CN114974647A - Ultrahigh-conductivity wire and cable and preparation method thereof - Google Patents
Ultrahigh-conductivity wire and cable and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 104
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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Abstract
The invention discloses an ultrahigh-conductivity wire and cable and a preparation method thereof. The method comprises the steps of mixing dendritic copper powder and anti-sintering agent powder, carrying out plasma treatment, then depositing graphene by hydrogen reduction and a CVD method, and obtaining the ultrahigh conductive wire and cable through SPS sintering and cable drawing processes. According to the ultrahigh-conductivity wire and cable and the preparation method thereof, the single crystal copper is used, the corresponding parameters such as temperature and the like are controlled, the number of layers of the graphene can be better controlled, the large-scale preparation of the single crystal copper-based graphene composite material is realized, the conductivity of the material is improved to the greatest extent, and ultrahigh conductivity (> 100% IACS) is realized.
Description
Technical Field
The invention relates to the technical field of wires and cables, in particular to an ultrahigh-conductivity wire and cable and a preparation method thereof.
Background
With the rapid development of science and technology, the performance requirements of many emerging technology industries on copper materials are higher and higher, and even the demand on ultra-high conductive copper materials with higher conductivity than pure copper is urgent.
The current ultrahigh conductive copper materials can be roughly divided into three categories, namely pure copper, alloy copper and copper-based composite materials. The conductivity of pure copper materials and alloy copper materials has great limitation. The copper-based composite material uses copper as a matrix, improves the conductivity by adding a reinforcement and combining a composite effect and a synergistic effect, has excellent performances of electric conduction, heat conduction, wear resistance and the like, and is widely applied to the aspects of wires and cables, integrated circuits, electric contact materials and the like. In copper-based composites, the reinforcement is the most important factor affecting their electrical conductivity. Graphene is a newly discovered two-dimensional plane structure material, and has excellent electrical, thermal and mechanical properties. The single-layer graphene has the carrier mobility as high as 15000cm2 (V.S), the thermal conductivity of 5150W (m.K) and the Young modulus as high as 130GPa, and is an ideal reinforcement material.
At present, the graphene-copper composite material is mainly prepared by a mechanical ball milling method, an in-situ growth method and the like. The methods are easy to cause the phenomena of excessive graphene layers, agglomeration and the like, and the obtained composite material has low conductivity. And the chemical vapor deposition method (CVD method) can prepare high-quality graphene with few layers and good uniformity, and can realize large-scale continuous production. However, the CVD method has the disadvantage that the prepared graphene has a large amount of grain boundaries, which causes electron scattering and greatly reduces the conductivity of the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultrahigh-conductivity wire cable.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ultrahigh-conductivity wire and cable is made of graphene coated copper powder, the copper powder comprises single crystal copper, and the coated area of the graphene layer is 90% -100% of the surface area of the copper powder.
Preferably, the content of the single crystal copper in the copper powder is 80-100%.
Preferably, the single crystal copper has a crystal plane index of (111).
Preferably, the number of the graphene coating layers is 1-2.
Preferably, the graphene with 1-2 layers in the graphene coating layer accounts for 20% -30% of the total amount of the graphene-coated copper powder, the number of the graphene coating layers of the rest graphene-coated copper powder is more than 5, and the coating area is 100% of the surface area of the copper powder.
Preferably, the number of graphene coating layers is greater than or equal to 5, and the coated area is 100% of the surface area of the copper powder.
Another objective of the present invention is to provide a method for manufacturing an ultra-high conductive wire and cable, which solves the problem of extremely low conductivity caused by electron scattering due to a large number of grain boundaries in graphene manufactured by chemical vapor deposition.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an ultrahigh conductive wire and cable comprises the following steps:
step S1: uniformly mixing dendritic copper powder and anti-sintering agent powder according to the mass ratio of 4:1 to obtain mixed powder;
step S2: putting the mixed powder obtained in the step S1 into a quartz tube, and vacuumizing;
step S3: keeping introducing hydrogen and methane into the quartz tube to grow graphene, wherein the flow rate of the hydrogen is fixed, the flow rate of the methane is increased at a fixed flow rate according to a time interval, stopping introducing the methane after the temperature is continuously increased to be higher than 1000 ℃, quickly cooling, and stopping introducing the hydrogen when the temperature is reduced to 200 ℃ to obtain the graphene-coated copper powder/anti-sintering agent composite powder;
step S4: repeatedly cleaning the graphene-coated copper powder/anti-sintering agent composite powder with deionized water, performing ultrasonic dispersion, performing suction filtration, and drying to obtain graphene-coated copper powder;
step S5: loading the graphene-coated copper powder obtained in the step S4 into a graphite die for spark plasma sintering to obtain a blank;
step S6: and (5) preheating the blank obtained in the step (S5) and a wire drawing die together, then carrying out extrusion wire drawing, and then carrying out annealing treatment to obtain the ultrahigh conductive wire and cable.
