CN115012007B - Copper-graphene electroplating solution, copper-graphene composite foil and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of composite foils, and discloses a copper-graphene electroplating solution, a copper-graphene composite foil and a preparation method thereof. The electroplating solution comprises copper sulfate, graphene, an additive A, an additive B, a cationic surfactant and a Cl-containing agent ^‑ An electrolyte; the additive A is selected from one or more of sodium 2-mercapto-5-benzimidazole sulfonate, sodium 2-methoxy-2-oxo-ethane sulfonate and 4-nitro-N-methylbenzenesulfonic acid amide; the additive B is one or more selected from sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl-dithio carbonyl propane sulfonate and sodium 3-thio-isothiourea propane sulfonate. The electroplating solution is more than or equal to 30A/dm ² And (3) electrodepositing under the current density to obtain the copper-graphene composite foil. The thickness of the copper-graphene composite foil is smaller than 4 mu m, and the high-temperature mechanical property is stable. According to the invention, graphene is introduced into the copper foil as a reinforcing phase, and the copper-graphene composite foil with high tensile strength is prepared on the premise of ensuring the low roughness value of the copper foil.

Description

Copper-graphene electroplating solution, copper-graphene composite foil and preparation method thereof

Technical field

The invention relates to the technical field of composite foils, specifically to copper-graphene electroplating solutions, copper-graphene composite foils and preparation methods thereof.

Background technique

Copper foil is a cathodic electrolytic material. According to its different properties, copper foil can be divided into standard copper foil and high-performance copper foil. In recent years, due to the upgrading of the electronic information industry, various components have developed towards miniaturization and multi-function. Traditional standard copper foil has gradually been unable to meet the performance requirements of emerging high-tech products for copper foil. How to make copper foil ultra-thin? The case with high tensile strength and low profile has become one of the research hot spots.

As a two-dimensional carbon nanomaterial, graphene has excellent electrical, mechanical and thermal properties. Introducing graphene as a reinforcing phase into copper foil can improve the overall performance of copper foil and meet the performance requirements of high-end precision instruments. Require. However, graphene is a two-dimensional carbon material that is prone to agglomeration in the electroplating solution, resulting in its inability to be uniformly dispersed in the copper matrix, which will affect the performance of the copper-graphene composite material; in addition, graphene itself has The matrix compatibility is poor. Simply introducing graphene into the copper matrix will cause the copper foil to have large surface roughness and low tensile strength, which cannot meet the performance requirements of the copper foil.

CN104711443A discloses a graphene-reinforced copper-based composite material and its preparation method. It uses mechanical ball milling to mix copper-nickel alloy powder and flake graphite, and then obtains graphene/copper composite material through powder metallurgy and rolling. The graphite The thickness of the vinyl/copper composite tape material is 0.1mm-2mm, and the tensile strength is 246-250MPa.

CN112063998A discloses a method for preparing an ultra-thin copper-graphene composite foil, which is obtained by ultrasonically dispersing a certain mass of single-layer graphene oxide powder in an electroless copper plating solution, and then adding an active substrate into the electroless copper plating solution for reaction. The copper-plated substrate is finally produced with a copper-graphene composite foil with a thickness of only 0.8-5 μm. Although an ultra-thin copper-graphene composite foil is produced, its tensile strength is lower than 350MPa.

How to prepare graphene/copper composite materials with excellent performance has become an urgent technical problem to be solved in the metallurgical field.

Contents of the invention

The purpose of the present invention is to overcome the existing problems of ultra-thin copper-graphene composite foils with large surface roughness and low tensile strength in the prior art, and to provide copper-graphene electroplating solutions, copper-graphene composite foils and their According to the preparation method, the copper-graphene composite foil can ensure a low roughness surface while still maintaining high tensile strength under ultra-thin condition.

In order to achieve the above object, the first aspect of the present invention provides a copper-graphene electroplating solution, the electroplating solution includes copper sulfate, graphene, additive A, additive B, cationic surfactant and Cl ^- containing electrolyte; wherein, the The additive A is selected from one of 2-mercapto-5-benzimidazole sodium sulfonate, 2-methoxy-2-oxoethanesulfonate sodium and 4-nitro-N-methylbenzenesulfonamide. A variety of; the additive B is selected from one of sodium polydisulfide propane sulfonate, sodium N, N-dimethyl-dithiocarbonylpropane sulfonate and sodium 3-thioisothiourea propane sulfonate, or Various.

