CN112342596B - 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 53
- 239000010949 copper Substances 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000007747 plating Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000009713 electroplating Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 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 4
- 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 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 238000002490 spark plasma sintering Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 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 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
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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
- 230000005540 biological transmission 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
- 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
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 230000001105 regulatory effect 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
Classifications
-
- 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; 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 copper ions to be jointly deposited on a cathode substrate; and after electroplating, taking the composite film off the electrode, reducing the composite film by using a tube furnace under nitrogen-hydrogen atmosphere after drying treatment, superposing the composite film to a certain thickness after reduction treatment, putting the composite film into a graphite mold, and sintering the composite film by adopting a proper sintering process to obtain the compact carbon nano tube copper-based composite material. In the composite codeposition process, the carbon nanotubes are distributed in two dimensions and mainly fill gaps, so that the composite material has conductivity and extensibility 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 composite material preparation.
Background
As a typical one-dimensional nanomaterial, carbon nanotubes have unique structures and excellent electrical properties as well as suitable mechanical properties. In the aspect of conductivity, the average free path and the electron state density jointly determine the conductivity of the material, and the combination of the two characteristics of the larger average free path of the carbon nano tube and the higher electron density of the copper matrix can realize the breakthrough of the composite material in the aspect of conductive application. The electrical conductivity of the carbon nanotubes is greatest in the axial (longitudinal) direction, so the arrangement of the carbon nanotubes in the matrix can affect the electrical conductivity of the composite. At low temperature, since there are no scattering centers in the structure of the carbon nanotube, it is hardly resistant to movement of electrons. This ideal transport process of carbon nanotubes, the so-called ballistic transport, is achieved by a defect-free hexagonal structure of carbon, avoiding the presence of scattering centers such as grain boundaries and impurities.
Carbon nanotubes have excellent electrical conductivity, but the decrease in electrical conductivity of the composite structure is due to the high specific surface area of the nanotubes, creating a larger interface region of reinforcement and matrix; in some cases, the interface causes scattering during electron transfer, and the conductivity of the composite is hindered, resulting in an increase in resistivity; the presence of carbon nanotubes also results in 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 nanotubes in the obtained copper-based composite material are uniformly dispersed, have complete structure and have good electrical contact interface with a copper matrix, and specifically comprise the following steps:
(1) Preparing a coating: uniformly dispersing carbon nanotubes in a copper sulfate solution, and adding H into the plating solution 2 SO 4 Adjusting the pH value, taking a metal plate as an anode and another metal plate as a cathode, and leading current into the composite solution to enable the carbon nano tube and copper ions to be jointly deposited on a cathode substrate; in the electroplating process, mechanically stirring the plating solution to maintain the dispersibility of the solution; after the electrodeposition is finished, the plating layer is taken out from the negative after being dried in a drying boxAnd taking down the polar plate.
(2) Reduction of the coating: heating the coating in a nitrogen-hydrogen mixed atmosphere, and reducing and eliminating internal stress; after the reduction is finished, observing that the surface of the plating layer is of pure copper, and no obvious holes are formed in the surface;
(3) Sintering of a coating: sintering the plating layer by adopting a spark plasma sintering process to obtain a compact block, and polishing the sample after the sintering is finished.
Preferably, the anode in step (1) of the present invention is made of a phosphor-copper alloy, the cathode is made of a titanium plate, and other copper and copper alloys satisfying the conditions or cathodes may be used in the present invention.
The addition amount of the copper sulfate and the carbon nano tube is determined according to the actual required materials, and preferably, the concentration of the copper sulfate solution in the step (1) is 0.64mol/L, and the addition amount of the carbon nano tube is 10-20 g/L.
Preferably, the current density of the electroplating process in step (1) of the present invention is 0.5A.dm -2 ～4A•dm -2 The electrodeposition time is 5-10 h, and the pH value is 1-7.
Preferably, in the step (2) of the invention, the reduction temperature is 100-350 ℃ and the reduction time is 1-6 hours.
