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

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

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CN115012007B
CN115012007B CN202210853853.4A CN202210853853A CN115012007B CN 115012007 B CN115012007 B CN 115012007B CN 202210853853 A CN202210853853 A CN 202210853853A CN 115012007 B CN115012007 B CN 115012007B
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copper
graphene
groups
additive
solution
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CN115012007A (en
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樊小伟
张钰松
唐云志
陆冰沪
李大双
孙桢
谭育慧
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Anhui Tongguan Copper Foil Group Co ltd
Jiangxi University of Science and Technology
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Anhui Tongguan Copper Foil Group Co ltd
Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

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, in particular to a copper-graphene electroplating solution, a copper-graphene composite foil and a preparation method thereof.
Background
Copper foil is a negative electrolytic material, and can be classified into a standard copper foil and a high-performance copper foil according to the difference in performance. In recent years, due to the upgrading and upgrading of the electronic information industry, various components are miniaturized and multifunctional, the performance requirements of the copper foil by the emerging high-tech products are not met by the traditional standard copper foil, and how to enable the copper foil to have high tensile strength and low profile under the ultra-thin condition becomes one of the research hotspots.
Graphene is used as a two-dimensional carbon nanomaterial, and is used as a reinforcing phase to be introduced into the copper foil due to excellent electric, force and thermal properties, so that the comprehensive performance of the copper foil can be improved, and the performance requirement of a high-end precise instrument on the copper foil is met. However, graphene is a two-dimensional carbon material, and aggregation easily occurs in an electroplating solution, so that the graphene cannot be uniformly dispersed in a copper matrix, which affects the performance of the copper-graphene composite material; in addition, the compatibility of the graphene and the copper matrix is poor, and the pure introduction of the graphene into the copper matrix can cause large surface roughness and low tensile strength of the copper foil, so that the performance requirement of the copper foil cannot be met.
CN104711443a discloses a graphene reinforced copper-based composite material and a preparation method thereof, wherein copper-nickel alloy powder and crystalline flake graphite are mixed in a mechanical ball milling mode, and then the graphene/copper composite material is obtained through powder metallurgy and rolling, wherein the thickness of the graphene/copper composite material is 0.1mm-2mm, and the tensile strength is 246-250MPa.
CN112063998A discloses a method for preparing an ultrathin copper-graphene composite foil, which comprises the steps of ultrasonically dispersing a single-layer graphene oxide powder with a certain mass in an electroless copper plating solution, adding an active substrate into the electroless copper plating solution to react to obtain a copper plating substrate, and finally preparing the copper-graphene composite foil with the thickness of only 0.8-5 μm, wherein the tensile strength of the copper-graphene composite foil is lower than 350MPa although the copper-graphene composite foil is prepared.
How to prepare graphene/copper composite materials with excellent performance becomes a technical problem to be solved in the metallurgical field.
Disclosure of Invention
The invention aims to solve the problems of large surface roughness, low tensile strength and the like of an ultrathin copper-graphene composite foil in the prior art, and provides a copper-graphene electroplating solution, a copper-graphene composite foil and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a copper-graphene electroplating solution comprising copper sulfate, graphene, an additive A, an additive B, a cationic surfactant, and a Cl-containing agent - An electrolyte; wherein 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 second aspect of the invention provides a preparation method of a copper-graphene composite foil, which comprises the following steps: 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 third aspect of the invention provides a copper-graphene composite foil, which has a lamellar network structure, and takes copper foil as a matrix and graphene as a reinforcing phase;
preferably, the thickness of the copper-graphene composite foil is smaller than 4 mu m, the roughness Rz is smaller than 2.0 mu m, the tensile strength is more than 470MPa, and the tensile strength after being baked at the high temperature of 200 ℃ for 10min is more than 450MPa;
preferably, the copper-graphene composite foil is prepared by the preparation method provided in the second aspect.
