CN112981470B - Electroforming copper solution, preparation method and application thereof, and copper electrode - Google Patents
Electroforming copper solution, preparation method and application thereof, and copper electrode Download PDFInfo
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Abstract
The invention is suitable for the technical field of electroforming processing, and provides an electroforming copper solution, a preparation method and application thereof and a copper electrode, wherein the electroforming copper solution comprises the following components in percentage by mass: 90-270 g/L of blue vitriol, 30-90 g/L of sulfuric acid, 20-70 g/L of boric acid, 0.1-0.5 g/L of sodium chloride and/or hydrochloric acid, 0.1-0.5 g/L of polyethylene glycol, 0.5-1.2 g/L of sodium polydithio dipropyl sulfonate and 0.0063-0.04 g/L of sulfhydryl compound. The embodiment of the invention provides an electroforming copper solution, which is characterized in that boric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl-containing compound are added into the electroforming copper solution to be used as an inhibitor and are acted with chloride ions together, so that a uniform copper casting layer with fine crystal grains and good compactness can be processed.
Description
Technical Field
The invention belongs to the technical field of electroforming processing, and particularly relates to an electroforming copper solution, a preparation method and application thereof and a copper electrode.
Background
As one of special processing methods, electroforming has the advantages of high replication precision, wide processing range, material saving and the like, so the method can be used for preparing a mould with a fine pattern structure, such as a slush mould and an injection mould for instrument panel skin molding.
However, when the method is used to manufacture an electric discharge machining copper electrode, as the thickness of the cast layer increases, the cast layer is likely to have coarse grains, poor denseness, unevenness of the cast layer, and the like, which seriously affect the effect of fine texture replication.
Disclosure of Invention
An embodiment of the present invention is directed to provide an electroforming copper solution, which aims to solve the problems in the background art.
The embodiment of the invention is realized in such a way that the electroforming copper solution comprises the following components by mass concentration: 90-270 g/L of blue vitriol, 30-90 g/L of sulfuric acid, 20-70 g/L of boric acid, 0.1-0.5 g/L of sodium chloride and/or hydrochloric acid, 0.1-0.5 g/L of polyethylene glycol, 0.5-1.2 g/L of sodium polydithio dipropyl sulfonate and 0.0063-0.04 g/L of sulfhydryl compound.
As a preferable aspect of the embodiment of the present invention, the electroforming copper solution includes the following components by mass concentration: 150-200 g/L of copper sulfate pentahydrate, 50-70 g/L of sulfuric acid, 40-50 g/L of boric acid, 0.2-0.4 g/L of sodium chloride and/or hydrochloric acid, 0.2-0.4 g/L of polyethylene glycol, 0.8-1 g/L of sodium polydithio dipropyl sulfonate and 0.01-0.03 g/L of sulfhydryl compound.
In another preferable embodiment of the invention, the number average molecular weight of the polyethylene glycol is 5000-6000.
As another preferable mode of the embodiment of the present invention, the mercapto compound is a short chain mono mercapto compound.
In another preferred embodiment of the present invention, the mercapto compound is at least one of 3-mercaptopropionic acid, ethyl thioglycolate, 4-mercaptobenzoic acid, and butyl thioglycolate.
Another object of an embodiment of the present invention is to provide a method for preparing the above-mentioned copper electroforming solution, which includes the following steps:
weighing copper sulfate pentahydrate, sulfuric acid, boric acid, sodium chloride and/or hydrochloric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl compound according to the mass concentration of the components;
dissolving copper sulfate pentahydrate in deionized water to obtain a copper sulfate pentahydrate solution;
adding sulfuric acid into the copper sulfate pentahydrate solution, cooling, then respectively adding boric acid, sodium chloride and/or hydrochloric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl compound, stirring uniformly, and then carrying out constant volume with deionized water to obtain the electroforming copper solution.
Another object of the present invention is to provide an electroformed copper solution prepared by the above preparation method.
Another objective of the embodiments of the present invention is to provide an application of the above-mentioned electroforming copper solution in the preparation of a copper electrode containing precise texture by electroforming.
