CN113293417A - Preparation method of bright high-conductivity graphene/copper composite material - Google Patents
Preparation method of bright high-conductivity graphene/copper composite material Download PDFInfo
- Publication number
- CN113293417A CN113293417A CN202110618921.4A CN202110618921A CN113293417A CN 113293417 A CN113293417 A CN 113293417A CN 202110618921 A CN202110618921 A CN 202110618921A CN 113293417 A CN113293417 A CN 113293417A
- Authority
- CN
- China
- Prior art keywords
- deposition
- graphene
- copper
- preparation
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- 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
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
The invention belongs to the technical field of signal transmission, and particularly relates to a preparation method of a bright high-conductivity graphene/copper composite material. Aiming at the technical problem that the bright high-conductivity graphene/copper composite material is difficult to prepare, the graphene/copper deposition solution and the electrodeposition method are provided, wherein the graphene/copper deposition solution is reasonable in proportion, green and environment-friendly, cost-saving and controllable in coating thickness, and the bright high-conductivity graphene/copper composite material which is high in bonding strength with a substrate and smooth in surface is prepared. Firstly, preparing graphene/copper deposition solution A containing gelatin and sodium dodecyl sulfate as additives; and preparing pure copper deposition solution B containing polyacrylamide and thiourea as additives. The deposition mode is alternate deposition solution deposition, and the bright high-conductivity graphene/copper composite material is obtained. The composite material prepared by the invention has the advantages of smooth and bright surface, high conductivity, uniform coating thickness, high bonding strength with a substrate, and difficult peeling and falling.
Description
Technical Field
The invention belongs to the technical field of signal transmission, and particularly relates to a preparation method of a bright high-conductivity graphene/copper composite material.
Background
In the current era, with the rapid development of technologies such as 5G communication, cloud computing, big data and the like, high-speed transmission and real-time processing of large-batch data have become bottleneck technologies. The size of the copper wire is miniaturized (the roughness of the wire is larger and larger) due to the skin effect and high density development of the copper conductor in the PCB, so that the signal transmission is more and more concentrated on the surface layer of the wire due to the high speed/high frequency of signals, and as a result, the signal transmission is lost or distorted due to the standing wave, reflection and the like generated on the roughness layer of the signal transmission, and the signal transmission is failed in serious cases, so that the surface roughness of the copper wire is reduced by adopting a proper method so as to reduce the loss in the high-frequency signal transmission process.
At present, there are many preparation methods of graphene/metal-based composite materials, mainly including various methods such as powder metallurgy, chemical vapor deposition, electrodeposition and the like, wherein the electrodeposition is a method of uniformly depositing graphene on the surface of a metal substrate by means of redox reaction, and has the advantages of simple process, controllable coating thickness and the like, but the electrodeposition still has the following problems: (1) the components and process parameters of the electrodeposition liquid can directly influence the tissue and the performance of the prepared composite material; (2) the graphite coating is poor in combination with a matrix, and is easy to fall off and oxidize, and the problems limit the application of an electrodeposition method in the aspect of preparing the graphene/metal matrix composite material.
Disclosure of Invention
The invention aims to provide the graphene/copper deposition solution and the electrodeposition method which are reasonable in proportion, green, environment-friendly, cost-saving and controllable in coating thickness, so that the bright high-conductivity graphene/copper composite material which is high in bonding strength with a substrate and smooth in surface is prepared.
Graphene is called an ideal reinforcement material of a metal matrix composite material due to its excellent mechanical properties (the Young modulus of single-layer graphene reaches 1TPa, and the tensile strength reaches 130 GPa). Graphene is uniformly dispersed in copper sulfate pentahydrate solution to form copper sulfate pentahydrate/graphene composite electrodeposition solution, so that on one hand, the material performance can be improved, and on the other hand, the deposition solution can be recycled, and the cost is saved. The deposition solution provided by the invention is matched with the process of the invention to prepare the graphene/copper composite material, and the obtained graphene/copper composite material coating has the advantages of smooth and bright surface, uniform thickness, high bonding strength with a substrate and difficult shedding.
