and the anti-sintering agent are mixed and then subjected to chemical vapor deposition to grow the graphene in situ, so that sintering agglomeration of the metal powder in a high-temperature deposition process can be effectively avoided, the anti-sintering agent is removed in a post-treatment process, and the quality of the graphene-coated metal composite powder is not affected. The metal powder is coated with the graphene by a chemical in-situ growth method, so that the graphene has few structural defects and high quality. The anti-sintering agent can be washed away by water, and the purification treatment is simple in operation, low in cost, economic and environment-friendly.
The invention prepares the metal matrix-graphene wire and cable conductor according to the following steps:
step S5: and dispersing graphene in a dispersing agent to prepare graphene slurry.
The dispersant adopted in the step is one or more of N, N-dimethylacetamide, ethylene glycol carbonate, ethyl acetate and tetrahydrofuran. In the third embodiment of the invention, the dispersant in the third step is N, N-dimethylacetamide, and in the fourth embodiment, the dispersant in the fourth step is ethyl acetate, and experiments prove that ethylene carbonate and tetrahydrofuran are also suitable as the dispersants in the third step. The ratio of graphene to the dispersing agent in the graphene slurry is 1g to 200 ml. The graphene powder adopted in the step is high-quality graphene with 80-1000 meshes and 1-20 layers by using natural or artificial graphite as a raw material and adopting a graphite physical stripping method.
Step S6: and fully mixing the graphene slurry with the graphene-coated metal powder prepared in the steps S1-S4, and evaporating to dryness to obtain the metal-based graphene composite powder.
Specifically, fully mixing the graphene slurry and the graphene-coated metal powder by a mixer for 1-24 hours; and evaporating the mixed graphene slurry and the graphene-coated metal powder to dryness by using a vacuum oven at the temperature of 100-250 ℃ for 1-24 h to obtain the metal matrix-graphene composite powder.
The graphene-coated metal powder adopted in the step is 100-1000-mesh electrolytic metal powder or spherical metal powder coated with graphene.
Step S7: the metal-based graphene wire and cable conductor is prepared by the traditional wire and cable conductor preparation process of the metal-based graphene composite powder, and the content of graphene-coated metal powder in the metal-based graphene wire and cable conductor is 80-100 wt%.
The metal matrix-graphene wire and cable conductor prepared by the steps comprises the following components: the content of the graphene-coated metal powder is 80-100 wt%; 0 wt% -20 wt% of graphene.
According to the metal matrix-graphene wire and cable conductor and the preparation method thereof, the performance of the metal matrix-graphene wire and cable conductor is further enhanced through a proper amount of additional graphene powder, and the metal matrix-graphene wire and cable conductor is obtained through a traditional wire and cable conductor preparation process. The graphene in the conductor is in a 3D network structure, the electrical conductivity, the thermal conductivity and the mechanical property of the conductor are superior to those of a pure metal conductor, and the metal-based-graphene wire and cable conductor prepared by the method is simple in process, low in cost and easy to realize industrial production. The novel copper-aluminum composite wire can gradually replace the market positions of the existing copper wire and aluminum wire in the wire and cable, and obtain great economic benefits on the premise of saving a large amount of resources.
The metal matrix-graphene wire and cable conductor and the preparation method thereof according to the present invention will be described in more detail with reference to examples one to five.
Example one
The metal-based graphene wire and cable conductor comprises 100 wt% of graphene-coated copper powder.
The method for preparing the graphene coated copper powder comprises the following steps:
firstly, copper powder with the grain size of 200 meshes and magnesium oxide with the grain size of 1 mu m are uniformly mixed according to the mass ratio of 5: 2 to obtain 280g of mixed powder, and the 280g of mixed powder is placed in a chemical vapor deposition quartz tube chamber.
Then, the CVD quartz tube chamber was evacuated to 10 deg.C-3And kPa, introducing argon at a flow rate of 513sccm to enable the indoor pressure of the chemical vapor deposition quartz tube to reach a normal pressure state, adjusting the flow rate of the argon to 300sccm, introducing hydrogen at a flow rate of 20sccm, after the gases are uniformly mixed, raising the temperature to 1000 ℃ at a speed of 20 ℃/min, then introducing methane gas at a flow rate of 10sccm, keeping the temperature at 1000 ℃ for 30min, after the chemical vapor deposition process is finished, closing the methane and the hydrogen, and cooling to room temperature to obtain the copper/graphene and magnesium oxide mixed powder.