Preferably, in step S1, the dendritic copper powder has a particle size of 200-500 meshes, and the copper powder includes single crystal copper, wherein the content of the single crystal copper is 80% -100%, and the crystal plane index of the single crystal copper is (111); the sintering-resistant agent powder is one or more of magnesium oxide, graphite, chromium powder or silver powder, and the particle size is 2-50 mu m.
Preferably, in the step S1, the mixed powder is subjected to a plasma treatment using argon or argon oxygen plasma at a temperature of 40 to 100 ℃ and a vacuum degree of 10 to 400Pa for 30 to 120 min.
Preferably, in step S2, after the vacuum is removed, hydrogen is introduced into the quartz tube, and the mixed powder is reduced at a high temperature.
Preferably, in the step S2, the flow rate of the hydrogen gas is 200 to 800 sccm; the reduction temperature is 800-1050 ℃; the reduction time is 60-180 min.
Preferably, in the step S3, the flow rate of the hydrogen gas is 500 to 1000 sccm; the initial flow rate of the methane is 20-110 sccm, and then the flow rate of the methane is increased by 10-50 sccm every 5-15 min; the time for growing the graphene is 45-150 min.
Preferably, in the step S4, the time duration of each cleaning and ultrasonic dispersion is 30 to 120S; the suction filtration time is 5-20 min; the drying temperature is 60-150 ℃, and the drying time is 5-30 min.
Preferably, in the step S5, the temperature rise rate of the sintering is 10-100 ℃/min, and the temperature is kept for 2-20 min at 400-500 ℃, the pressure is 50-200 KN, the final sintering temperature is 800-950 ℃, the temperature is kept for 5-20 min, and the pressure is 200-1200 KN.
Preferably, in the step S6, the preheating temperature is 800 to 900 ℃, and the extrusion ratio of the extrusion is 10:1 to 20: 1; the temperature of the annealing treatment is 200-400 ℃, and the time is 120-300 min.
According to the ultrahigh-conductivity wire and cable and the preparation method thereof, the single crystal copper is used, the corresponding parameters such as temperature and the like are controlled, the number of layers of graphene can be better controlled, the large-scale preparation of the single crystal copper-based graphene composite material is realized, the conductivity of the material is improved to the greatest extent, and ultrahigh conductivity (> 100% IACS) is realized.
In addition, the copper powder is directly treated by using the plasma at low temperature (40-100 ℃), so that an antioxidant on the surface of the copper powder can be removed, the roughness of the surface of the copper powder is greatly reduced, nucleation sites are reduced, formation of single crystal copper with a crystal face index (111) and growth of thin graphene are facilitated, the number of deposited graphene layers is small, the graphene layers are distributed uniformly and completely coated, the treatment condition is simple and controllable, large-scale production is facilitated, the quality of the obtained copper graphene alloy powder is high, the conducting capacity of a wire and cable can be improved, and the wire and cable with ultrahigh conductivity is finally obtained. In addition, the mode of gradually increasing the flow rate of methane is adopted in the growth process of graphene, so that CH is increased according to the saturation degree of the reaction 4 So that the reaction rate can be secured and waste can be avoided.
Drawings
FIG. 1 is an SEM image of copper powder coated with graphene prepared in example III of the present invention;
FIG. 2 is a TEM image of graphene-coated copper powder prepared in example III of the present invention;
fig. 3 is a raman detection image of graphene-coated copper powder prepared in example three of the present invention;
fig. 4 is an XRD detection image of graphene-coated copper powder prepared in example three of the present invention.
Detailed Description
The following embodiments of the ultra-high conductive wire and cable and the method for manufacturing the same according to the present invention will be further described with reference to the accompanying drawings of fig. 1 to 4. The ultra-high conductive wire cable and the method of manufacturing the same of the present invention are not limited to the description of the following embodiments.