A second aspect of the present invention provides a method for preparing a copper-graphene composite foil. The preparation method includes: electrodepositing the aforementioned electroplating solution at a current density of ≥30A/ ^dm2 to obtain a copper-graphene composite foil. .

A third aspect of the present invention provides a copper-graphene composite foil. The copper-graphene composite foil has a lamellar network structure, with copper foil as the base and graphene as the reinforcing phase;

Preferably, the thickness of the copper-graphene composite foil is less than 4 μm, the roughness Rz<2.0 μm, the tensile strength>470MPa, and the tensile strength after baking at high temperature 200°C for 10 minutes>450MPa;

Preferably, the copper-graphene composite foil is prepared by the preparation method provided in the second aspect.

Through the above technical solutions, the beneficial technologies obtained by the present invention are as follows:

1. The electroplating solution provided by the present invention includes copper sulfate, graphene, additive A, additive B, cationic surfactant and Cl ^- containing electrolyte; the nucleation rate of copper foil electrodeposition can be improved through high current deposition conditions, Under the synergistic effect of Additive A, Additive B, cationic surfactant and Cl ^- , graphene is introduced into the copper foil as a reinforcing phase, and a high tensile strength copper-graphene composite is prepared while ensuring the low roughness value of the copper foil. foil.

2. The copper-graphene composite foil prepared by the present invention can still have low roughness and high tensile strength despite being ultra-thin, and can meet the mechanical performance requirements of high-end equipment for copper foil at high temperatures.

3. The ultra-thin high-tensile low-profile copper-graphene composite foil prepared by the present invention has a thickness of less than 4 μm, a roughness Rz<2.0 μm, a tensile strength of >470MPa, and stable high-temperature mechanical properties. After baking at a high temperature of 200°C for 10 minutes The tensile strength is still greater than 450MPa.

Description of the drawings

Figure 1 is a schematic structural diagram of a copper-graphene composite foil provided by one embodiment of the present invention;

Figure 2 is an SEM image of the surface morphology of the copper-graphene composite foil prepared in Example 1 of the present invention;

Figure 3 is a cross-sectional SEM image of the copper-graphene composite foil prepared in Example 1 of the present invention;

Figure 4 is the stress-strain curve of the copper-graphene composite foil prepared in Example 1, Comparative Example 4 and Comparative Example 6 of the present invention.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.

A first aspect of the present invention provides a copper-graphene electroplating solution. The electroplating solution includes copper sulfate, graphene, additive A, additive B, cationic surfactant and Cl ^- containing electrolyte; wherein, the additive A is selected from One or more of 2-mercapto-5-benzimidazole sodium sulfonate, 2-methoxy-2-oxoethanesulfonate sodium and 4-nitro-N-methylbenzenesulfonate amide; said Additive B is selected from one or more of sodium polydisulfidepropanesulfonate, sodium N,N-dimethyl-dithiocarbonylpropanesulfonate and sodium 3-thioisothioureapropanesulfonate.

The copper-graphene electroplating solution of the present invention is added selected from the group consisting of sodium 2-mercapto-5-benzimidazole sulfonate, sodium 2-methoxy-2-oxoethanesulfonate and 4-nitro-N-methylbenzene. One or more sulfonamides selected from the group consisting of sodium polydisulfidepropanesulfonate, sodium N,N-dimethyl-dithiocarbonylpropanesulfonate and sodium 3-thioisothioureapropanesulfonate One or more additives B, etc., can reduce the surface roughness of the copper foil, reduce the internal stress of the copper foil, and prevent the copper foil from warping when preparing copper-graphene composite foil by electrodeposition.

The present invention adds a cationic surfactant to the electroplating solution to make the graphene surface positively charged, and utilizes the principle of mutual repulsion of the same kind of charges to prevent the graphene from agglomerating and make it evenly distributed inside the copper foil and serve as a reinforcing phase. To prepare high-performance copper-graphene composite foils.

In some embodiments, the mass ratio of the additive A to the additive B is 0.5-30:1, preferably 1.5-5:1.