And then, uniformly dispersing the mixed powder of copper/graphene and magnesium oxide in water, carrying out ultrasonic layered cleaning for many times to remove the magnesium oxide dispersion liquid on the upper layer, and carrying out vacuum drying to obtain the lower graphene coated copper powder.
A raman spectrogram of the graphene coated copper powder prepared in the implementation is shown in fig. 1, and the number of layers of the graphene coated copper powder is 2, so that the structure defects are few, and the quality is good as can be known through calculation of the positions of D, G and 2D peaks and peak areas in the raman spectrum; as shown in fig. 2, a scanning electron microscope of the graphene-coated copper powder showed that the coverage of graphene on the surface of copper powder was high.
The method for preparing the copper-graphene wire and cable conductor is specifically carried out according to the following steps:
the prepared graphene-coated copper powder is subjected to a traditional wire and cable conductor preparation process to obtain a copper-graphene wire and cable conductor, wherein the content of graphene-coated copper powder in the copper-graphene wire and cable conductor is 100 wt%.
As shown in fig. 3, the resistivity of the copper-graphene wire and cable conductor is 1.5x10-6Omega cm, thermal conductivity of 429w/m k, lower than the best conductive silver. The copper-graphene wire and cable conductor has the advantages of lowest resistivity, highest thermal conductivity and optimal performance, and is simple in preparation process and low in cost.
Example two
The metal-based graphene wire and cable conductor comprises 100 wt% of graphene-coated copper powder.
The method for preparing the graphene coated copper powder comprises the following steps:
firstly, copper powder with the grain size of 100 meshes and alumina with the grain size of 10 mu m are uniformly mixed according to the mass ratio of 5:4 to obtain 280g of mixed powder, and the 280g of mixed powder is placed in a chemical vapor deposition quartz tube chamber.
Then, the CVD quartz tube chamber was evacuated to 10 deg.C-3Introducing argon at the flow rate of 150sccm to enable the pressure in the chemical vapor deposition quartz tube chamber to reach the normal pressure state, adjusting the flow rate of the argon to 300sccm, introducing hydrogen at the flow rate of 10sccm, raising the temperature to 1050 ℃ at the speed of 10 ℃/min after the gases are uniformly mixed, then introducing methane gas, wherein the methane gas flowsKeeping the temperature at 1050 ℃ for 30min at the amount of 10sccm, closing methane and hydrogen after the chemical vapor deposition process is finished, and cooling to room temperature to obtain the copper/graphene and aluminum oxide mixed powder.
And then, uniformly dispersing the mixed powder of copper/graphene and aluminum oxide in water, ultrasonically layering and cleaning for multiple times to remove the aluminum oxide dispersion liquid on the upper layer, and drying in vacuum to obtain the lower graphene coated copper powder.
The method for preparing the copper-graphene wire and cable conductor is specifically carried out according to the following steps:
the prepared graphene-coated copper powder is processed by a traditional wire and cable conductor preparation process to prepare a copper-graphene wire and cable conductor, wherein the content of the graphene-coated copper powder in the copper-graphene wire and cable conductor is 100 wt%.
The resistivity of the copper-graphene wire and cable conductor prepared in the embodiment is 1.6x10-6Omega cm, thermal conductivity 409 w/m.k.
EXAMPLE III
The metal-based graphene wire and cable conductor comprises 80 wt% of graphene-coated silver powder and 20 wt% of graphene powder.
The method for preparing the graphene-coated silver powder comprises the following steps:
firstly, silver powder with the grain diameter of 1000 meshes and graphite with the grain diameter of 100nm are evenly mixed according to the mass ratio of 10:3 to obtain 280g of mixed powder, and the mixed powder is placed in a chemical vapor deposition quartz tube chamber.