Another object of the present invention is to provide a copper electrode, which is obtained by electroforming a conductive pattern having fine texture using the above electroforming copper solution.
In another preferred embodiment of the present invention, the electroforming temperature is 20 to 30 ℃ and the cathode current density is 1 to 2.5A/dm2。
In the invention, the number average molecular weight of polyethylene glycol (PEG) used in the electroforming copper solution is 5000-6000. Compared with polyethylene glycol with a small number average molecular weight, PEG with the molecular weight of 5000-6000 has stronger adsorption capacity on the surface of a copper layer, the roughness of an electroformed copper layer is smaller, and in addition, PEG with the high molecular weight has higher polarization resistance and has enough inhibition effect on reduction of copper ions, so that a more compact and smaller copper particle deposit can be obtained. However, when the molecular weight of the polyethylene glycol is too high, the solubility of the polyethylene glycol is limited, so that the PEG with the molecular weight of 5000-6000 is optimally mixed with the rest of the components in the casting solution.
In addition, the processing parameters of the electroforming process are as follows: the electroforming temperature is 20-30 ℃, and the cathode current density is 1-2.5A/dm2. Experiments show that the temperature and the current density can influence the inhibition effect of the sulfhydryl compound on copper deposition. When the temperature is too high, the surface of the copper cast layer becomes uneven and the bonding force becomes poor. When the current density is too high, the structure of the casting layer becomes loose and the crystallization becomes coarse, a copper casting layer with fine and compact crystal grains can be obtained under lower current density, but when the current density is too low, the electroforming copper rate is influenced, so the optimal current density range selected by the invention is 1-2.5A/dm2. The electroforming copper solution added with different kinds of sulfhydryl compounds can be used for electroforming a fine-grained and compact copper electrode containing fine textures.
According to the electroforming copper solution provided by the embodiment of the invention, boric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl-containing compound are added into the electroforming copper solution to serve as an inhibitor and are subjected to combined action with chloride ions, so that a uniform copper casting layer with fine crystal grains and good compactness can be processed.
Drawings
FIG. 1 is a cyclic voltammogram of 3-mercaptopropionic acid (MPA).
FIG. 2 is a scanned topography of a copper cast layer from a copper electroforming solution containing a mercapto compound.
FIG. 3 is a gold phase diagram of a copper cast layer obtained by electroforming a copper solution containing a mercapto compound.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 270g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining and injecting 90g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 60g of boric acid, 0.3g of sodium chloride, 0.45g of polyethylene glycol, 0.99g of sodium polydithio-dipropyl sulfonate and 0.009g of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water, thus obtaining the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 6000; the mercapto compound is 3-mercaptopropionic acid.
Example 2
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 270g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining and injecting 90g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 60g of boric acid, 0.3g of sodium chloride, 0.45g of polyethylene glycol, 0.99g of sodium polydithio-dipropyl sulfonate and 0.012g of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water, thus obtaining the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 6000; the mercapto compound is 3-mercaptopropionic acid.
Example 3
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 270g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining and injecting 90g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 60g of boric acid, 0.3g of sodium chloride, 0.45g of polyethylene glycol, 0.99g of sodium polydithio-dipropyl sulfonate and 0.0063 of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water, thus obtaining the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 6000; the mercapto compound is 3-mercaptopropionic acid.
Example 4
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 90g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, injecting 30g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod for drainage, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 20g of boric acid, 0.1g of hydrochloric acid, 0.1g of polyethylene glycol, 0.5g of sodium polydithio-dipropyl sulfonate and 0.0063g of sulfhydryl compound, stirring uniformly, and then using deionized water for constant volume to 1L to obtain the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5000; the mercapto compound is ethyl thioglycolate.
Example 5
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 270g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining and injecting 90g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 70g of boric acid, 0.5g of sodium chloride, 0.5g of hydrochloric acid, 0.5g of polyethylene glycol, 1.2g of sodium polydithio-dipropyl sulfonate and 0.04g of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water, thus obtaining the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 6000; the mercapto compound is 4-mercaptobenzoic acid.