The technical solution of the invention is as follows:
a preparation method of a bright high-conductivity graphene/copper composite material is specifically implemented as follows:
(1) preparing graphene/copper deposition liquid, namely A, wherein gelatin and sodium dodecyl sulfate are used as additives and added into A;
the sediment liquid A comprises the following components in percentage by mass: 100-200 g/L of copper sulfate pentahydrate, 0.1-0.8 g/L of graphene, 0.1-0.8 g/L of sodium dodecyl sulfate, 5-25 mg/L of gelatin and the balance of deionized water;
the preparation method of the electrodeposition solution A comprises the following steps: mixing graphene and sodium dodecyl sulfate, performing ultrasonic dispersion, and performing high-speed homogeneous dispersion at a speed of 3000-6000 r/min; mixing gelatin and copper sulfate pentahydrate solution, mechanically stirring, mixing with graphene solution, stirring with an electric stirrer, and homogenizing at high speed to obtain deposition solution A.
(2) Preparing a pure copper deposition solution, namely B, wherein polyacrylamide and thiourea are used as additives to be added into B;
the sediment liquid B comprises the following components in percentage by mass: 100-200 g/L of copper sulfate pentahydrate, 3-20 mg/L of polyacrylamide, 6-40 mg/L of thiourea and the balance of deionized water.
The preparation method of the electrodeposition solution B comprises the following steps: mixing polyacrylamide and thiourea, performing ultrasonic dispersion, mixing with copper sulfate pentahydrate, stirring by using an electric stirrer, and performing high-speed homogeneous dispersion at the speed of 1000-3000r/min to obtain a deposition solution B.
(3) And (3) performing electrodeposition by adopting a direct current electrodeposition method, wherein the deposition mode is alternate deposition liquid deposition.
The technological parameters in the electrodeposition process are as follows: the temperature of the electrodeposition solution is 20-35 ℃, and the pH value is 1-3.
The deposition mode in the electrodeposition process is alternate deposition liquid deposition, namely depositing in the deposition liquid A for 20-60 min, cleaning and drying with absolute ethyl alcohol and deionized water, and then depositing in the deposition liquid B for 10-30 min to obtain the bright high-conductivity graphene/copper composite material.
The composite material prepared by the method is a wire or foil, the electric conductivity is 61-115% IACS, and the surface roughness (Ra) is 0.807-4.211 μm. Through a plating layer binding force test, the copper plating layer technical condition (QJ454-88) standard of the aerospace industry department of the people's republic of China is referred to and reached, and the plating layer does not peel off or fall off, so that the plating layer binding force is good.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention provides the graphene/copper deposition solution with reasonable proportion, cost saving and controllable coating thickness and the electrodeposition method. The invention adopts an alternate deposition mode, on one hand, the conductivity of the composite material can be improved, and on the other hand, the surface roughness of the composite material can be reduced through the leveling effect of the deposition liquid, so that the loss of high-frequency signals in the transmission process can be reduced. In addition, the process parameters and the plating thickness of the graphene/copper composite material in the preparation process are controllable, and the graphene/copper composite material can be directly applied to industrial production and preparation.
Drawings
Fig. 1 is a process flow chart of preparing a bright high-conductivity graphene/copper composite material by an electrodeposition method.
Detailed Description
The invention will be further described with reference to the following examples, which are intended to illustrate the invention without limiting its scope: the following examples all illustrate the preparation of 1L of the deposition solution.
Example 1
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 0.1g/L of graphene, 5mg/L of gelatin, 0.1g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 3mg/L of polyacrylamide, 6mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 20 ℃, and the pH value of the sediment liquid is 3. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition liquid deposition, namely deposition is firstly carried out in the deposition liquid A for 20min, and deposition is carried out in the deposition liquid B for 10min after cleaning and drying by absolute ethyl alcohol and deionized water.
The prepared graphene/copper composite wire has a basically flat surface, a uniform plating layer thickness, a surface roughness (Ra) of 2.675 mu m, a deposition solution leveling capability of 3.1% and a composite wire conductivity of 87% IACS.
The prepared bright high-conductivity graphene/copper composite wire is bent for a plurality of times at any position, and the technical conditions of copper plating (QJ454-88) which are standard by the ministry of aerospace industry of the people's republic of China are referred to and reached, and the results show that the plating layer does not peel off or fall off after being bent for 5 times at 90 degrees, and the bonding force of the plating layer is good.