Then, the CVD quartz tube chamber was evacuated to 10 deg.C-3Introducing argon at the flow rate of 400sccm so that the pressure in the chemical vapor deposition quartz tube chamber reaches the normal pressure state, adjusting the flow rate of the argon to 300sccm, introducing hydrogen at the flow rate of 20sccm, after the gases are uniformly mixed, raising the temperature to 850 ℃ at the speed of 10 ℃/min, introducing methane gas at the flow rate of 5sccm, keeping the temperature at 850 ℃ for 60min, closing the methane and the hydrogen after the chemical vapor deposition process is finished, cooling, and keeping the temperature for 60minAnd cooling to room temperature to obtain the silver/graphene and graphite mixed powder.
And then, uniformly dispersing the silver/graphene and graphite mixed powder in water, ultrasonically cleaning and removing the upper graphite dispersion liquid layer by layer for multiple times, and drying in vacuum to obtain lower graphene coated silver powder.
The method for preparing the silver-graphene wire and cable conductor is specifically carried out according to the following steps:
and dispersing graphene in a dispersing agent to prepare graphene slurry. The adopted dispersant is N, N-dimethylacetamide, and the ratio of graphene to the dispersant in the graphene slurry is 1g:200 ml. The adopted graphene powder is natural graphite, and the high-quality graphene with 80 meshes and 20 layers is prepared by adopting a graphite physical stripping method.
Then, fully mixing the graphene slurry and the prepared graphene-coated silver powder by using a mixer for 1 h; and (3) evaporating the mixed graphene slurry and graphene-coated silver powder to dryness by using a vacuum oven at the temperature of 250 ℃ for 1h to obtain silver-graphene composite powder, wherein the mass ratio of the graphene powder to the graphene-coated silver powder is 1: 4.
Finally, the silver-graphene composite powder is prepared into the silver-graphene wire and cable conductor through a traditional wire and cable conductor preparation process, wherein the content of the graphene-coated silver powder in the silver-graphene wire and cable conductor is 80 wt%.
The resistivity of the silver-graphene wire and cable conductor prepared in the embodiment is 1.7x10-6Omega cm, thermal conductivity of 388 w/m.k.
Example four
A metal-based graphene wire and cable conductor comprises graphene-coated aluminum powder and graphene powder, wherein the content of the graphene-coated aluminum powder is 95%, and the content of the graphene powder is 5 wt%.
The method for preparing the graphene-coated aluminum powder is specifically carried out according to the following steps:
firstly, aluminum powder with the grain diameter of 400 meshes and graphite with the grain diameter of 10 mu m are uniformly mixed according to the mass ratio of 2: 1 to obtain 280g of mixed powder, and the 280g of mixed powder is placed in a chemical vapor deposition quartz tube chamber.
Then, the CVD quartz tube chamber was evacuated to 10 deg.C-3And introducing argon at the flow rate of 400sccm under the kPa condition to ensure that the pressure in the chemical vapor deposition quartz tube chamber reaches the normal pressure state, adjusting the flow rate of the argon to be 200sccm, introducing hydrogen at the flow rate of 20sccm, raising the temperature to 600 ℃ after the gases are uniformly mixed, introducing methane gas at the flow rate of 8sccm, and keeping the temperature at 600 ℃ for 40 min. And after the chemical vapor deposition process is finished, closing methane and hydrogen, and cooling to room temperature to obtain the aluminum/graphene and graphite mixed powder.
And then, uniformly dispersing the aluminum/graphene and graphite mixed powder in water, ultrasonically cleaning and removing the upper graphite dispersion liquid in a layering manner for multiple times, and drying in vacuum to obtain lower graphene-coated aluminum powder.
The method for preparing the aluminum-graphene wire and cable conductor is specifically carried out according to the following steps:
and dispersing graphene in a dispersing agent to prepare graphene slurry. The adopted dispersant is ethyl acetate, and the ratio of graphene to the dispersant in the graphene slurry is 1g:200 ml. The adopted graphene powder is artificial graphite, and the high-quality graphene with 1000 meshes and 1 layer is prepared by adopting a graphite physical stripping method.