Example 6
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 95g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, injecting 85g of sulfuric acid into the copper sulfate pentahydrate solution by using a glass rod in a drainage mode, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 65g of boric acid, 0.2g of sodium chloride, 0.2g of hydrochloric acid, 0.5g of polyethylene glycol, 1.1g of sodium polydithio dipropyl sulfonate and 0.035g of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water, thus obtaining the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5500; the mercapto compound is butyl thioglycolate.
Example 7
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 260g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, pouring 35g of sulfuric acid into the blue vitriol solution by using a glass rod in a drainage mode, waiting for the temperature of the solution to be reduced to room temperature, then respectively adding 25g of boric acid, 0.2g of sodium chloride, 0.15g of hydrochloric acid, 0.15g of polyethylene glycol, 0.6g of sodium polydithio dipropyl sulfonate and 0.008g of sulfhydryl compound, stirring uniformly, and then carrying out constant volume to 1L by using deionized water to obtain the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5000; the mercapto compound is a mixture of 3-mercaptopropionic acid and ethyl thioglycolate in equal mass ratio.
Example 8
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 150g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining 50g of sulfuric acid by using a glass rod, injecting the sulfuric acid into the copper sulfate pentahydrate solution, waiting for the temperature of the solution to be reduced to room temperature, respectively adding 40g of boric acid, 0.2g of sodium chloride, 0.2g of polyethylene glycol, 0.8g of sodium polydithio-dipropyl sulfonate and 0.01g of sulfhydryl compound, uniformly stirring, and then using deionized water to perform constant volume to 1L to obtain the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5500; the mercapto compound is a mixture of 3-mercaptopropionic acid, ethyl thioglycolate and 4-mercaptobenzoic acid in equal mass ratio.
Example 9
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 200g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining 70g of sulfuric acid by using a glass rod, injecting the sulfuric acid into the copper sulfate pentahydrate solution, waiting for the temperature of the solution to be reduced to room temperature, respectively adding 50g of boric acid, 0.4g of sodium chloride, 0.4g of polyethylene glycol, 1g of sodium polydithio-dipropyl sulfonate and 0.03g of sulfhydryl compound, uniformly stirring, and then carrying out constant volume to 1L by using deionized water to obtain the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5500; the mercapto compound is a mixture of 4-mercaptobenzoic acid and butyl thioglycolate in equal mass ratio.
Example 10
The embodiment provides an electroforming copper solution, and the preparation method comprises the following steps:
s1, adding 180g of copper sulfate pentahydrate into 800mL of deionized water, and stirring until the copper sulfate pentahydrate is completely dissolved to obtain a copper sulfate pentahydrate solution.
S2, draining 60g of sulfuric acid by using a glass rod, injecting the sulfuric acid into the copper sulfate pentahydrate solution, waiting for the temperature of the solution to be reduced to room temperature, respectively adding 45g of boric acid, 0.3g of sodium chloride, 0.3g of polyethylene glycol, 0.9g of sodium polydithio-dipropyl sulfonate and 0.02g of sulfhydryl compound, uniformly stirring, and then using deionized water to perform constant volume to 1L to obtain the electroforming copper solution. Wherein the number average molecular weight of the polyethylene glycol is 5500; the mercapto compound is 3-mercaptopropionic acid.
Example 11
This example provides a copper electrode produced by electroforming a conductive pattern having fine textures using the electroforming copper solution provided in example 1. Wherein, in the electroplating process, the electroforming temperature is 20 ℃, and the cathode current density is 1A/dm2。
Example 12
This example provides a copper electrode produced by electroforming a conductive pattern having fine textures using the electroforming copper solution provided in example 1. Wherein, during the electroplating process, the electroforming temperature is 30 ℃, and the cathode current density is 2.5A/dm2。
Example 13
This example provides a copper electrode produced by electroforming a conductive pattern having fine textures using the electroforming copper solution provided in example 1. Wherein, during the electroplating process, the electroforming temperature is 20-30 ℃, and the cathode current density is 1.8A/dm2。
Comparative example 1
This comparative example was conducted in the same manner as in example 1 except that the tetramercapto compound, pentaerythritol (tetramercaptoacetic acid) ester, was used in place of 3-mercaptopropionic acid. This comparative example serves as a control experiment to illustrate the influence of the number of mercapto functional groups in the monothiol compound on the electrocast copper crystal, and the monothiol compound has a more excellent effect of grain refinement in the electrocast copper solution.