The added amount of graphene has a significant impact on the performance of copper foil. If the added amount of graphene is too small, the performance improvement of the copper foil will not be obvious; but if the added amount of graphene is too large, graphene will easily The internal agglomeration of the copper foil reduces the mechanical properties of the copper foil. In order to ensure the dispersion of graphene and improve the mechanical properties of the copper foil. In some embodiments, based on copper sulfate pentahydrate, the mass ratio of copper sulfate to graphene is 270-315:0.01-0.5, preferably 270-315:0.1-0.15.

In some embodiments, based on copper sulfate pentahydrate, the mass ratio of the cationic surfactant to copper sulfate is 0.01-0.015:270-315.

In some embodiments, based on copper sulfate pentahydrate, the mass ratio of the Cl ^- containing electrolyte to copper sulfate is 0.01-0.02:270-315.

In the present invention, the amount of copper sulfate added is calculated based on copper sulfate pentahydrate.

In some embodiments, the cationic surfactant is selected from one or more of stearyltrimethylammonium chloride, Tween 20, Tween 40, Tween 60 and Tween 80.

In some embodiments, the Cl ^- containing electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride, and perchloric acid.

A second aspect of the present invention provides a method for preparing a copper-graphene composite foil. The preparation method includes: electroplating the electroplating solution described in any one of the foregoing first aspects at a current density of ≥30A/ ^dm2 . Deposition to obtain copper-graphene composite foil.

In some embodiments, the preparation method of the electroplating solution includes the following steps:

(1) Mix copper sulfate pentahydrate, concentrated sulfuric acid and a Cl ^- containing electrolyte accounting for 10-15wt% of the total Cl ^- containing electrolyte to obtain a Cl ^- containing copper sulfate solution;

(2) Mix the cationic surfactant, the remaining 85-90wt% Cl ^- containing electrolyte, additive A and additive B with the Cl ^- containing copper sulfate solution to obtain a mixed solution;

(3) Mix the mixed liquid with the graphene aqueous solution and disperse it ultrasonically to obtain an electroplating liquid.

In some embodiments, in step (3), the mass ratio of the mixed liquid to the graphene aqueous solution is 15-19:5-1.

In some embodiments, the ultrasonic dispersion conditions are: ultrasonic dispersion for 30 minutes under room temperature water bath conditions.

In some embodiments, in step (1), in the Cl ^- containing copper sulfate solution, the concentration of copper ions is 60-90g/L, preferably 70-80g/L; the concentration of SO ₄ ^2- is 80 -110g/L, preferably 90-100g/L; the mass concentration of Cl ^- is 1-5ppm; preferably 1-3ppm.

In some embodiments, in step (2), in the mixed liquid, the mass concentration of the cationic surfactant is 5-20 ppm, preferably 10-15 ppm; the mass concentration of ^Cl- is 5-30 ppm, preferably 10 -20ppm; the mass concentration of the additive A is 10-30ppm, preferably 15-25ppm; the mass concentration of the additive B is 1-20ppm, preferably 5-10ppm.

In some embodiments, the concentration of graphene in the electroplating solution is 0.1-0.2g/L, preferably 0.1-0.15g/L.

In order to further prevent graphene from agglomerating and allowing it to be evenly distributed inside the copper foil and serve as a reinforcing phase. In some embodiments, the graphene aqueous solution contains a second cationic surfactant.

The second cationic surfactant may or may not be added to the graphene aqueous solution. If there are enough cationic surfactants in step (2), the second cationic surfactant may not be added to the graphene aqueous solution. The second cationic surfactant may be the same as the cationic surfactant in step (2), or may be different. For example, the cationic surfactant in step (2) selects Tween 20, and the second cationic surface in the graphene aqueous solution The active agent can be Tween 20 or Tween 40.

In the present invention, the cationic surfactant is mainly used to enhance the dispersion of graphene and prevent agglomeration. Cationic surfactants can make the surface of graphene positively charged, increase the dispersion of graphene in the electroplating solution, and move toward the cathode during electrodeposition, so cationic surfactants can be one or more combinations.

In some embodiments, the cationic surfactant is selected from one or more of stearyltrimethylammonium chloride, Tween 20, Tween 40, Tween 60 and Tween 80.

In some embodiments, the additive A is selected from the group consisting of sodium 2-mercapto-5-benzimidazole sulfonate, sodium 2-methoxy-2-oxethanesulfonate, and 4-nitro-N-methylbenzene One or more types of sulfonamides.