Through the technical scheme, the beneficial technology obtained by the invention is as follows:
1. the electroplating solution provided by the invention comprises copper sulfate, graphene, an additive A, an additive B, a cationic surfactant and a catalyst containing Cl - Is an electrolyte of (a); the nucleation rate of the electrodeposit of the copper foil can be improved by the high-current deposition condition, and the nucleation rate is improved by the high-current deposition condition of the copper foil, namely the additive A, the additive B, the cationic surfactant and the Cl - Is a synergy of (a)Under the action, the 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.
2. The copper-graphene composite foil prepared by the method can still have low roughness and high tensile strength under the ultra-thin condition, and meets the mechanical property requirement of high-end equipment on copper foil at high temperature.
3. The ultrathin high-tensile low-profile copper-graphene composite foil prepared by the method is smaller than 4 mu m in thickness, has roughness Rz smaller than 2.0 mu m, has tensile strength larger than 470MPa, is stable in high-temperature mechanical property, and has tensile strength still larger than 450MPa after being baked at the high temperature of 200 ℃ for 10 min.
Drawings
Fig. 1 is a schematic structural diagram of a copper-graphene composite foil according to an embodiment of the present invention;
FIG. 2 is a SEM image of the surface morphology of the copper-graphene composite foil prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional SEM image of a copper-graphene composite foil prepared in example 1 of the present invention;
fig. 4 is a stress-strain curve of the copper-graphene composite foils prepared in example 1, comparative example 4 and comparative example 6 according to the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a copper-graphene electroplating solution comprising copper sulfate, graphene, an additive A, an additive B, a cationic surfactant and a Cl-containing agent - An electrolyte; wherein 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 addition ofThe agent 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 copper-graphene electroplating solution is added with one or more of sodium 2-mercapto-5-benzimidazole sulfonate, sodium 2-methoxy-2-oxo-ethanesulfonate and 4-nitro-N-methylbenzenesulfonamide and one or more of additive B selected from sodium polydithio-dipropanesulfonate, sodium N, N-dimethyl-dithiocarbonyl propane sulfonate and sodium 3-thio-isothiourea propane sulfonate, and the like, so that the surface roughness of copper foil can be reduced, the internal stress of the copper foil can be reduced, and the warping of the copper foil can be prevented when the copper-graphene composite foil is prepared by electrodeposition.
According to the invention, the cationic surfactant is added into the electroplating solution to enable the surface of the graphene to be positively charged, and the principle that the same charges repel each other is utilized, so that the graphene is prevented from agglomerating and is uniformly distributed in the copper foil and is used as a reinforcing phase, and the high-performance copper-graphene composite foil is prepared.
In some embodiments, the mass ratio of additive a to additive B is 0.5-30:1, preferably 1.5-5:1.
The addition amount of the graphene has obvious influence on the copper foil performance, and if the addition amount of the graphene is too small, the copper foil performance is not obviously improved; however, if the addition amount of the graphene is too large, the graphene is easy to agglomerate in the copper foil, and the mechanical property of the copper foil is reduced. In order to ensure the dispersibility of graphene, the mechanical properties of the copper foil are improved. In some embodiments, the mass ratio of copper sulfate to graphene is 270-315:0.01-0.5, preferably 270-315:0.1-0.15, based on copper sulfate pentahydrate.
In some embodiments, the mass ratio of cationic surfactant to copper sulfate is from 0.01 to 0.015:270 to 315, based on copper sulfate pentahydrate.
In some embodiments, the Cl-containing material is calculated as copper sulfate pentahydrate - The mass ratio of the electrolyte to the copper sulfate is 0.01-0.02:270-315.
In the present invention, the addition amount of copper sulfate is calculated based on copper sulfate pentahydrate.
In some embodiments, the cationic surfactant is selected from one or more of octadecyl trimethyl ammonium chloride, tween 20, tween 40, tween 60 and tween 80.