The ultrahigh conductive wire and cable is prepared by coating copper powder with graphene, wherein the copper powder comprises single crystal copper, and the coated area of the graphene layer is 90-100% of the surface area of the copper powder.
Further, the content of the single crystal copper in the copper powder is 80% -100%.
Preferably, the single crystal copper has a crystal plane index of (111). The conductive capability of the single crystal copper is stronger than that of common copper powder, wherein the selection of the crystal face index (111) can effectively reduce work function and further improve the conductive capability, and the surface performance is improved to a certain extent through exposed points on the structure, so that the vapor deposition growth of graphene is facilitated.
The number of layers of the graphene coating layer is 1-2. Or the number of graphene layers in the graphene coating layer is 1-2, and accounts for 20% -30% of the total amount of the graphene-coated copper powder, the number of graphene coating layers of the rest graphene-coated copper powder is more than 5, and the coating area is 100% of the surface area of the copper powder. Or the number of the graphene coating layers is more than or equal to 5, and the coating area is 100% of the surface area of the copper powder.
The preparation method of the ultrahigh conductive wire and cable comprises the following steps:
step S1: uniformly mixing the dendritic copper powder and the anti-sintering agent powder according to the mass ratio of 4:1 to obtain mixed powder.
Specifically, in step S1, the dendritic copper powder has a particle size of 200 to 500 meshes, and the copper powder includes single crystal copper, wherein the content of the single crystal copper is 80 to 100%, and the crystal plane index of the single crystal copper is (111); the sintering-resistant agent powder is one or more of magnesium oxide, graphite, chromium powder or silver powder, and the particle size is 2-50 mu m. Of course, other sintering inhibitors can also play a role in preventing sintering and do not influence the reaction.
Preferably, in this step, the mixed powder is subjected to plasma treatment under vacuum conditions. The plasma treatment is carried out for 30-120 min by using argon or argon oxygen plasma at the temperature of 40-100 ℃ and the vacuum degree of 10-400 Pa.
Step S2: the mixed powder obtained in step S1 was put into a quartz tube, and vacuum-pumping was performed.
Preferably, in step S2, after vacuum-pumping, hydrogen gas is introduced into the quartz tube, and the mixed powder is reduced at a high temperature. Used for exhausting gas such as air in the reaction vessel and reducing the copper surface. Specifically, the flow rate of the hydrogen is 200-800 sccm; the reduction temperature is 800-1050 ℃; the reduction time is 60-180 min. It should be noted that, in the present invention, the mixed powder is first plasma-treated and then placed in the quartz tube, but it is needless to say that the mixed powder may be first placed in the quartz tube and then plasma-treated.
Step S3: and (2) keeping introducing hydrogen and methane into the quartz tube to grow the graphene, wherein the flow velocity of the hydrogen is fixed, the flow velocity of the methane is increased at fixed flow velocity according to time intervals, the methane is stopped introducing after the temperature is continuously increased to be over 1000 ℃, the methane is quickly cooled, and the hydrogen is stopped introducing when the temperature is reduced to 200 ℃, so that the graphene-coated copper powder/anti-sintering agent composite powder is obtained.
Specifically, in step S3, the flow rate of the hydrogen gas is 500-1000 sccm; the initial flow rate of the methane is 20-110 sccm, and then the flow rate of the methane is increased by 10-50 sccm every 15 min; the time for growing the graphene is 45-150 min.
Step S4: and repeatedly cleaning the graphene-coated copper powder/anti-sintering agent composite powder with deionized water, performing ultrasonic dispersion, performing suction filtration, and drying to obtain the graphene-coated copper powder.
Specifically, in step S4, the time length of each cleaning and ultrasonic dispersion is 30-120S; the suction filtration time is 5-20 min; the drying temperature is 60-150 ℃, and the drying time is 5-30 min.
Step S5: and (5) loading the graphene-coated copper powder obtained in the step (S4) into a graphite die for Spark Plasma Sintering (SPS) to obtain a blank.
Specifically, in step S5, the temperature rise rate of the sintering is 10 to 100 ℃/min, and the temperature is maintained for 2 to 20min at 400 to 500 ℃, the pressure is 50 to 200KN, the final sintering temperature is 800 to 950 ℃, the temperature is maintained for 5 to 20min, and the pressure is 200 to 1200 KN.