In some embodiments, the additive B is selected from the group consisting of sodium polydisulfidepropanesulfonate, sodium N,N-dimethyl-dithiocarbonylpropanesulfonate, and sodium 3-thioisothioureapropanesulfonate. one or more.

In some embodiments, the Cl ^- containing electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride, and perchloric acid.

In some preferred embodiments, the sheet diameter (D90) of the graphene is 10-20 μm, preferably 10-15 μm.

In some preferred embodiments, the aspect ratio of the graphene is 9000-10000, preferably 9000-9500.

In some embodiments, the current density is 30-50 A/dm ² , preferably 30-40 A/dm ² .

In some embodiments, the electrodeposition time is 20-35s, preferably 25-35s.

In some embodiments, the electrodeposition temperature is 30-70°C, preferably 50-60°C.

In some embodiments, the electrodeposition uses a pure copper plate as an anode, a titanium plate as a cathode, and a bubbling method is used to stir the electroplating solution.

In the present invention, the purpose of bubbling is to make the copper sulfate electroplating solution flow, so that the copper ions consumed on the cathode plate during electrodeposition can be replenished in time, reduce concentration polarization, and prevent copper foil from powdering; if during electrodeposition, The consumption of copper ions is not replenished in time. Under this current condition, powder is easily produced on the surface of the copper foil. The present invention does not have much requirements on the type of gas, as long as it can make the electroplating liquid flow. For example, the bubbling uses air, and the air intake volume is 200-300L/min, preferably 250-300L/min.

A third aspect of the present invention provides a copper-graphene composite foil. The copper-graphene composite foil has a lamellar network structure, with copper foil as a base and graphene as a reinforcing phase.

In some embodiments, graphene is relatively uniformly distributed in the copper foil. Figure 1 is a schematic structural diagram of a copper-graphene composite foil, where 1 is copper foil, 2 is graphene, and graphene 2 is relatively uniform. The ground is distributed in copper foil 1.

In the present invention, graphene, as a reinforcing phase, can steadily improve the mechanical properties of the copper foil without affecting the conductivity in the copper foil matrix due to its excellent conductivity; at the same time, when graphene is co-deposited with the copper foil, it can effectively reduce the electrical conductivity of the copper foil. It reduces the grain boundary energy of copper foil crystal grains, reduces stress and strain, maintains the diffraction peak shape of crystal grains unchanged for a long time, reduces changes in grain texture, thereby improving the high temperature stability of copper foil and further improving mechanical properties.

In some embodiments, the thickness of the copper-graphene composite foil is <4 μm, the roughness Rz is <2.0 μm, the tensile strength is >470 MPa, and the tensile strength after baking at 200°C for 10 minutes is >450 MPa.

The copper-graphene composite foil of the present invention still has high tensile strength despite being ultra-thin, and has stable high-temperature mechanical properties. After baking at a high temperature of 200°C for 10 minutes, the mechanical properties do not drop significantly, and can be used to prepare lithium-ion batteries.

In some embodiments, the copper-graphene composite foil is prepared by the preparation method described in any one of the second aspects.

Since the copper-graphene composite foil of the present invention has a lamellar network structure, has high tensile strength despite being ultra-thin, and has stable high-temperature mechanical properties, it can be used in lithium-ion batteries, new energy vehicles or big data storage. middle.

In order to further understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of the embodiments. . Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

Unless otherwise specified, the reagents involved in the examples of the present invention are all commercially available products and can be purchased through commercial channels.

In the following examples and comparative examples:

Thickness is measured by weight density per unit area method.

Surface roughness Rz is measured using a roughness meter.

Tensile strength was measured using a universal testing machine.

Example 1

(1) Weigh 275g of copper sulfate pentahydrate and dissolve it in 945mL of pure water. Stir with a glass rod. While stirring, slowly add 55mL of concentrated sulfuric acid to completely dissolve the copper sulfate. Add 5μL of concentrated hydrochloric acid. After cooling to room temperature, weigh it in a 1000mL volumetric flask. Set aside to obtain copper sulfate solution;

(2) Add 15 ppm octadecyltrimethylammonium chloride, 20 ppm sodium 2-mercapto-5-benzimidazole sulfonate, 35 μL concentrated hydrochloric acid, and 5 ppm sodium polydisulfide propane sulfonate to the copper sulfate solution. Stir to evenly disperse the additives in the copper sulfate solution to obtain a mixed solution;