Comparative example 2
The comparative example was conducted in the same manner as in example 1 except that isooctyl 3-mercaptopropionate, a long-chain monothio compound, was used instead of 3-mercaptopropionic acid. This comparative example is a control experiment to show the influence of the alkyl chain length in the monothiol compound on the electrocast copper crystal, and the short-chain mercapto compound has more excellent effect of grain refinement in the electrocast copper solution.
Experimental example:
in order to determine the effect of the mercapto compound in the electrocast copper solution containing the mercapto compound of the present invention, the present invention has conducted a number of research experiments, and the specific experimental conditions are as follows:
experimental materials: the silica gel with the surface subjected to conductive treatment and the precise texture is cut into a cuboid with the size of 3.5cm multiplied by 5.5cm multiplied by 0.5cm as a matrix.
Experimental reagent: copper sulfate pentahydrate, sulfuric acid, boric acid, sodium chloride, polyethylene glycol, sodium polydithio dipropyl sulfonate and 3-mercaptopropionic acid.
An experimental instrument: an electroforming Power supply (Long WEI DC Power supply PS-305 DM), a constant temperature water bath (DF-101S heat collection type constant temperature heating magnetic stirrer), a metallographic microscope, a metallographic polishing and grinding machine and an electrochemical workstation (CHI 660e, Shanghai Chenghua).
Preparing an electrochemical test mother solution (electroforming copper solution):
weighing 90g of copper sulfate pentahydrate, adding into a beaker, adding 800mL of deionized water, stirring until the copper sulfate pentahydrate is completely dissolved, draining the weighed sulfuric acid by using a glass rod, injecting into a copper sulfate solution, after the temperature of the solution is reduced to room temperature, respectively adding 20g of boric acid, 0.1g of sodium chloride, 0.15g of polyethylene glycol, 0.33g of sodium polydithio dipropyl sulfonate and 0.0252g of 3-mercaptopropionic acid, stirring uniformly, and preparing into an electroformed copper solution by using deionized water to fix the volume to 1L for later use.
1. Effect of mercapto compound in electrocasting copper solution:
the prepared solution of the electroformed copper is taken out by 100mL, and a CV curve is measured by using a three-electrode system at a constant temperature of 25 ℃. Taking 3-mercaptopropionic acid (MPA) as an example, whether it acts as an inhibitor during electroforming to thereby achieve a grain refining effect was measured and compared with an electroforming copper solution without a mercapto compound, as shown in FIG. 1. As can be seen from FIG. 1, the significantly negative shift of the oxidation peak of the CV curve measured in the electrocasting solution containing 3-mercaptopropionic acid indicates that 3-mercaptopropionic acid acts as an inhibitor during the electrocasting process, and this inhibitor prevents the rapid growth of grains, prevents the formation of a coarse grain structure, and restricts the growth of grains, thereby refining the grains of the copper cast layer.
2. And (3) observing the appearance of the electroformed copper layer:
the electroforming copper solution prepared in the embodiment 1 of the present invention and the electroforming copper solution without the mercapto compound are respectively adopted to carry out electroforming on the cuboid matrix according to the conventional electroforming copper process, a field emission scanning electron microscope is used for shooting the surface of the copper layer after electroforming, a metallographic microscope is used for shooting a sample after polishing and corrosion, and the shot photos are respectively shown in fig. 2 and fig. 3. As can be seen from fig. 2, under the same electroforming conditions, the surface of the copper layer electroformed by the mercapto compound-free electroforming copper solution (see a (low power) in fig. 2 and b (high power) in fig. 2) is very rough, and the raised columnar copper grains grow in all directions, and the copper cast layer with such morphology is not dense; the copper layer electroformed by the electroforming copper solution containing 3-mercaptopropionic acid (see c (low power) of figure 2 and d (high power) of figure 2) has no convex sharp columnar grains on the surface, only a small amount of cellular grains are present, and the flat copper casting layer is more compact; the copper layer electroformed from the electroforming copper solution containing pentaerythritol (tetramercaptoacetate) (see e (lower power) of fig. 2 and f (higher power) of fig. 2) has raised columnar copper grains on the surface, and the copper grains under this condition grow in a single direction; the copper layer electroformed in the electroforming copper solution containing isooctyl 3-mercaptopropionate (see g (lower power) of fig. 2 and h (higher power) of fig. 2) still has raised columnar copper grains on the surface. The surface of the cast layer obtained by the long-chain mercapto compound and the multi-mercapto compound is rougher than that of the short-chain mono-mercapto compound.