In some embodiments, the Cl-containing - The electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride and perchloric acid.
The second aspect of the invention provides a preparation method of a copper-graphene composite foil, which comprises the following steps: the plating solution according to any one of the first aspect is used in a range of 30A/dm or more 2 And (3) electrodepositing under the current density to obtain the copper-graphene composite foil.
In some embodiments, the method of preparing the plating solution includes 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.
In some embodiments, in step (3), the mass ratio of the mixed solution to the graphene aqueous solution is 15-19:5-1.
In some embodiments, the conditions of the ultrasonic dispersion are: under the condition of water bath at room temperature, the ultrasonic dispersion is carried out for 30min.
In some embodiments, in step (1), the Cl-containing compound - The concentration of copper ions in the copper sulfate solution is 60-90g/L, preferably 70-80g/L; SO (SO) 4 2- The concentration of (C) is 80-110g/L, preferably 90-100g/L; cl - The mass concentration of (2) is 1-5ppm; preferably 1-3ppm.
In some embodiments, in step (2), the mass concentration of the cationic surfactant in the mixed liquor is 5-20ppm, preferably 10-15ppm; cl - The mass concentration is as follows5-30ppm, 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 plating solution is 0.1-0.2g/L, preferably 0.1-0.15g/L.
To further prevent the graphene from agglomerating and to uniformly distribute it inside the copper foil and 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, and if the cationic surfactant in step (2) is sufficient, the second cationic surfactant may or may not be added to the graphene aqueous solution, and the second cationic surfactant may or may not be the same as the cationic surfactant in step (2), for example, the cationic surfactant in step (2) may be tween 20, and the second cationic surfactant in the graphene aqueous solution may be tween 20, or tween 40.
In the invention, the cationic surfactant is mainly used for enhancing the dispersibility of graphene and preventing agglomeration. The cationic surfactant can make the surface of the graphene carry positive charges, increase the dispersibility of the graphene in the electroplating solution, and move towards the cathode during electrodeposition, so the cationic surfactant can be one or a combination of more of the cationic surfactants.
In some embodiments, the cationic surfactant is selected from one or more of octadecyl trimethyl ammonium chloride, tween 20, tween 40, tween 60 and tween 80.
In some embodiments, the additive a is selected from one or more of sodium 2-mercapto-5-benzimidazole sulfonate, sodium 2-methoxy-2-oxoethanesulfonate, and 4-nitro-N-methylbenzenesulfonamide.
In some embodiments, the additive B is selected from one or more of sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl-dithiocarbonyl propane sulfonate, and sodium 3-thio-isothiourea propane sulfonate.
In some embodiments, the Cl-containing - The electrolyte is selected from one or more of hydrochloric acid, sodium chloride, potassium chloride and perchloric acid.
In some preferred embodiments, the graphene has a sheet diameter (D90) of 10-20 μm, preferably 10-15 μm.
In some preferred embodiments, the graphene has a aspect ratio of 9000-10000, preferably 9000-9500.
In some embodiments, the current density is from 30 to 50A/dm 2 Preferably 30-40A/dm 2 。
In some embodiments, the electrodeposition time is 20 to 35s, preferably 25 to 35s.
In some embodiments, the temperature of the electrodeposition is 30-70 ℃, preferably 50-60 ℃.
In some embodiments, the electrodeposition uses a pure copper plate as an anode and a titanium plate as a cathode, and the electroplating solution is stirred by bubbling.
In the invention, the purpose of bubbling is to enable the copper sulfate plating solution to flow, copper ions consumed in a cathode plate during electrodeposition can be timely supplemented, concentration polarization is reduced, and copper foil powder discharge is prevented; if the consumption of copper ions is not timely supplemented during electrodeposition, powder is easy to be discharged from the surface of the copper foil under the current condition. The invention has no great requirement on the gas type, and only needs to enable the electroplating solution to flow. For example, the bubbling uses air, and the air inflow is 200-300L/min, preferably 250-300L/min.