(3) Weigh 0.1g of graphene, slowly add the graphene aqueous solution containing the cationic surfactant octadecyltrimethylammonium chloride to the copper sulfate solution, and disperse it ultrasonically in an ultrasonic cleaner for 30 minutes to allow the graphene to Evenly disperse in the mixed solution to obtain electroplating solution;

(4) Use a pure copper plate as the anode and a titanium plate as the cathode. Turn on the bubbling device, set the air inlet volume to 300L/min, and conduct electrodeposition for 35 seconds at a current density of 30A/dm ² and a temperature of 50°C to obtain copper. -Graphene composite foil. Figure 2 is an SEM image of the surface morphology of the obtained copper-graphene composite foil. It can be seen from Figure 2 that the surface of the copper-graphene composite foil is relatively smooth and has small surface roughness. Figure 3 is a cross-sectional SEM image of the obtained copper-graphene composite foil. By testing three points 1, 2 and 3 in Figure 3 with a scanning electron microscope (EDS), the atomic percentage (%) of these three points is obtained. The results are shown in Table 1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2, and the stress-strain curve of the prepared copper-graphene composite foil is shown in Figure 4.

Table 1

Atomic percentage (%) C N O S Cl Cu 1 24.21 2.54 29.38 0.00 0.12 43.75 2 16.44 0.43 22.86 0.23 0.00 60.03 3 8.69 0.00 5.87 0.04 0.59 84.82

It can be seen from the data in Table 1 that there is a high content of carbon element inside the copper foil, indicating that graphene exists inside the obtained composite foil.

Example 2

A copper-graphene composite foil was prepared according to the method of Example 1. The difference is that in the mixed solution obtained in step (2), the ratio of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfide propane sulfonate The mass ratio is 1.5:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Example 3

A copper-graphene composite foil was prepared according to the method of Example 1. The difference is that in the mixed solution obtained in step (2), the ratio of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfide propane sulfonate The mass ratio is 5:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Example 4

A copper-graphene composite foil was prepared according to the method of Example 1. The difference is that in the mixed solution obtained in step (2), the ratio of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfide propane sulfonate The mass ratio is 25:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Example 5

The copper-graphene composite foil was prepared according to the method of Example 1, except that the cationic surfactant in step (2) used Tween 20 and Tween 40 with a mass ratio of 1:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Example 6

The copper-graphene composite foil was prepared according to the method of Example 1, except that in the electroplating solution obtained in step (3), the mass ratio of copper sulfate to graphene was 270:0.05.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Example 7

The copper-graphene composite foil was prepared according to the method of Example 1, except that the mass ratio of copper sulfate to cationic surfactant was 270:0.02, and the mass ratio of copper sulfate to Cl ^- containing electrolyte was 270:0.005.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Comparative example 1

A copper-graphene composite foil was prepared according to the method of Example 1. The difference is that in the mixed solution obtained in step (2), the ratio of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfide propane sulfonate The mass ratio is 0.1:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Comparative example 2

A copper-graphene composite foil was prepared according to the method of Example 1, except that sodium 2-mercapto-5-benzimidazolesulfonate dihydrate was not added in step (2).

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Comparative example 3

A copper-graphene composite foil was prepared according to the method of Example 1. The difference is that in the mixed solution obtained in step (2), the ratio of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfide propane sulfonate The mass ratio is 50:1.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Comparative example 4

The copper-graphene composite foil was prepared according to the method of Example 1, except that sodium polydisulfide propane sulfonate was not added in step (2).

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2, and the stress-strain curve of the prepared copper-graphene composite foil is shown in Figure 4.

Comparative example 5

The copper-graphene composite foil was prepared according to the method of Example 1. The difference is that the current density in step (4) is 10A/dm ² , and a copper foil with a tight organizational structure cannot be formed.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Comparative example 6

A copper-graphene composite foil was prepared according to the method of Example 1, except that step (3) was omitted.

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2, and the stress-strain curve of the prepared copper-graphene composite foil is shown in Figure 4.

Comparative example 7

The copper-graphene composite foil was prepared according to the method of Example 1, except that no bubbling device was used in step (4).

After testing, the performance results of the prepared copper-graphene composite foil are shown in Table 2.

Table 2

It can be seen from the results in Table 2 that the mass ratios of sodium 2-mercapto-5-benzimidazole sulfonate and sodium polydisulfidepropane sulfonate in Examples 1-4 are different. Within this range, copper-graphite Ethylene composite foil has lower surface roughness, higher tensile strength and high temperature stability. In Comparative Example 4, since sodium polydisulfide dipropane sulfonate was not used and graphene itself had poor compatibility with the copper matrix, in the absence of an effective leveling agent, the roughness of the copper foil increased, resulting in stretching. Intensity also decreases. In Comparative Example 5, the prepared copper coating has a loose structure and cannot be separated from the titanium plate. It is speculated that due to the low current density, when graphene is electrodeposited at the cathode, there are not enough copper ions to quickly co-deposit with the graphene, resulting in inability to Form a copper foil with a tight organizational structure. In Comparative Example 6, since there is no graphene in the electroplating solution, the prepared copper foil is pure copper foil, and there is no graphene reinforcement phase inside the copper foil. The tensile test results in Comparative Example 2 show that the tensile strength of the copper foil is only 326 MPa, which is not much different from ordinary pure copper foil and much lower than the copper-graphene composite foil of the present invention.

It can be seen from Figure 4 that the copper-graphene composite foil prepared in Example 1 of the present invention has higher tensile strength than the composite foils of Comparative Examples 4 and 6.

It can be seen from the above that the copper-graphene composite foil of the present invention has lower surface roughness, higher tensile strength and high temperature stability.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, many simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (19)

1. A copper-graphene electroplating solution is characterized by comprising copper sulfate, graphene, an additive A, an additive B, a cationic surfactant and a catalyst containing Cl ^- An electrolyte; wherein the additive A is selected from sodium 2-mercapto-5-benzimidazole sulfonate; the additive B is selected from sodium polydithio-dipropyl sulfonate;

the mass ratio of the additive A to the additive B is 0.5-30:1;

the mass ratio of the copper sulfate to the graphene is 270-315:0.01-0.5 based on the copper sulfate pentahydrate; the mass ratio of the cationic surfactant to the copper sulfate is 0.01-0.015:270-315; the Cl-containing ^- The mass ratio of the electrolyte to the copper sulfate is 0.01-0.02:270-315.

2. The plating solution of claim 1, wherein the mass ratio of the additive a to the additive B is 1.5-5:1.

3. The plating solution according to claim 1 or 2, wherein the cationic surfactant is selected from one or more of octadecyl trimethyl ammonium chloride, tween 20, tween 40, tween 60 and tween 80; and/or the number of the groups of groups,

the Cl-containing ^- Electrolyte selectionFrom one or more of hydrochloric acid, sodium chloride, potassium chloride and perchloric acid.

4. A method for preparing a copper-graphene composite foil, the method comprising: the plating solution according to any one of claims 1 to 3 at 30A/dm or more ² And (3) electrodepositing under the current density to obtain the copper-graphene composite foil.

5. The method of manufacturing according to claim 4, wherein the method of manufacturing the plating solution comprises the steps of:

(1) Copper sulfate pentahydrate, concentrated sulfuric acid and Cl-contained ^- Cl-containing electrolyte in an amount of 10-15wt% based on the total electrolyte ^- Electrolyte is mixed to obtain the Cl-containing material ^- Copper sulfate solution of (a);

(2) The cationic surfactant and the rest 85 to 90 weight percent of the catalyst contain Cl ^- Electrolyte, additive A and additive B and the Cl-containing material ^- Mixing the copper sulfate solution to obtain a mixed solution;

(3) And mixing the mixed solution with a graphene aqueous solution, and performing ultrasonic dispersion to obtain the electroplating solution.

6. The preparation method according to claim 5, wherein in the step (3), the mass ratio of the mixed solution to the graphene aqueous solution is 15-19:5-1.

7. The production process according to claim 5 or 6, wherein in the step (1), the Cl-containing compound is ^- The concentration of copper ions in the copper sulfate solution is 60-90g/L; SO (SO) ₄ ^2- The concentration of (2) is 80-110g/L; cl ^- The mass concentration of (2) is 1-5ppm; and/or the number of the groups of groups,

in the step (2), the mass concentration of the cationic surfactant in the mixed solution is 5-20ppm; cl ^- The mass concentration is 5-30ppm; the mass concentration of the additive A is 10-30ppm; the mass concentration of the additive B is 1-20ppm; and/or the number of the groups of groups,

in the step (3), the concentration of graphene in the electroplating solution is 0.1-0.2g/L; and/or the number of the groups of groups,

in the step (3), the graphene aqueous solution contains a second cationic surfactant.