Wherein, the testing method of the leveling capability L of the deposition solution is a roughness method, wherein L ═ R-R0) R, R is the roughness of the substrate before electrodeposition, R0The roughness of the plated layer after electrodeposition.
Example 2
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 120g/L of copper sulfate pentahydrate, 0.2g/L of graphene, 10mg/L of gelatin, 0.2g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 120g/L of copper sulfate pentahydrate, 6mg/L of polyacrylamide, 12mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 25 ℃, and the pH value of the sediment liquid is 2.5. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition liquid deposition, namely deposition is firstly carried out in the deposition liquid A for 30min, and deposition is carried out in the deposition liquid B for 15min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 2.583 mu m, leveling capability of a deposition solution of 6.4 percent and conductivity of 93 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 3
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 140g/L of copper sulfate pentahydrate, 0.4g/L of graphene, 15mg/L of gelatin, 0.4g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 140g/L of copper sulfate pentahydrate, 10mg/L of polyacrylamide, 20mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 30 ℃, and the pH value of the sediment liquid is 2. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition liquid deposition, namely depositing in the deposition liquid A for 40min, cleaning and drying by absolute ethyl alcohol and deionized water, and then depositing in the deposition liquid B for 20 min.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 2.373 mu m, leveling capacity of a deposition solution of 14.1 percent and conductivity of 96 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 4
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 0.6g/L of graphene, 20mg/L of gelatin, 0.6g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 20mg/L of polyacrylamide, 30mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the deposition solution is 30 ℃, and the pH value of the deposition solution is 1. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition solution deposition, namely deposition is firstly carried out in the deposition solution A for 25min, and deposition is carried out in the deposition solution B for 15min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 1.497 mu m, leveling capability of a deposition solution of 45.8 percent and conductivity of 115 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 5
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 0.8g/L of graphene, 20mg/L of gelatin, 0.8g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 20mg/L of polyacrylamide, 20mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 35 ℃, and the pH value of the sediment liquid is 1. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition liquid deposition, namely deposition is firstly carried out in the deposition liquid A for 30min, and deposition is carried out in the deposition liquid B for 25min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 1.885 mu m, leveling capability of a deposition solution of 31.8 percent and conductivity of 111 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 6
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 0.6g/L of graphene, 20mg/L of gelatin, 0.6g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 20mg/L of polyacrylamide, 30mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 30 ℃, and the pH value of the sediment liquid is 2. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition solution deposition, namely deposition is firstly carried out in the deposition solution A for 25min, and deposition is carried out in the deposition solution B for 15min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, uniform coating thickness, surface roughness (Ra) of 2.053 mu m, leveling capability of a deposition solution of 25.7 percent and electrical conductivity of 106 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 7
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 0.6g/L of graphene, 20mg/L of gelatin, 0.6g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 25mg/L of polyacrylamide, 30mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the deposition solution is 30 ℃, and the pH value of the deposition solution is 1. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition solution deposition, namely deposition is firstly carried out in the deposition solution A for 25min, and deposition is carried out in the deposition solution B for 15min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 2.217 microns, a deposition solution leveling capability of 19.7 percent and composite wire conductivity of 103 percent IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Example 8
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 0.6g/L of graphene, 20mg/L of gelatin, 0.6g/L of sodium dodecyl sulfate and the balance of deionized water; the pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 20mg/L of polyacrylamide, 30mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 30 ℃, and the pH value of the sediment liquid is 1.5. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition solution deposition, namely deposition is firstly carried out in the deposition solution A for 25min, and deposition is carried out in the deposition solution B for 15min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite foil prepared under the formula, the process environment and the electrodeposition parameters has a smooth and bright surface, a uniform coating thickness, surface roughness (Ra) of 0.807 mu m, a deposition solution leveling capability of 47.3 percent and a composite foil conductivity of 110 percent IACS. In addition, after the composite foil is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the bonding force of the plating layer is good.