Preferably, the condition of spark plasma sintering in step (3) of the present invention is: the sintering temperature is 500-800 ℃, and the sintering pressure is 10-50 MPa, and the sintering process is carried out for 10-120 minutes.
The principle of the invention is as follows: the process of carrying out composite electrodeposition on metallic copper and carbon nano tubes is carried out by the following steps: the copper ions in the solution of the first step are adsorbed to the surface of the carbon nano tube, especially the tube end part, to form Cu 2+ CNT complex; the second step is that the complex moves directionally to the cathode under the action of electrophoresis; the third step is Cu when the complex is weakly absorbed on the cathode surface 2+ The electron transfer process is reduced following a two-step sequence; the final step is that as the carbon nanotube continuously reaches the surface of the cathode, because the charges at the end of the carbon nanotube are more, the two ends of the carbon nanotube are embedded into the metal copper coating, and finally the carbon nanotube forms a unique network structure in the metal copper coatingAnd (3) a composite film. In addition, when the temperature is too high, the copper particles grow too fast, 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 nano tube reinforced copper-based composite material prepared by composite electrodeposition has good dispersibility in a matrix, maintains a relatively complete self structure and is well combined with the matrix, and the performance of the carbon nano tube can be well exerted. Compared with the traditional flake powder metallurgy, the electrodeposition can enable the carbon nano tube to be embedded into the metal matrix instead of being adhered to the surface of the metal matrix, so that the contact area between 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; in the composite codeposition process, the carbon nanotubes are distributed in two dimensions and mainly fill gaps, so that the composite material has conductivity and extensibility equivalent to those of pure copper.
(2) The composite material prepared by the process has proper mechanical properties and ultrahigh conductivity at the same time; the process test conditions are relatively safe, the preparation process is simple and efficient, and the process parameters of the test system can be conveniently regulated and controlled; the method is mainly applied to the fields of different types of nanosensors, electrodes, computer applications and the like.
Drawings
Fig. 1 is a process flow diagram of the present invention.
FIG. 2 is a scanning electron microscope topography of a carbon nanotube/copper composite film.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the above.
Example 1
The preparation method of the copper-based composite material with high conductivity specifically comprises the following steps:
(1) The preparation process of the plating layer comprises the following steps: weigh 240g of CuSO 4 ·5H 2 O, weighing 30g of multiwall carbon nanotube dispersion, pouring the multiwall carbon nanotube dispersion into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, and continuously adding the ultrapure water to a constant volume of 1500ml, wherein the pH value of the solution is 3; the prepared solution was placed on a magnetic stirrer and stirred for 15 minutes.
(2) Pouring electroplating solution into a Hall groove, placing two phosphorus copper anodes on two mutually parallel side surfaces in the Hall groove, 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 groove on a magnetic stirrer, opening a magnetic stirrer switch, and selecting a proper stirring speed; using 0.5A.dm -2 And (3) electroplating, namely, after electroplating for 10 hours, putting the cathode titanium plate into a drying oven for drying, wherein the temperature in the drying oven is 60 ℃, taking out after drying is finished, and taking the plating layer off the titanium plate.
(4) The coatings were cut into circles of 20mm diameter, and these coatings were reduced using a tube furnace in an atmosphere of a nitrogen-hydrogen mixture, programmed to heat up to 250℃at a rate of 5K/min, and incubated at 250℃for 6 hours.
(5) Superposing the reduced coatings together along the same direction, placing the coatings into a graphite die cavity, prepressing the coatings under 20MPa, and keeping the prepressing pressure 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 spark plasma sintering on the pre-pressed composite material, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50MPa.
The composite block is subjected to mechanical property and electrical property test, and has the tensile strength of 235MPa and the conductivity of 100.9 percent IACS. The surface morphology of the composite film obtained in this embodiment is shown in fig. 1, and the carbon nanotubes have a relatively complete structure while maintaining good dispersion in the copper matrix.