8. The process according to claim 7, wherein in the step (1), the Cl-containing component ^- The concentration of copper ions in the copper sulfate solution is 70-80g/L; SO (SO) ₄ ^2- The concentration of (2) is 90-100g/L; cl ^- The mass concentration of (2) is 1-3ppm; and/or the number of the groups of groups,

in the step (2), the mass concentration of the cationic surfactant in the mixed solution is 10-15ppm; cl ^- The mass concentration is 10-20ppm; the mass concentration of the additive A is 15-25ppm; the mass concentration of the additive B is 5-10ppm; and/or the number of the groups of groups,

in the step (3), the concentration of graphene in the electroplating solution is 0.1-0.15g/L.

9. The production method according to any one of claims 4 to 6 and 8, wherein the cationic surfactant is selected from one or more of octadecyl trimethyl ammonium chloride, tween 20, tween 40, tween 60 and tween 80; and/or the number of the groups of groups,

the Cl-containing ^- The electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride and perchloric acid; and/or the number of the groups of groups,

the sheet diameter D90 of the graphene is 10-20 mu m; and/or the number of the groups of groups,

the diameter-thickness ratio of the graphene is 9000-10000.

10. The preparation method of claim 9, wherein the graphene has a sheet diameter D90 of 10-15 μm; and/or the number of the groups of groups,

the diameter-thickness ratio of the graphene is 9000-9500.

11. The preparation method of claim 7, wherein the cationic surfactant is selected from one or more of octadecyl trimethyl ammonium chloride, tween 20, tween 40, tween 60 and tween 80; and/or the number of the groups of groups,

the Cl-containing ^- The electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride and perchloric acid; and/or the number of the groups of groups,

the sheet diameter D90 of the graphene is 10-20 mu m; and/or the number of the groups of groups,

the diameter-thickness ratio of the graphene is 9000-10000.

12. The preparation method of claim 11, wherein the graphene has a sheet diameter D90 of 10-15 μm; and/or the number of the groups of groups,

the diameter-thickness ratio of the graphene is 9000-9500.

13. The production method according to any one of claims 4 to 6, 8 and 10 to 12, wherein the current density is 30 to 50A/dm ² ；

And/or the electrodeposition time is 20-35s;

and/or, the temperature of the electrodeposition is 30-70 ℃;

and/or the electro-deposition uses a pure copper plate as an anode, uses a titanium plate as a cathode, and adopts a bubbling mode to stir the electroplating solution.

14. The production method according to claim 13, wherein the current density is 30 to 40A/dm ² ；

And/or the electrodeposition time is 25-35s;

and/or the temperature of the electrodeposition is 50-60 ℃.

15. The production method according to claim 7, wherein the current density is 30 to 50A/dm ² ；

And/or the electrodeposition time is 20-35s;

and/or, the temperature of the electrodeposition is 30-70 ℃;

and/or the electro-deposition uses a pure copper plate as an anode, uses a titanium plate as a cathode, and adopts a bubbling mode to stir the electroplating solution.

16. According to claimThe production method according to claim 9, wherein the current density is 30 to 50A/dm ² ；

And/or the electrodeposition time is 20-35s;

and/or, the temperature of the electrodeposition is 30-70 ℃;

and/or the electro-deposition uses a pure copper plate as an anode, uses a titanium plate as a cathode, and adopts a bubbling mode to stir the electroplating solution.

17. The production method according to claim 15 or 16, wherein the current density is 30 to 40A/dm ² ；

And/or the electrodeposition time is 25-35s;

and/or the temperature of the electrodeposition is 50-60 ℃.

18. The copper-graphene composite foil prepared by the preparation method according to any one of claims 4 to 17, wherein the copper-graphene composite foil has a lamellar network structure, which uses copper foil as a matrix and graphene as a reinforcing phase.

19. The preparation method of claim 18, wherein the copper-graphene composite foil has a thickness of < 4 μm, a roughness Rz of < 2.0 μm, a tensile strength of > 470MPa, and a tensile strength of > 450MPa after baking at 200 ℃ for 10 min.