Step S6: and (5) preheating the blank obtained in the step (S5) and a wire drawing die together, then carrying out extrusion wire drawing, and then carrying out annealing treatment to obtain the ultrahigh-conductivity wire and cable.
Specifically, in step S6, the preheating temperature is 800 to 900 ℃, the extrusion ratio of the extrusion is 10:1 to 20: 1; the temperature of the annealing treatment is 200-400 ℃, and the time is 120-300 min.
The inventor notices that a large amount of crystal boundaries exist in graphene prepared by a graphene-copper composite material prepared by a conventional CVD method, so that electron scattering is caused, and the conductivity of the material is greatly reduced. Therefore, the invention provides the ultrahigh conductive wire and cable and the preparation method thereof, which can better control the layer number of the graphene by using the single crystal copper and controlling corresponding parameters such as temperature and the like, realize the large-scale preparation of the single crystal copper-based graphene composite material, improve the conductivity of the material to the maximum extent, and realize ultrahigh conductivity>100% IACS). In addition, the copper powder is directly treated by using the plasma at low temperature (40-100 ℃), so that the antioxidant on the surface of the copper powder can be removed, the roughness of the surface of the copper powder is greatly reduced, nucleation sites are reduced, the formation of single crystal copper with a crystal face index (111) and the growth of thin graphene layers are facilitated, the number of deposited graphene layers is small, the distribution is uniform, the coating is complete, the treatment conditions are simple and controllable, the large-scale production is facilitated, the quality of the obtained copper graphene alloy powder is high, the conductivity of the wire and cable can be improved, and the wire and cable with ultrahigh conductivity is finally obtained. The argon plasma is preferably used for treating the copper powder, is stable, cannot chemically react with copper, is easy to ensure and reduce the surface roughness of the copper powder, and is beneficial to subsequent growth of single-layer graphene. In addition, the mode of gradually increasing the flow rate of methane is adopted in the growth process of graphene, so that CH is increased according to the saturation degree of the reaction 4 So that the reaction rate can be secured and waste can be avoided.
Example one
The embodiment provides a preparation method of an ultrahigh-conductivity wire and cable, which is specifically carried out according to the following steps:
step S1: uniformly mixing 200-mesh dendritic copper powder and graphite powder with the particle size of 2 mu m according to the mass ratio of 4: 1. Wherein the dendritic copper powder comprises single crystal copper, the content of the single crystal copper is 100%, and the crystal face index of the single crystal copper is (111).
Step S2: putting the powder into a quartz tube, and vacuumizing.
Step S3: h 2 CH was introduced at a flow rate of 500sccm and 20sccm 4 Increasing 10sccm CH every 15min 4 And growing for 45min, and continuously heating to 1065 ℃. Close CH 4 Quickly cooling, and closing hydrogen at 200 ℃.
Step S4: and repeatedly cleaning the composite powder with deionized water and carrying out ultrasonic treatment for 120S each time. And (4) after cleaning, carrying out suction filtration for 20min, and drying at 60 ℃ for 30min to obtain the graphene-coated copper powder.
Step S5: and (3) filling the graphene-coated copper powder into a graphite die for SPS sintering, wherein the heating rate is 100 ℃/min, the temperature is kept for 2min at 500 ℃, the pressure is 200KN, the final sintering temperature is 950 ℃, the temperature is kept for 20min, and the pressure is 1200 KN.
Step S6: and preheating the sintered blank body and a wire drawing die to 800 ℃, and extruding into a cable with the extrusion ratio of 10: 1. And finally, annealing the cable at 400 ℃ for 120 min.
The surface of the graphene-coated copper powder prepared in the embodiment is multi-layer (more than or equal to 5 layers) graphene, the coated area is 100% of the surface area of the copper powder, and the conductivity of the corresponding ultrahigh-conductivity wire and cable at room temperature is more than or equal to 89.5% IACS.
When the number of piles of graphite alkene is greater than 5 layers, its electric conductive property that corresponds slightly influences, but relative reduction the preparation degree of difficulty that corresponds, preparation that can be easier goes out the graphite alkene coating of surface coating rate 100% to further promote electric conductive property through corresponding structure.
Example two
The embodiment provides a preparation method of an ultrahigh conductive wire and cable, which is specifically carried out according to the following steps:
step S1: uniformly mixing 200-mesh dendritic copper powder and magnesium oxide powder with the particle size of 2 mu m according to the mass ratio of 4: 1. Wherein the dendritic copper powder comprises single crystal copper, the content of the single crystal copper is 100%, and the crystal face index of the single crystal copper is (111). Then, the mixture was treated with argon oxygen plasma (power 2000W) at 80 ℃ under a vacuum of 400Pa for 30 min.
Step S2: and putting the mixed powder into a quartz tube, and vacuumizing.
Step S3: h 2 CH is introduced at a flow rate of 1000sccm and 110sccm 4 Increasing 30sccm CH every 15min 4 And growing for 45min, and continuously heating to 1065 ℃. Close CH 4 Quickly cooling, and closing hydrogen at 200 ℃.
Step S4: and repeatedly cleaning the composite powder with deionized water and carrying out ultrasonic treatment for 120S each time. And (4) after cleaning, carrying out suction filtration for 20min, and drying at 60 ℃ for 30min to obtain the graphene-coated copper powder.
Step S5: and (3) filling the graphene-coated copper powder into a graphite die for SPS sintering, wherein the heating rate is 100 ℃/min, the temperature is kept for 2min at 500 ℃, the pressure is 200KN, the final sintering temperature is 950 ℃, the temperature is kept for 20min, and the pressure is 1200 KN.
Step S6: and preheating the sintered blank body and a wire drawing die to 800 ℃, and extruding into the cable with the extrusion ratio of 10: 1. And finally, annealing the cable at 400 ℃ for 120 min.
In the graphene-coated copper powder prepared in the embodiment, the Cu (111) accounts for 5-10%, the number of layers in the graphene coating layer is 1-2, the ratio is 20-30%, the rest is multiple layers (> 5), the coated area is 100% of the surface area of the copper powder, and the conductivity of the corresponding ultrahigh-conductivity wire and cable at room temperature is greater than or equal to 99.5% IACS.
The characteristics of the two-dimensional material of the graphene are fully exerted by the 1-2 layer structure of the graphene, the conductivity advantage of the graphene is optimally exerted, the surface coating rate of 90% -100% effectively modifies the surface of copper, the isotropy of the material performance is ensured, and the performance of single crystal copper is stably improved. When the number of piles of graphite alkene is greater than 5 layers, its electric conductive property that corresponds slightly influences, but relative reduction the preparation degree of difficulty that corresponds, preparation that can be easier goes out the graphite alkene coating of surface coating rate 100% to further promote electric conductive property through corresponding structure. The copper powder is coated by the graphene with the two structures, so that the conductivity is improved to the maximum extent, and the manufacturing difficulty is considered. Meanwhile, when the graphene accounts for 20-30% of the coating layer with 1-2 layers, the corresponding composite material can achieve the best conductivity.
EXAMPLE III
The embodiment provides a preparation method of an ultrahigh conductive wire and cable, which is specifically carried out according to the following steps:
step S1: uniformly mixing 200-mesh dendritic copper powder and magnesium oxide powder with the particle size of 2 mu m according to the mass ratio of 4: 1. Wherein the dendritic copper powder comprises single crystal copper, the content of the single crystal copper is 100%, and the crystal face index of the single crystal copper is (111). Then, the mixture was treated with argon oxygen plasma (power 2000W) at 50 ℃ and a vacuum degree of 400Pa for 30 min.
Step S2: putting the powder into a quartz tube, vacuumizing, and introducing H into the quartz tube at 200sccm 2 And reducing at 1050 ℃ for 60 min.
Step S3: changing H 2 CH was introduced at a flow rate of 500sccm and 20sccm 4 Increasing 10sccm CH every 15min 4 And growing for 45min, and continuously heating to 1065 ℃. Close CH 4 Quickly cooling, and closing hydrogen at 200 ℃.
Step S4: and repeatedly cleaning the composite powder with deionized water and carrying out ultrasonic treatment for 120S each time. And (4) after cleaning, carrying out suction filtration for 20min, and drying at 60 ℃ for 30min to obtain the graphene-coated copper powder.
Step S5: and (3) filling the graphene coated copper powder into a graphite die for SPS sintering, wherein the heating rate is 100 ℃/min, the temperature is kept at 500 ℃ for 2min, the pressure is 200KN, the final sintering temperature is 950 ℃, the temperature is kept for 20min, and the pressure is 800 KN.
Step S6: and preheating the sintered blank body and a wire drawing die to 800 ℃, and extruding into the cable with the extrusion ratio of 10: 1. And finally, annealing the cable at 400 ℃ for 120 min.