Comparative example 1
The graphene/copper deposition solution is called A and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 0.1g/L of graphene, 5mg/L of gelatin, 0.1g/L of sodium dodecyl sulfate and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 20 ℃, and the pH value of the sediment liquid is 3. The adopted method is a direct current deposition method, and the deposition mode is that the deposition is only carried out in the deposition solution A for 30 min.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a large amount of convex particles on the surface, the thickness of a coating is uneven, the surface roughness (Ra) is 2.668 mu m, the leveling capability of a deposition solution is 3.4 percent, and the conductivity of the composite wire is 76 percent IACS. In addition, after the composite conductor plating layer is pasted for 50 times and bent for 5 times at the same position for 90 degrees by adopting the transparent adhesive tape, the stripping or falling phenomenon appears at the position of the plating layer, which indicates that the bonding force of the plating layer is poor.
Comparative example 2
The pure copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 20mg/L of polyacrylamide, 30mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the deposition solution is 30 ℃, and the pH value of the deposition solution is 1. The adopted method is a direct current deposition method, and the deposition mode is that the deposition is only carried out in the deposition solution B for 40 min.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has the advantages of smooth surface, uniform coating thickness, 2.266 mu m of surface roughness (Ra), 18 percent of leveling capability of a deposition solution and 99 percent of IACS (International Annealed copper System) of electrical conductivity. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the plating layer does not peel or fall off, which indicates that the plating layer has good bonding force.
Comparative example 3
The pure copper deposition solution is called A and comprises the following components in percentage by mass: 200g/L of copper sulfate pentahydrate, 20mg/L of gelatin, 0.8g/L of sodium dodecyl sulfate and the balance of deionized water; the graphene/copper deposition solution is called B and comprises the following components in percentage by mass: 100g/L of copper sulfate pentahydrate, 0.8g/L of graphene, 20mg/L of polyacrylamide, 20mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 35 ℃, and the pH value of the sediment liquid is 1. The adopted method is a direct current deposition method, and the deposition mode is alternate deposition solution deposition, namely deposition is firstly carried out in the deposition solution B for 30min, and deposition is carried out in the deposition solution A for 25min after cleaning and drying by absolute ethyl alcohol and deionized water.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has the advantages that the surface of the graphene/copper composite wire is provided with a plurality of convex particles, the thickness of a plating layer is uneven, the surface roughness (Ra) is 3.088 mu m, the leveling capability of a deposition solution is-11.8%, and the conductivity of the composite wire is 77% IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, the position of the plating layer is stripped or dropped, which indicates that the bonding force of the plating layer is poor.
Comparative example 4
Preparing graphene/copper deposition solution, wherein the graphene/copper deposition solution comprises the following components in percentage by mass: 280g/L of copper sulfate pentahydrate, 0.4g/L of graphene, 15mg/L of gelatin, 0.4g/L of sodium dodecyl sulfate, 10mg/L of polyacrylamide, 20mg/L of thiourea and the balance of deionized water.
The environment of the electrodeposition process is as follows: the temperature of the sediment liquid is 30 ℃, and the pH value of the sediment liquid is 2. The adopted method is a direct current deposition method, and the deposition time is 60 min.
The graphene/copper composite wire prepared under the formula, the process environment and the electrodeposition parameters has a large number of convex particles on the surface, the coating is uneven in thickness and black in color, the surface roughness (Ra) is 4.211 mu m, the leveling capability of the deposition solution is-52.5%, and the electrical conductivity of the composite wire is 61% IACS. In addition, after the composite lead is bent for 5 times at 90 degrees at any position, most positions of the plating layer are stripped or shed, which indicates that the bonding force of the plating layer is poor.
The examples selected are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or alterations can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a bright high-conductivity graphene/copper composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparing graphene/copper deposition liquid, namely A, and adding gelatin and sodium dodecyl sulfate serving as additives into A;
(2) preparing pure copper deposition liquid, namely B, and adding polyacrylamide and thiourea serving as additives into B;
(3) and depositing by adopting a direct current deposition method, wherein the deposition mode is alternate deposition solution deposition.
2. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: the deposition solution A in the step (1) comprises the following components in percentage by mass: 100-200 g/L of copper sulfate pentahydrate, 0.1-0.8 g/L of graphene, 0.1-0.8 g/L of sodium dodecyl sulfate, 5-25 mg/L of gelatin and the balance of deionized water.
3. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: the deposition solution B in the step (2) comprises the following components in percentage by mass: 100-200 g/L of copper sulfate pentahydrate, 3-20 mg/L of polyacrylamide, 6-40 mg/L of thiourea and the balance of deionized water.
4. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: the preparation method of the electrodeposition solution in the step (1) comprises the following steps: mixing graphene and sodium dodecyl sulfate, performing ultrasonic dispersion, and performing high-speed homogeneous dispersion at a speed of 3000-6000 r/min; mixing gelatin and copper sulfate pentahydrate solution, mechanically stirring, mixing with graphene solution, stirring with an electric stirrer, and homogenizing at high speed to obtain deposition solution A.
5. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: the preparation method of the electrodeposition solution in the step (2) comprises the following steps: mixing polyacrylamide and thiourea, performing ultrasonic dispersion, mixing with copper sulfate pentahydrate, stirring by using an electric stirrer, and performing high-speed homogeneous dispersion at the speed of 1000-3000r/min to obtain a deposition solution B.
6. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: the technological parameters in the electrodeposition process in the step (3) are as follows: the temperature of the electrodeposition solution is 20-35 ℃, and the pH value is 1-3.
7. The preparation method of the bright-type high-conductivity graphene/copper composite material according to claim 1, wherein the preparation method comprises the following steps: and (3) depositing in an alternate deposition solution deposition manner in the electrodeposition process, namely depositing in the deposition solution A for 20-60 min, cleaning and drying with absolute ethyl alcohol and deionized water, and depositing in the deposition solution B for 10-30 min to obtain the bright high-conductivity graphene/copper composite material.
8. The bright high-conductivity graphene/copper composite material prepared by the method according to any one of claims 1 to 7, wherein: the composite material is a wire or foil, the electrical conductivity of the composite material is 61-115% IACS, and the surface roughness (Ra) is 0.807-4.211 μm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110618921.4A CN113293417A (en) | 2021-06-03 | 2021-06-03 | Preparation method of bright high-conductivity graphene/copper composite material |
| PCT/CN2022/095458 WO2022253114A1 (en) | 2021-06-03 | 2022-05-27 | Method for preparing bright high-conductivity graphene/copper composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110618921.4A CN113293417A (en) | 2021-06-03 | 2021-06-03 | Preparation method of bright high-conductivity graphene/copper composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113293417A true CN113293417A (en) | 2021-08-24 |
Family
ID=77326977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110618921.4A Pending CN113293417A (en) | 2021-06-03 | 2021-06-03 | Preparation method of bright high-conductivity graphene/copper composite material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113293417A (en) |
| WO (1) | WO2022253114A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115418200A (en) * | 2022-09-02 | 2022-12-02 | 常州大学 | High-strength high-heat-conductivity low-roughness graphene/copper composite material and preparation method thereof |
| WO2022253114A1 (en) * | 2021-06-03 | 2022-12-08 | 常州大学 | Method for preparing bright high-conductivity graphene/copper composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233379A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Electro-deposition preparation method of carbon nano tube-copper base composite powder |
| CN108396346A (en) * | 2018-02-06 | 2018-08-14 | 常州大学 | A kind of preparation method and application of graphene copper/steel composite material |
| CN110408969A (en) * | 2019-08-09 | 2019-11-05 | 常州大学 | A kind of preparation method of high heat-conducting copper-based graphene composite material |
| CN110670093A (en) * | 2019-10-21 | 2020-01-10 | 湖北中科铜箔科技有限公司 | Production method of 4.5-micron double-sided photoelectrolysis copper foil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11843153B2 (en) * | 2019-03-12 | 2023-12-12 | Te Connectivity Solutions Gmbh | Use of enhanced performance ultraconductive copper materials in cylindrical configurations and methods of forming ultraconductive copper materials |
| CN112064077B (en) * | 2020-09-21 | 2021-05-14 | 江西理工大学 | Preparation method of copper foil/carbon nanotube/copper foil composite foil |
| CN113293417A (en) * | 2021-06-03 | 2021-08-24 | 常州大学 | Preparation method of bright high-conductivity graphene/copper composite material |