Example 2
The preparation method of the copper-based composite material with high conductivity specifically comprises the following steps:
(1) The preparation process of the plating layer comprises the following steps: weigh 240g of CuSO 4 ·5H 2 O，Weighing 30g of multiwall carbon nanotube dispersion, pouring the multiwall carbon nanotube dispersion into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into the beaker, and continuously adding the ultrapure water to a constant volume of 1500ml, wherein the pH value of the solution is 3; the prepared solution was placed on a magnetic stirrer and stirred for 15 minutes.
(2) Pouring electroplating solution into a Hall groove, placing two phosphorus copper anodes on two mutually parallel side surfaces in the Hall groove, 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 groove on a magnetic stirrer, opening a magnetic stirrer switch, and selecting a proper stirring speed; using 0.5A.dm -2 And (3) electroplating, namely, after electroplating for 10 hours, putting the cathode titanium plate into a drying oven for drying, wherein the temperature in the drying oven is 60 ℃, taking out after drying is finished, and taking the plating layer off the titanium plate.
(4) The coatings were cut into circles of 20mm diameter, and these coatings were reduced using a tube furnace in an atmosphere of a nitrogen-hydrogen mixture, programmed to warm to 150℃at a rate of 5K/min, and incubated at 150℃for 6 hours.
(5) Superposing the reduced coatings together along the same direction, placing the coatings into a graphite die cavity, prepressing the coatings under 20MPa, and keeping the prepressing pressure 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 spark plasma sintering on the pre-pressed composite material, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50MPa.
The composite block is tested for mechanical property and electrical property, the tensile strength is 265MPa, and the conductivity is 97.5% IACS.
Example 3
The preparation method of the copper-based composite material with high conductivity specifically comprises the following steps:
(1) The preparation process of the plating layer comprises the following steps: weigh 240g of CuSO 4 ·5H 2 O, weighing 30g of multiwall carbon nanotube dispersion, pouring into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring into the beaker, continuously adding the ultrapure water to a volume of 1500ml, and keeping the pH value of the solution at a value of3, a step of; the prepared solution was placed on a magnetic stirrer and stirred for 15 minutes.
(2) Pouring electroplating solution into a Hall groove, placing two phosphorus copper anodes on two mutually parallel side surfaces in the Hall groove, 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) The Hall groove is placed on the magnetic stirrer, a switch of the magnetic stirrer is turned on, and a proper stirring speed is selected. Using 0.5A.dm -2 And (3) electroplating, namely, after electroplating for 10 hours, putting the cathode titanium plate into a drying oven for drying, wherein the temperature in the drying oven is 60 ℃, taking out after drying is finished, and taking the plating layer off the titanium plate.
(4) The coatings were cut into circles of 20mm diameter, and these coatings were reduced using a tube furnace in an atmosphere of a nitrogen-hydrogen mixture, programmed to heat up to 250℃at a rate of 5K/min, and incubated at 250℃for 6 hours.
(5) Superposing the reduced coatings together along the same direction, placing the coatings into a graphite die cavity, prepressing the coatings under 20MPa, and keeping the prepressing pressure 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 spark plasma sintering on the pre-pressed composite material, wherein the sintering temperature is 750 ℃, and the sintering pressure is 50MPa.
The composite block is tested for mechanical property and electrical property, the tensile strength is 275.8MPa, and the electrical conductivity is 98.8% IACS.
Example 4
The preparation method of the copper-based composite material with high conductivity specifically comprises the following steps:
(1) The preparation process of the plating layer comprises the following steps: weigh 240g of CuSO 4 ·5H 2 O, weighing 30g of multiwall carbon nanotube dispersion, pouring into a beaker, adding 1200ml of ultrapure water into the beaker, weighing concentrated sulfuric acid, pouring into the beaker, continuously adding the ultrapure water to a constant volume of 1500ml, keeping the pH value of the solution at 7, and putting the prepared solution on a magnetic stirrer to stir for 15 minutes.
(2) Pouring electroplating solution into a Hall groove, placing two phosphorus copper anodes on two mutually parallel side surfaces in the Hall groove, 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) The Hall groove is placed on the magnetic stirrer, a switch of the magnetic stirrer is turned on, and a proper stirring speed is selected. 1.5A dm was used -2 And (3) electroplating, namely, after 5 hours of electroplating, putting the cathode titanium plate into a drying oven for drying, wherein the temperature in the drying oven is 60 ℃, taking out after the drying is finished, and taking the plating layer off the titanium plate.
(4) The coatings were cut into circles of 20mm diameter, and these coatings were reduced using a tube furnace in an atmosphere of a nitrogen-hydrogen mixture, programmed to heat up to 250℃at a rate of 5K/min, and incubated at 250℃for 6 hours.
(5) Superposing the reduced coatings together along the same direction, placing the coatings into a graphite die cavity, prepressing the coatings under 20MPa, and keeping the prepressing pressure 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 spark plasma sintering on the pre-pressed composite material, wherein the sintering temperature is 800 ℃, and the sintering pressure is 50MPa. The composite block is subjected to mechanical property and electrical property tests, the tensile strength of the composite block is 288.3MPa, and the electrical conductivity of the composite block is 96.9% IACS.
The improvement of the electrical property of the composite material is attributed to the low current density, low carbon nanotube content, relatively high annealing temperature, long annealing time, large grain size of the copper matrix, reduced electron scattering and reduced resistance of the composite material; the uniform dispersion of the carbon nanotubes is important for conductivity, and by the method, the uniform distribution and good arrangement of the carbon nanotubes in a metal matrix can be realized.
Observing the coating, wherein the average grain size of the composite film is obviously reduced along with the increase of the current density at the same annealing temperature and sintering temperature; under the condition of small current density, the surface is smoother, no obvious particles appear, the plating layer has better toughness, and under the condition of larger current density, the surface of the plating layer becomes rough; the addition of the carbon nano tube promotes load transmission, the current density is increased to increase the content of the carbon nano tube, the number of reinforcing bodies capable of bearing the additional load is increased, and the material can obtain proper tensile strength without basically losing conductivity; experiments prove that the thickness of the plating layer is gradually increased along with the extension of the deposition time, and the average thickness of the prepared composite film is 50-300 mu m by using vernier caliper measurement.
Claims (4)
1. The preparation method of the copper-based composite material with high conductivity is characterized by comprising the following steps of:
(1) Preparing a coating: uniformly dispersing carbon nanotubes in a copper sulfate solution, and adding H into the plating solution 2 SO 4 Adjusting the pH value, taking a metal plate as an anode and another metal plate as a cathode, and leading current into the composite solution to enable the carbon nano tube and copper ions to be jointly deposited on a cathode substrate; in the electroplating process, mechanically stirring the plating solution to maintain the dispersibility of the solution; after the electrodeposition is finished, the anode plate is put into a drying oven to be dried and taken out, and the plating layer is taken down from the anode plate;
(2) Reduction of the coating: heating the coating in a nitrogen-hydrogen mixed atmosphere, and reducing and eliminating internal stress;
(3) Sintering of a coating: sintering the plating layer by adopting a spark plasma sintering process to obtain a compact block, and polishing a sample after sintering;
the current density of the electroplating process in the step (1) is 0.5A.dm -2 ～4A•dm -2 The electrodeposition time is 5-10 h, and the pH value is 1-7;
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, and the sintering process is carried out for 10-120 minutes.
2. The method for producing a copper-based composite material having a high electrical conductivity according to claim 1, wherein: 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 having 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 addition amount of the carbon nano tube is 10-20 g/L.
4. The method for producing a copper-based composite material having a high electrical conductivity according to claim 1, wherein: in the step (2), the reduction temperature is 100-350 ℃ and the reduction time is 1-6 h.
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