Then, fully mixing the graphene slurry and the prepared graphene-coated aluminum powder by using a mixer for 24 hours; and (3) evaporating the mixed graphene slurry and graphene-coated aluminum powder to dryness by using a vacuum oven at the temperature of 100 ℃ for 24 hours to obtain aluminum-graphene composite powder, wherein the mass ratio of the graphene powder to the graphene-coated aluminum powder is 1: 19.
Finally, the aluminum-graphene composite powder is prepared into the aluminum-graphene wire and cable conductor through a traditional wire and cable conductor preparation process, wherein the content of graphene-coated aluminum powder in the aluminum-graphene wire and cable conductor is 95 wt%.
The aluminum-graphene wire and cable conductor prepared by the implementationHas a resistivity of 2.8x10-6Omega cm, thermal conductivity 225w/m k.
EXAMPLE five
A metal-based graphene wire and cable conductor comprises 100 wt% of graphene-coated aluminum powder.
The method for preparing the graphene-coated aluminum powder is specifically carried out according to the following steps:
firstly, aluminum powder with the particle size of 300 meshes and magnesium oxide with the particle size of 1 mu m are uniformly mixed according to the mass ratio of 5:4 to obtain 280g of mixed powder, and the 280g of mixed powder is placed in a chemical vapor deposition quartz tube chamber.
Then, the CVD quartz tube chamber was evacuated to 10 deg.C-3And kPa, introducing argon at the flow rate of 300sccm to enable the indoor pressure of the chemical vapor deposition quartz tube to reach a normal pressure state, adjusting the flow rate of the argon to be 200sccm, introducing hydrogen at the flow rate of 15sccm, raising the temperature to 650 ℃ at the speed of 15 ℃/min after the gases are uniformly mixed, then introducing methane gas at the flow rate of 10sccm, keeping the temperature at 650 ℃ for 30min, closing the methane and the hydrogen after the chemical vapor deposition process is finished, and cooling to room temperature to obtain the aluminum/graphene and magnesium oxide mixed powder.
And then, uniformly dispersing the mixed powder of aluminum/graphene and magnesium oxide in water, ultrasonically cleaning and removing the magnesium oxide dispersion liquid on the upper layer for multiple times in a layered manner, and drying in vacuum to obtain lower-layer graphene-coated aluminum powder.
The method for preparing the aluminum-graphene wire and cable conductor is specifically carried out according to the following steps:
the prepared graphene-coated aluminum powder is subjected to a traditional wire and cable conductor preparation process to prepare an aluminum-graphene wire and cable conductor, wherein the content of the graphene-coated aluminum powder in the aluminum-graphene wire and cable conductor is 100 wt%.
The resistivity of the aluminum-graphene wire and cable conductor prepared in the embodiment is 2.3x10-6Omega cm, thermal conductivity 285 w/m.k.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (11)
1. A preparation method of graphene-coated metal powder is characterized by comprising the following steps: the method comprises the following steps:
step S1: uniformly mixing metal powder and an anti-sintering agent to obtain first mixed powder of the metal and the anti-sintering agent;
step S2: reacting the metal-anti-sintering agent first mixed powder with reducing gas in an oxygen-free high-temperature environment at 600-1050 ℃ to obtain metal-anti-sintering agent second mixed powder;
step S3: performing chemical vapor deposition on the metal-anti-sintering agent second mixed powder and methane gas at 600-1050 ℃, and cooling after the chemical vapor deposition process is finished to obtain metal/graphene and anti-sintering agent mixed powder;
step S4: and dispersing the mixed powder of the metal/graphene and the sintering inhibitor in a dispersing agent, carrying out ultrasonic layering, and separating out sintering inhibitor dispersion liquid and graphene-coated metal powder.
2. The method for preparing graphene-coated metal powder according to claim 1, wherein: in the step S1, the metal powder is one or more of 100 to 1000 mesh copper, silver, and aluminum.
3. The method for preparing graphene-coated metal powder according to claim 1, wherein: in the step S1, the anti-sintering agent is one or more of powders of magnesium oxide, aluminum oxide or graphite with the particle size of 100 nm-10 μm, and the mass ratio of the metal powder to the anti-sintering agent is 10: 3-5: 4.
4. The method for preparing graphene-coated metal powder according to claim 1, wherein:the steps S2 and S3 are performed in a CVD quartz tube chamber, and the CVD quartz tube chamber is evacuated to 10 degrees in the step S2-3Introducing argon at the flow rate of 150-513 sccm below kPa to enable the pressure in the chemical vapor deposition vacuum device to reach a normal pressure state and an oxygen-free environment; in the step S2, introducing reducing gas hydrogen into a chemical vapor deposition quartz tube chamber at a flow rate of 10-20 sccm; in the step S3, methane gas is introduced into the chemical vapor deposition quartz tube chamber with a flow rate of 5-10 sccm.
5. The method for preparing graphene-coated metal powder according to claim 1, wherein: in the step S2, the temperature is raised at a speed of 10-20 ℃/min, so that the temperature in the chemical vapor deposition quartz tube chamber reaches a high-temperature environment of 600-1050 ℃.
6. The method for preparing graphene-coated metal powder according to claim 1, wherein: the dispersant in step S4 is water.
7. The method for preparing graphene-coated metal powder according to claim 1, wherein: in the step S2, the temperature of the reaction of the first mixed powder of the metal-anti-sintering agent and the reducing gas is 850-1050 ℃; in the step S3, the temperature of the metal-anti-sintering agent second mixed powder and the methane gas for chemical vapor deposition is 850-1050 ℃.
8. A preparation method of a metal matrix-graphene wire and cable conductor is characterized by comprising the following steps: the method comprises the following steps:
step S5: dispersing graphene in a dispersing agent to prepare graphene slurry;
step S6: fully mixing the graphene slurry with the graphene-coated metal powder prepared by the method for preparing the graphene-coated metal powder according to any one of claims 1 to 7, and evaporating to dryness to obtain metal matrix-graphene composite powder;
step S7: preparing the metal-based graphene composite powder into a metal-based graphene wire and cable conductor, wherein the content of graphene-coated metal powder in the metal-based graphene wire and cable conductor is 80-100 wt%.
9. The method of preparing a metal matrix-graphene wire and cable conductor of claim 8, wherein: the dispersant in the step S5 is one or more of N, N-dimethylacetamide, ethylene glycol carbonate, ethyl acetate, and tetrahydrofuran, and the ratio of graphene to the dispersant in the graphene slurry is 1g:200 ml.
10. The method of preparing a metal matrix-graphene wire and cable conductor of claim 8, wherein: the graphene-coated metal powder in the step S6 is 100-1000 mesh graphene-coated electrolytic metal powder or spherical metal powder.
11. The utility model provides a metal matrix-graphite alkene wire and cable conductor which characterized in that: the preparation method of the metal matrix-graphene wire and cable conductor according to any one of claims 8 to 10.
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| CN110216282B (en) * | 2019-05-30 | 2024-03-26 | 上海新池能源科技有限公司 | Preparation method of copper-based alloy contact |
| CN110170655A (en) * | 2019-06-04 | 2019-08-27 | 浙江正泰电器股份有限公司 | A kind of preparation method of metal matrix three-dimensional graphene composite material |
| CN110828024B (en) * | 2019-11-20 | 2020-08-04 | 北京清大际光科技发展有限公司 | Conducting wire prepared from conductive graphene coated copper and preparation method and application thereof |
| CN112542279B (en) * | 2020-11-25 | 2021-08-27 | 诺正集团股份有限公司 | Preparation method of homogeneous graphene aluminum alloy cable |
| CN112899649A (en) * | 2021-01-15 | 2021-06-04 | 姜达 | Method for wrapping graphene on copper powder |
| CN114974647A (en) * | 2021-02-18 | 2022-08-30 | 上海新池能源科技有限公司 | Ultrahigh-conductivity wire and cable and preparation method thereof |
| CN115505780A (en) * | 2021-06-21 | 2022-12-23 | 上海新池能源科技有限公司 | Preparation method of metal-based graphene composite material and metal-based graphene electrical contact |
| CN113643854B (en) * | 2021-08-24 | 2023-02-03 | 西北有色金属研究院 | Preparation method of graphene composite Fe (Se, te) superconducting material |
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