The SEM image of the powder in FIG. 1 shows that the surface area of the graphene-coated copper powder is 90-100%. The TEM image of FIG. 2 and the Raman image of FIG. 3 show that the number of graphene layers is 1-2. Fig. 4 shows that there is only one kind of diffraction peak in the XRD pattern of the graphene copper powder, which corresponds to the Cu (111) diffraction peak, and the Cu (111) accounts for about 100% of the graphene-coated copper powder prepared in this example. The conductivity of the corresponding ultrahigh conductive wire and cable at room temperature is more than or equal to 104.6% IACS, and the modification effect is obvious.
The characteristics of the two-dimensional material of the graphene are fully exerted by the 1-2 layer structure of the graphene, the conductivity advantage of the graphene is optimally exerted, the surface coating rate of 90% -100% effectively modifies the surface of copper, the isotropy of the material performance is ensured, and the performance of single crystal copper is stably improved.
Example four
The embodiment provides a preparation method of an ultrahigh-conductivity wire and cable, which is specifically carried out according to the following steps:
step S1: uniformly mixing 500-mesh dendritic copper powder and silver powder with the particle size of 50 mu m according to the mass ratio of 4: 1. Wherein the dendritic copper powder comprises single crystal copper, the content of the single crystal copper is 100%, and the crystal face index of the single crystal copper is (111). Then, the mixture was treated with argon-oxygen plasma (power 2000W) at 100 ℃ under a vacuum of 10Pa for 60 min.
Step S2: putting the powder into a quartz tube, vacuumizing, and introducing H into the quartz tube at 800sccm 2 Reducing at 900 deg.c for 100 min.
Step S3: change H 2 CH was introduced at a flow rate of 600sccm and 20sccm 4 Increasing the flow rate of 50sccm CH every 5min 4 Growing for 150min, and continuously heating to 1065 ℃. Close CH 4 Quickly cooling, and closing hydrogen at 200 ℃.
Step S4: and repeatedly cleaning the composite powder with deionized water and carrying out ultrasonic treatment for 30S each time. And (4) after cleaning, carrying out suction filtration for 10min, and drying at 150 ℃ for 5min to obtain the graphene-coated copper powder.
Step S5: and (3) filling the graphene-coated copper powder into a graphite die for SPS sintering, wherein the heating rate is 10 ℃/min, the temperature is kept for 20min at 400 ℃, the pressure is 90KN, the final sintering temperature is 800 ℃, the temperature is kept for 5min, and the pressure is 200 KN.
Step S6: and preheating the sintered blank body and a wire drawing die to 900 ℃, and extruding into a cable with the extrusion ratio of 20: 1. And finally, annealing the cable at 200 ℃ for 300 min.
The surface area of the graphene-coated copper powder prepared in the embodiment is 90-100%. The number of graphene layers is 1-2. The Cu (111) content of the graphene-coated copper powder prepared in this example was 100%. The conductivity of the corresponding ultrahigh conductive wire and cable at room temperature is more than or equal to 104.9% IACS, and the modification effect is obvious.
EXAMPLE five
The embodiment provides a preparation method of an ultrahigh-conductivity wire and cable, which is specifically carried out according to the following steps:
step S1: uniformly mixing 500-mesh dendritic copper powder and chromium powder with the particle size of 10 mu m according to the mass ratio of 4: 1. Wherein the dendritic copper powder comprises single crystal copper, the content of the single crystal copper is 80%, and the crystal face index of the single crystal copper is (111). Then, the mixture was treated with argon-oxygen plasma (power 2000W) at 40 ℃ under a vacuum of 100Pa for 120 min.
Step S2: putting the powder into a quartz tube, vacuumizing, and introducing H into the quartz tube at 500sccm 2 And reducing at 800 ℃ for 180 min.
Step S3: change H 2 CH was introduced at a flow rate of 900sccm and 100sccm 4 Increasing 30sccm CH every 15min 4 Growing for 120min, and continuously heating to 1065 ℃. Close CH 4 Quickly cooling, and closing hydrogen at 200 ℃.
Step S4: and repeatedly cleaning the composite powder by using deionized water and carrying out ultrasonic treatment for 60S each time. And (4) after cleaning, carrying out suction filtration for 5min, and drying at 120 ℃ for 10min to obtain the graphene-coated copper powder.