The third aspect of the invention provides a copper-graphene composite foil having a lamellar network structure, which uses copper foil as a substrate and graphene as a reinforcing phase.
In some embodiments, the graphene is more uniformly distributed in the copper foil, as shown in fig. 1, which is a schematic structural diagram of a copper-graphene composite foil, wherein 1 is the copper foil, 2 is the graphene, and 2 is more uniformly distributed in the copper foil 1.
In the invention, the graphene is used as the reinforcing phase, and the mechanical property of the copper foil can be stably improved under the action of not influencing the conductivity in the copper foil matrix by virtue of the excellent conductivity; meanwhile, when the graphene and the copper foil are co-deposited, the crystal grain boundary energy of crystal grains of the copper foil can be effectively reduced, stress strain is reduced, diffraction peaks of the crystal grains are maintained unchanged for a long time, and change of grain textures is reduced, so that the high-temperature stability of the copper foil is improved, and the mechanical property is further improved.
In some embodiments, 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 high temperature 200 ℃ for 10 min.
The copper-graphene composite foil still has higher tensile strength under the ultrathin condition, has stable high-temperature mechanical property, has insignificant mechanical property reduction after being baked for 10min at the high temperature of 200 ℃, and can be used for preparing lithium ion batteries.
In some embodiments, the copper-graphene composite foil is prepared by the preparation method of any one of the preceding second aspects.
The copper-graphene composite foil has a lamellar network structure, still has higher tensile strength under the ultrathin condition, has stable high-temperature mechanical property, and can be used in lithium ion batteries, new energy automobiles or big data storage.
In order to further understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise specified, all reagents involved in the examples of the present invention are commercially available products and are commercially available.
In the following examples and comparative examples:
the thickness was measured by the weight density per unit area method.
The surface roughness Rz was measured using a roughometer.
Tensile strength was measured using a universal tester.
Example 1
(1) 275g of copper sulfate pentahydrate is weighed and dissolved in 945mL of pure water, a glass rod is used for stirring, 55mL of concentrated sulfuric acid is slowly added while stirring, so that the copper sulfate is completely dissolved, 5 mu L of concentrated hydrochloric acid is added, and after cooling to room temperature, the copper sulfate solution is obtained for volume reservation in a 1000mL volumetric flask;
(2) Respectively adding 15ppm of octadecyl trimethyl ammonium chloride, 20ppm of 2-mercapto-5-benzimidazole sodium sulfonate, 35 mu L of concentrated hydrochloric acid and 5ppm of polydithio-dipropyl sodium sulfonate into a copper sulfate solution, and stirring to uniformly disperse an additive in the copper sulfate solution to obtain a mixed solution;
(3) Weighing 0.1g of graphene, slowly adding a graphene aqueous solution containing a cationic surfactant octadecyl trimethyl ammonium chloride into a copper sulfate solution, and performing ultrasonic dispersion in an ultrasonic cleaner for 30min to uniformly disperse the graphene in a mixed solution to obtain an electroplating solution;
(4) Taking a pure copper plate as an anode, a titanium plate as a cathode, opening a bubbling device, setting the air inflow to 300L/min, and setting the current density to 30A/dm 2 And (3) carrying out electrodeposition for 35s at the temperature of 50 ℃ to obtain the copper-graphene composite foil. Fig. 2 is an SEM image of the surface morphology of the obtained copper-graphene composite foil, and as can be seen from fig. 2, the surface of the copper-graphene composite foil is relatively flat and has relatively small surface roughness. Fig. 3 is a cross-sectional SEM image of the resulting copper-graphene composite foil. The atomic percentages (%) of the three points were obtained by testing the three points 1, 2 and 3 in fig. 3 by a scanning electron spectroscopy (EDS), and the results are shown in table 1.