-
2021
- 2021-06-03 CN CN202110618921.4A patent/CN113293417A/en active Pending
-
2022
- 2022-05-27 WO PCT/CN2022/095458 patent/WO2022253114A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233379A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Electro-deposition preparation method of carbon nano tube-copper base composite powder |
| CN108396346A (en) * | 2018-02-06 | 2018-08-14 | 常州大学 | A kind of preparation method and application of graphene copper/steel composite material |
| CN110408969A (en) * | 2019-08-09 | 2019-11-05 | 常州大学 | A kind of preparation method of high heat-conducting copper-based graphene composite material |
| CN110670093A (en) * | 2019-10-21 | 2020-01-10 | 湖北中科铜箔科技有限公司 | Production method of 4.5-micron double-sided photoelectrolysis copper foil |
Non-Patent Citations (4)
| Title |
|---|
| FEI LONG JIA等: "Enhanced Thermal Conductivity and Tensile Strength of Copper Matrix Compositewith Few-Layer Graphene Nanoplates", 《JOURNAL OF MATERIALS ENGINEERING AND PERFORMANCE》 * |
| KUNXIA WEI等: "Mechanical behaviors of graphene/copper matrix composite foils fabricated by pulse electrodeposition", 《SURFACES AND INTERFACES》 * |
| 吕欣蕊: "电沉积铜箔的工艺参数和拉伸性能研究", 《中国学位论文全文数据库》 * |
| 程军等: "连续电解精炼阴极铜过程中添加剂的作用", 《电镀与装饰》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022253114A1 (en) * | 2021-06-03 | 2022-12-08 | 常州大学 | Method for preparing bright high-conductivity graphene/copper composite material |
| CN115418200A (en) * | 2022-09-02 | 2022-12-02 | 常州大学 | High-strength high-heat-conductivity low-roughness graphene/copper composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022253114A1 (en) | 2022-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5497183B2 (en) | Silver-coated spherical resin, production method thereof, anisotropic conductive adhesive containing silver-coated spherical resin, anisotropic conductive film, and conductive spacer | |
| CN113293417A (en) | Preparation method of bright high-conductivity graphene/copper composite material | |
| CN109423637B (en) | Preparation method of high-conductivity material | |
| CN108728835B (en) | Preparation method of material with silver-plated surface | |
| KR20170094134A (en) | Free grounding film and manufacturing method therefor, and shielding circuit board including free grounding film and grounding method | |
| CN108396346B (en) | Preparation method and application of graphene copper/steel composite material | |
| US20170253750A1 (en) | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet, each of which uses said silver-coated copper powder | |
| US20170274453A1 (en) | Silver-coated copper powder, and conductive paste, conductive coating material and conductive sheet each of which uses same | |
| CN111394754A (en) | Copper foil additive for fifth-generation mobile communication board, copper foil and production process of copper foil | |
| CN102534710A (en) | Black coarsening treatment process for surface of very-low-profile copper foil | |
| CN112853408B (en) | Preparation method of ultrathin carrier-attached copper foil easy to peel and pure in interface | |
| CN107236973A (en) | Preparation method, product and its application of flexibility coat copper plate additive for electrolytic copper foil | |
| TWI583802B (en) | Conductive particles, a method for producing the same, a conductive resin composition containing the same, and a conductive coating | |
| CN102383148A (en) | Mixed additive for electrolytic copper foil, preparation method for mixed additive, and method for preparing ultralow-profile electrolytic copper foil | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same | |
| CN103103590A (en) | Direct-electroplating conductive liquid and preparation method thereof | |
| CN113463155A (en) | Roughening liquid for electronic copper foil surface roughening treatment and surface roughening treatment process | |
| CN107626917B (en) | Preparation method of silver-plated copper powder | |
| CN111394765A (en) | Electrolytic copper foil surface treatment process | |
| CN112111233A (en) | Thermosetting conductive shielding adhesive film and preparation method thereof | |
| CN1542073A (en) | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby | |
| CN114457325A (en) | Method for controlling thickness of nickel layer of nickel-plated polymer microsphere | |
| CN107645852A (en) | A kind of two-sided surface treatment process of copper foil of high frequency printed circuit boards | |
| CN114016098A (en) | Copper-clad plate electroplating Ni-Co-Ce film plating solution for PCB and film preparation method | |
| JP2002298654A (en) | Conductive powder and conductive composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |