CN112342596A - Preparation method of copper-based composite material with high conductivity - Google Patents
Preparation method of copper-based composite material with high conductivity Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000010949 copper Substances 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 238000007747 plating Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000009713 electroplating Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000004070 electrodeposition Methods 0.000 claims description 8
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002490 spark plasma sintering Methods 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000002048 multi walled nanotube Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004883 computer application Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001803 electron scattering Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Abstract
The invention discloses a preparation method of a copper-based composite material with high conductivity; uniformly dispersing the carbon nano material in a copper sulfate solution, adding sulfuric acid into the plating solution to adjust the pH value, and fully mixing the prepared solution by using a magnetic stirrer; the metal plate is taken as an anode, the other metal plate is taken as a cathode, and current is introduced into the composite solution, so that the carbon nano tube and the copper ions are jointly deposited on the cathode substrate; and after the electroplating is finished, taking the composite film off the electrode, reducing the composite film in a tubular furnace under a nitrogen-hydrogen atmosphere after drying, superposing the composite film to a certain thickness after reducing, putting the composite film into a graphite mold, and sintering the composite film by adopting a proper sintering process to obtain the compact carbon nanotube copper-based composite material. The carbon nano-tubes are distributed in two dimensions in the process of composite codeposition, and mainly fill gaps, so that the composite material obtains the conductivity and the elongation rate equivalent to those of pure copper.
Description
Technical Field
The invention relates to a preparation method of a copper-based composite material with high conductivity, belonging to the field of preparation of composite materials.
Background
As a typical one-dimensional nano material, the carbon nano tube has a unique structure and excellent electrical properties and appropriate mechanical properties. In the aspect of conductivity, the average free path and the electronic state density jointly determine the conductivity of the material, and the larger average free path of the carbon nano tube and the higher electronic density of the copper matrix are combined, so that the breakthrough of the composite material in the aspect of conductive application can be realized. The electrical conductivity of the carbon nanotubes is greatest in the axial (longitudinal) direction, so the alignment of the carbon nanotubes in the matrix can affect the electrical conductivity of the composite. At low temperature, since the carbon nanotube has no scattering center in its structure, it has little resistance to the movement of electrons. The ideal transmission process of the carbon nano tube, namely the ballistic transmission, is realized by a defect-free hexagonal structure of carbon, and the existence of scattering centers such as grain boundaries and impurities is avoided.
Carbon nanotubes have excellent electrical conductivity, but the decrease in conductivity of the composite structure is due to the high specific surface area of the nanotubes, resulting in a larger interface area of reinforcement and matrix; in some cases, the interface causes scattering during electron transfer, the conductivity of the composite is hindered, resulting in an increase in resistivity; the presence of carbon nanotubes can also cause lattice strain in the metal matrix, thereby reducing the conductivity of the matrix.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based composite material with high conductivity, wherein carbon nano tubes in the obtained copper-based composite material are uniformly dispersed and have complete structure, and a good electrical contact interface is formed between the carbon nano tubes and a copper matrix, and the preparation method specifically comprises the following steps:
(1) preparing a plating layer: dispersing carbon nanotube in copper sulfate solution, adding H into the solution2SO4Adjusting the pH value, taking a metal plate as an anode and another metal plate as a cathode, and introducing current into the composite solution to enable the carbon nano tube and the copper ions to be jointly deposited on a cathode substrate; in the electroplating process, the plating solution is mechanically stirred to keep the dispersibility of the solution; and after the electrodeposition is finished, putting the cathode plate into a drying box for drying, taking out the cathode plate, and taking down the coating from the cathode plate.
(2) And (3) reduction of the plating layer: heating the coating in a nitrogen-hydrogen mixed atmosphere, and eliminating internal stress while reducing; after the reduction is finished, the surface of the coating is observed to be in the color of pure metal copper, and no obvious holes are formed on the surface;
(3) and (3) sintering of the plating layer: and sintering the coating by adopting a spark plasma sintering process to obtain a compact block, and polishing the sample after sintering.
Preferably, the anode is made of phosphorus-copper alloy in step (1) of the invention, the cathode is made of titanium plate, and other copper and copper alloy or cathodes meeting the conditions can also be used in the invention.
The adding amount of the copper sulfate and the carbon nano tubes is determined according to the actual required materials, preferably, the concentration of the copper sulfate solution in the step (1) is 0.64mol/L, and the adding amount of the carbon nano tubes is 10-20 g/L.
Preferably, the current density of the electroplating process in step (1) of the present invention is 0.5 A.dm-2～4A•dm-2The electrodeposition time is 5-10 h, and the pH value is 1-7.
Preferably, in the step (2), the reduction temperature is 100-350 ℃, and the reduction time is 1-6 h.
Preferably, the conditions for spark plasma sintering in step (3) of the present invention are: the sintering temperature is 500-800 ℃, and the sintering pressure is 10-50 MPa for 10-120 minutes.
According to the inventionThe principle is as follows: the process of carrying out composite electrodeposition on the metal copper and the carbon nano tube comprises the following steps: the copper ions in the first step solution will adsorb to the surface of the carbon nanotube, especially the end part of the carbon nanotube, to form Cu2+a/CNT composite; the second step is that the complex moves towards the cathode in a directional way under the action of electrophoresis; the third step is Cu when the complex is weakly adsorbed on the cathode surface2+Reduced following a two-step sequential electron transfer process; the last step is that the carbon nano tube continuously reaches the surface of the cathode, because the electric charge of the end of the carbon nano tube is more, the two ends of the carbon nano tube are embedded into the coating of the metal copper, and finally the composite film with the unique network structure formed by the carbon nano tube in the coating of the metal copper is obtained. In addition, when the temperature is too high, the growth speed of copper particles is too fast, crystal grains are easy to grow, and when the temperature is too low, the chemical reaction speed is too slow, so that the electrodeposition occurs under the room temperature condition.
The invention has the beneficial effects that:
(1) the carbon nanotube reinforced copper-based composite material prepared by composite electrodeposition has good dispersibility in a matrix, maintains relatively complete self structure, is well combined with the matrix, and can well exert the performance of the carbon nanotube. Compared with the traditional sheet powder metallurgy, the carbon nano tube can be embedded into the metal matrix by electrodeposition instead of being adhered to the surface of the metal matrix, so that the contact area of the carbon nano tube and the metal matrix is greatly increased, metal ions are deposited on the surface or two ends of the carbon nano tube and form firm combination with the carbon nano tube, and the carbon nano tube plays a more effective role in strengthening the metal matrix; the carbon nano-tubes are distributed in two dimensions in the process of composite codeposition, and mainly fill gaps, so that the composite material obtains the conductivity and the elongation rate equivalent to those of pure copper.
(2) The composite material prepared by the process has ultrahigh conductivity while obtaining proper mechanical property; the process has relatively safe test conditions, simple and efficient preparation process and convenient regulation and control of process parameters of a test system; the method is mainly applied to the fields of different types of nano sensors, electrodes, computer application and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a scanning electron microscope image of the carbon nanotube/copper composite film.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the above description.
Example 1
A preparation method of a copper-based composite material with high conductivity specifically comprises the following steps:
(1) the preparation process of the plating layer comprises the following steps: 240g of CuSO are weighed4·5H2O, weighing 30g of multi-walled carbon nanotube dispersion liquid, pouring the multi-walled carbon nanotube dispersion liquid into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, continuously adding the ultrapure water to reach the constant volume of 1500ml, wherein the pH value of the solution is 3; the prepared solution was stirred on a magnetic stirrer for 15 minutes.
(2) Pouring electroplating solution into the Hall tank, placing two phosphorus-copper anodes on two parallel side surfaces in the Hall tank, connecting with the positive electrode of a direct current power supply, fixing a cathode titanium plate between the two anodes, and connecting with the negative electrode of the direct current power supply.
(3) Placing the Hall tank on a magnetic stirrer, turning on a switch of the magnetic stirrer, and selecting a proper stirring speed; using 0.5A dm-2The current density is electroplated, after electroplating is finished for 10 hours, the cathode titanium plate is put into a drying oven to be dried, the temperature in the drying oven is 60 ℃, the cathode titanium plate is taken out after drying is finished, and the coating is taken down from the titanium plate.
(4) The plating layers were cut into a circular shape having a diameter of 20mm, and these plating layers were reduced in a tube furnace in a nitrogen-hydrogen mixed gas atmosphere at a rate of 5K/min to 250 ℃ and held at 250 ℃ for 6 hours.
(5) Stacking the reduced coatings together along the same direction, putting the coatings into a graphite die cavity, prepressing at 20MPa for 3 minutes to ensure that the heights of the upper and lower pressure heads of the die exposed out of the die cavity are the same; and (3) performing discharge plasma sintering on the composite material after the pre-pressing is finished, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50 MPa.
The composite block is tested for mechanical property and electrical property, the tensile strength is 235MPa, and the electrical conductivity is 100.9% IACS. The surface topography of the composite film obtained in this example is shown in fig. 1, and the carbon nanotubes have a relatively complete structure while maintaining good dispersion in the copper matrix.
Example 2
A preparation method of a copper-based composite material with high conductivity specifically comprises the following steps:
(1) the preparation process of the plating layer comprises the following steps: 240g of CuSO are weighed4·5H2O, weighing 30g of multi-walled carbon nanotube dispersion liquid, pouring the multi-walled carbon nanotube dispersion liquid into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, continuously adding the ultrapure water to reach the constant volume of 1500ml, wherein the pH value of the solution is 3; the prepared solution was stirred on a magnetic stirrer for 15 minutes.
(2) Pouring electroplating solution into the Hall tank, placing two phosphorus-copper anodes on two parallel side surfaces in the Hall tank, connecting with the positive electrode of a direct current power supply, fixing a cathode titanium plate between the two anodes, and connecting with the negative electrode of the direct current power supply.
(3) Placing the Hall tank on a magnetic stirrer, turning on a switch of the magnetic stirrer, and selecting a proper stirring speed; using 0.5A dm-2The current density is electroplated, after electroplating is finished for 10 hours, the cathode titanium plate is put into a drying oven to be dried, the temperature in the drying oven is 60 ℃, the cathode titanium plate is taken out after drying is finished, and the coating is taken down from the titanium plate.
(4) The plating layers were cut into a circular shape having a diameter of 20mm, and these plating layers were reduced in a tube furnace in a nitrogen-hydrogen mixed gas atmosphere at a rate of 5K/min to 150 ℃ and held at 150 ℃ for 6 hours.
(5) Stacking the reduced coatings together along the same direction, putting the coatings into a graphite die cavity, prepressing at 20MPa for 3 minutes to ensure that the heights of the upper and lower pressure heads of the die exposed out of the die cavity are the same; and (3) performing discharge plasma sintering on the composite material after the pre-pressing is finished, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50 MPa.
The composite block is tested for mechanical property and electrical property, the tensile strength is 265MPa, and the electrical conductivity is 97.5% IACS.
Example 3
A preparation method of a copper-based composite material with high conductivity specifically comprises the following steps:
(1) the preparation process of the plating layer comprises the following steps: 240g of CuSO are weighed4·5H2O, weighing 30g of multi-walled carbon nanotube dispersion liquid, pouring the multi-walled carbon nanotube dispersion liquid into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, continuously adding the ultrapure water to reach the constant volume of 1500ml, wherein the pH value of the solution is 3; the prepared solution was stirred on a magnetic stirrer for 15 minutes.
(2) Pouring electroplating solution into the Hall tank, placing two phosphorus-copper anodes on two parallel side surfaces in the Hall tank, connecting with the positive electrode of a direct current power supply, fixing a cathode titanium plate between the two anodes, and connecting with the negative electrode of the direct current power supply.
(3) And (4) placing the Hall tank on a magnetic stirrer, turning on a switch of the magnetic stirrer, and selecting a proper stirring speed. Using 0.5A dm-2The current density is electroplated, after electroplating is finished for 10 hours, the cathode titanium plate is put into a drying oven to be dried, the temperature in the drying oven is 60 ℃, the cathode titanium plate is taken out after drying is finished, and the coating is taken down from the titanium plate.
(4) The plating layers were cut into a circular shape having a diameter of 20mm, and these plating layers were reduced in a tube furnace in a nitrogen-hydrogen mixed gas atmosphere at a rate of 5K/min to 250 ℃ and held at 250 ℃ for 6 hours.
(5) Stacking the reduced coatings together along the same direction, putting the coatings into a graphite die cavity, prepressing at 20MPa for 3 minutes to ensure that the heights of the upper and lower pressure heads of the die exposed out of the die cavity are the same; and (3) performing discharge plasma sintering on the composite material after the pre-pressing is finished, wherein the sintering temperature is 750 ℃, and the sintering pressure is 50 MPa.
The composite block is tested for mechanical property and electrical property, and the tensile strength is 275.8MPa, and the conductivity is 98.8% IACS.
Example 4
A preparation method of a copper-based composite material with high conductivity specifically comprises the following steps:
(1) the preparation process of the plating layer comprises the following steps: 240g of CuSO are weighed4·5H2And O, weighing 30g of multi-walled carbon nanotube dispersion liquid, pouring the multi-walled carbon nanotube dispersion liquid into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, continuously adding the ultrapure water to reach a constant volume of 1500ml, wherein the pH value of the solution is 7, and stirring the prepared solution on a magnetic stirrer for 15 minutes.
(2) Pouring electroplating solution into the Hall tank, placing two phosphorus-copper anodes on two parallel side surfaces in the Hall tank, connecting with the positive electrode of a direct current power supply, fixing a cathode titanium plate between the two anodes, and connecting with the negative electrode of the direct current power supply.
(3) And (4) placing the Hall tank on a magnetic stirrer, turning on a switch of the magnetic stirrer, and selecting a proper stirring speed. Using 1.5A dm-2The current density is electroplated, the electroplating is finished after 5 hours, the cathode titanium plate is put into a drying oven for drying, the temperature in the drying oven is 60 ℃, the cathode titanium plate is taken out after the drying is finished, and the coating is taken down from the titanium plate.
(4) The plating layers were cut into a circular shape having a diameter of 20mm, and these plating layers were reduced in a tube furnace in a nitrogen-hydrogen mixed gas atmosphere at a rate of 5K/min to 250 ℃ and held at 250 ℃ for 6 hours.
(5) Stacking the reduced coatings together along the same direction, putting the coatings into a graphite die cavity, prepressing at 20MPa for 3 minutes to ensure that the heights of the upper and lower pressure heads of the die exposed out of the die cavity are the same; and (3) performing discharge plasma sintering on the composite material after the pre-pressing is finished, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50 MPa. The composite block is tested for mechanical property and electrical property, the tensile strength is 288.3MPa, and the electrical conductivity is 96.9% IACS.
The improvement of the electrical property of the composite material is attributed to the fact that the current density is low, the content of the carbon nano tube is low, the annealing temperature is relatively high, the annealing time is long, the grain size of the copper matrix is large, the electron scattering is reduced, and the resistance is reduced; the carbon nano tube is dispersed uniformly, which is important for the electric conductivity, the method can realize the uniform distribution and good arrangement of the carbon nano tube in the metal matrix, and the carbon nano tube reinforced copper-based composite material prepared by the process has ultrahigh electric conductivity while ensuring certain mechanical property.
Observing the plating layer, and obviously reducing the average grain size of the composite film along with the increase of the current density at the same annealing temperature and sintering temperature; under the condition of low current density, the surface is relatively flat, no obvious particles appear, the coating has relatively good toughness, and under the condition of high current density, the surface of the coating becomes rough; the load transfer is promoted by adding the carbon nano tube, the content of the carbon nano tube is increased due to the increase of the current density, the number of the reinforcing bodies capable of bearing external load is increased, and the material obtains proper tensile strength while basically not losing the conductivity; experiments prove that the thickness of the coating is gradually increased along with the extension of the deposition time, and the average thickness of the prepared composite film is measured by using a vernier caliper and is 50-300 mu m.
Claims (6)
1. The preparation method of the copper-based composite material with high conductivity is characterized by comprising the following steps:
(1) preparing a plating layer: dispersing carbon nanotube in copper sulfate solution, adding H into the solution2SO4Adjusting the pH value, taking a metal plate as an anode and another metal plate as a cathode, and introducing current into the composite solution to enable the carbon nano tube and the copper ions to be jointly deposited on a cathode substrate; in the electroplating process, the plating solution is mechanically stirred to keep the dispersibility of the solution; after the electrodeposition is finished, the cathode plate is put into a drying oven to be dried and then taken out, and the coating is taken down from the cathode plate;
(2) and (3) reduction of the plating layer: heating the coating in a nitrogen-hydrogen mixed atmosphere, and eliminating internal stress while reducing;
(3) and (3) sintering of the plating layer: and sintering the coating by adopting a spark plasma sintering process to obtain a compact block, and polishing the sample after sintering.
2. The method for producing a copper-based composite material with high conductivity according to claim 1, characterized in that: in the step (1), the anode is made of phosphorus-copper alloy, and the cathode is a titanium plate.
3. The method for producing a copper-based composite material with high conductivity according to claim 1 or 2, characterized in that: the concentration of the copper sulfate solution in the step (1) is 0.64mol/L, and the adding amount of the carbon nano tube is 10-20 g/L.
4. The method for producing a copper-based composite material with high conductivity according to claim 3, characterized in that: the current density in the electroplating process in the step (1) is 0.5 A.dm-2～4A•dm-2The electrodeposition time is 5-10 h, and the pH value is 1-7.
5. The method for producing a copper-based composite material with high conductivity according to claim 1, characterized in that: in the step (2), the reduction temperature is 100-350 ℃, and the reduction time is 1-6 h.
6. The method for producing a copper-based composite material with high conductivity according to claim 4, characterized in that: the conditions of spark plasma sintering in the step (3) are as follows: the sintering temperature is 500-800 ℃, and the sintering pressure is 10-50 MPa for 10-120 minutes.
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