The performance results of the copper-graphene composite foil obtained through detection are shown in table 2, and the stress-strain curve of the copper-graphene composite foil obtained through detection is shown in fig. 4.
TABLE 1
Atomic percent (%) 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
As can be seen from the data in table 1, the presence of higher carbon element content in the copper foil indicates that graphene is present in the resulting composite foil.
Example 2
Copper-graphene composite foil was prepared according to the method of example 1, except that the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in the mixed solution obtained in step (2) was 1.5:1.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Example 3
Copper-graphene composite foil was prepared according to the method of example 1, except that the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in the mixed solution obtained in step (2) was 5:1.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Example 4
A copper-graphene composite foil was prepared in the same manner as in example 1, except that the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in the mixed solution obtained in step (2) was 25:1.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Example 5
A copper-graphene composite foil was prepared as in example 1, except that the cationic surfactant in step (2) was tween 20 and tween 40 in a mass ratio of 1:1.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Example 6
A copper-graphene composite foil was prepared according to the method of example 1, except that the mass ratio of copper sulfate to graphene in the plating solution obtained in step (3) was 270:0.05.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Example 7
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, copper sulfate to Cl-containing - The mass ratio of the electrolyte is 270:0.005.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Comparative example 1
Copper-graphene composite foil was prepared according to the method of example 1, except that the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in the mixed solution obtained in step (2) was 0.1:1.
The performance results of the copper-graphene composite foil obtained by detection 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-benzimidazole sulfonate dihydrate was not added in step (2).
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Comparative example 3
Copper-graphene composite foil was prepared according to the method of example 1, except that the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in the mixed solution obtained in step (2) was 50:1.
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
Comparative example 4
A copper-graphene composite foil was prepared according to the method of example 1, except that sodium polydithio-dipropyl sulfonate was not added in step (2).
The performance results of the copper-graphene composite foil obtained through detection are shown in table 2, and the stress-strain curve of the copper-graphene composite foil obtained through detection is shown in fig. 4.
Comparative example 5
A copper-graphene composite foil was prepared in accordance with the method of example 1, except that the current density in step (4) was 10A/dm 2 Failure to form tissueCopper foil with compact structure.
The performance results of the copper-graphene composite foil obtained by detection 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.
The performance results of the copper-graphene composite foil obtained through detection are shown in table 2, and the stress-strain curve of the copper-graphene composite foil obtained through detection is shown in fig. 4.
Comparative example 7
A copper-graphene composite foil was prepared according to the method of example 1, except that a bubbling device was not used in step (4).
The performance results of the copper-graphene composite foil obtained by detection are shown in table 2.
TABLE 2
As can be seen from the results of table 2, the mass ratio of the sodium 2-mercapto-5-benzimidazole sulfonate to the sodium polydithio-dipropyl sulfonate in examples 1 to 4 is different, and in this range, the copper-graphene composite foil has lower surface roughness, higher tensile strength and high temperature stability. In comparative example 4, since sodium polydithio-dipropyl sulfonate was not used, and at the same time, graphene itself had poor compatibility with the copper matrix, in the absence of an effective leveler, the copper foil roughness was increased, resulting in a decrease in tensile strength. In comparative example 5, the prepared copper plating layer had a loose structure, could not be separated from the titanium plate, and it was hypothesized that the copper foil having a compact structure could not be formed because a sufficient number of copper ions were not rapidly co-deposited with graphene during the cathodic electrodeposition, probably due to the small current density. In comparative example 6, since graphene is not present in the plating solution, the prepared copper foil belongs to a pure copper foil, and a graphene reinforcing phase is not present inside the copper foil. The tensile test results in comparative example 2 show that the tensile strength of the copper foil is only 326MPa, which is not much different from that of the common pure copper foil and is far lower than that of the copper-graphene composite foil.
As can be seen from fig. 4, 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.
From the above, the copper-graphene composite foil provided by the invention has the advantages of 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 idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the 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.
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