Step S5: and (3) filling the graphene-coated copper powder into a graphite die for SPS sintering, wherein the heating rate is 70 ℃/min, the temperature is kept for 10min at 400 ℃, the pressure is 50KN, the final sintering temperature is 900 ℃, the temperature is kept for 10min, and the pressure is 800 KN.
Step S6: and preheating the sintered blank body and a wire drawing die to 900 ℃, and extruding into a cable with the extrusion ratio of 15: 1. And finally, annealing the cable at 300 ℃ for 180 min.
The surface area of the graphene-coated copper powder prepared in the embodiment is 90-100%. The number of graphene layers is 1-2. The Cu (111) content of the graphene-coated copper powder prepared in this example was 80%. The conductivity of the corresponding ultrahigh conductive wire and cable at room temperature is more than or equal to 101.5% IACS, and the modification effect is obvious.
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 (10)
1. An ultra-high conductive wire cable, characterized in that: the graphene-coated copper powder is prepared by coating copper powder with graphene, wherein the copper powder comprises single crystal copper, and the coated area of the graphene layer is 90-100% of the surface area of the copper powder.
2. The ultra-high conductive wire cable of claim 1, wherein: the content of the single crystal copper in the copper powder is 80-100%.
3. The ultra-high conductive wire cable of claim 1, wherein: the crystal face index of the single crystal copper is (111).
4. The ultra-high conductive wire cable according to any one of claims 1 to 3, wherein: the number of layers of the graphene coating layer is 1-2.
5. The ultra-high conductive wire cable of any one of claims 1 to 3, wherein: the graphene with 1-2 layers in the graphene coating layer accounts for 20% -30% of the total amount of the graphene-coated copper powder, the number of the graphene coating layers of the rest graphene-coated copper powder is more than 5, and the coating area is 100% of the surface area of the copper powder.
6. The ultra-high conductive wire cable according to any one of claims 1 to 3, wherein: the number of layers of the graphene coating layers is more than or equal to 5, and the coating area is 100% of the surface area of the copper powder.
7. A preparation method of an ultrahigh conductive wire and cable is characterized by comprising the following steps: the method comprises the following steps:
step S1: uniformly mixing dendritic copper powder and anti-sintering agent powder according to the mass ratio of 4:1 to obtain mixed powder;
step S2: putting the mixed powder obtained in the step S1 into a quartz tube, and vacuumizing;
step S3: keeping introducing hydrogen and methane into the quartz tube to grow graphene, wherein the flow rate of the hydrogen is fixed, the flow rate of the methane is increased at a fixed flow rate according to a time interval, stopping introducing the methane after the temperature is continuously increased to be higher than 1000 ℃, quickly cooling, and stopping introducing the hydrogen when the temperature is reduced to 200 ℃ to obtain the graphene-coated copper powder/anti-sintering agent composite powder;
step S4: repeatedly cleaning the graphene-coated copper powder/anti-sintering agent composite powder with deionized water, performing ultrasonic dispersion, performing suction filtration, and drying to obtain graphene-coated copper powder;
step S5: loading the graphene-coated copper powder obtained in the step S4 into a graphite die for spark plasma sintering to obtain a blank;
step S6: and (5) preheating the blank obtained in the step (S5) and a wire drawing die together, then carrying out extrusion wire drawing, and then carrying out annealing treatment to obtain the ultrahigh-conductivity wire and cable.
8. The method for preparing an ultra-high conductive wire cable according to claim 7, wherein: in the step S1, the grain diameter of the dendritic copper powder is 200-500 meshes, the copper powder comprises single crystal copper, the content of the single crystal copper is 80-100%, and the crystal face index of the single crystal copper is (111); the sintering-resistant agent powder is one or more of magnesium oxide, graphite, chromium powder or silver powder, and the particle size is 2-50 mu m.
9. The method for preparing an ultra-high conductive wire cable according to claim 7, wherein: in the step S1, the mixed powder is subjected to plasma treatment, wherein the plasma treatment is performed by using argon or argon oxygen plasma at a temperature of 40 to 100 ℃ and a vacuum degree of 10 to 400Pa for 30 to 120 min.
10. The method for preparing an ultra-high conductive wire cable according to claim 7 or 9, wherein: in the step S2, after the vacuum is pumped, hydrogen is introduced into the quartz tube, and the mixed powder is reduced at a high temperature.
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