As can be seen from fig. 3, under the same electroforming conditions, the copper layer electroformed in the mercapto compound-free electroformed copper solution (see fig. 3 a (lower magnification) and fig. 3 b (higher magnification)) has larger grains, an average grain size of about 25 μm, and more massive grains; the copper layer electroformed by the electroforming copper solution containing 3-mercaptopropionic acid (see c (low power) of figure 3 and d (high power) of figure 3) has small crystal grains, the crystal grains are distributed uniformly, the average crystal grain size is about 8 mu m, and the arrangement among the crystal grains is very tight; the copper layer electroformed in the electroforming copper solution containing pentaerythritol (tetramercaptoacetate) has a distinct columnar crystal structure as shown in e (lower power) of fig. 3 and f (higher power) of fig. 3, and the average crystal grain size is about 20 μm; the copper layer electroformed in the electroforming copper solution containing isooctyl 3-mercaptopropionate, shown in g (lower power) of FIG. 3 and h (higher power) of FIG. 3, also had a distinct columnar texture and coarse grains. The long-chain mercapto and multi-mercapto compounds have a certain effect of grain refinement, but the crystal grains of the cast layer obtained by the long-chain mercapto and multi-mercapto compounds are coarser than those of the short-chain mono-mercapto compounds.
From the above, it is understood from fig. 2 and fig. 3 that under the same electroforming condition, the use of 3-mercaptopropionic acid as an inhibitor realizes the refinement of the electroformed copper crystal grains and further improves the denseness of the electroformed copper layer.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. An electroforming copper solution, which is characterized by comprising the following components in terms of mass concentration: 90-270 g/L of blue vitriol, 30-90 g/L of sulfuric acid, 20-70 g/L of boric acid, 0.1-0.5 g/L of sodium chloride and/or hydrochloric acid, 0.1-0.5 g/L of polyethylene glycol, 0.5-1.2 g/L of sodium polydithio dipropyl sulfonate and 0.0063-0.04 g/L of sulfhydryl compound; the mercapto compound is 3-mercaptopropionic acid.
2. The electroforming copper solution of claim 1, wherein the electroforming copper solution comprises the following components in mass concentration: 150-200 g/L of copper sulfate pentahydrate, 50-70 g/L of sulfuric acid, 40-50 g/L of boric acid, 0.2-0.4 g/L of sodium chloride and/or hydrochloric acid, 0.2-0.4 g/L of polyethylene glycol, 0.8-1 g/L of sodium polydithio dipropyl sulfonate and 0.01-0.03 g/L of sulfhydryl compound.
3. The electroforming copper solution according to claim 1 or 2, wherein the polyethylene glycol has a number average molecular weight of 5000 to 6000.
4. A method of producing the copper electroforming solution according to any of claims 1 to 3 comprising the steps of:
weighing copper sulfate pentahydrate, sulfuric acid, boric acid, sodium chloride and/or hydrochloric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl compound according to the mass concentration of the components;
dissolving copper sulfate pentahydrate in deionized water to obtain a copper sulfate pentahydrate solution;
adding sulfuric acid into the copper sulfate pentahydrate solution, cooling, then respectively adding boric acid, sodium chloride and/or hydrochloric acid, polyethylene glycol, sodium polydithio-dipropyl sulfonate and a sulfhydryl compound, stirring uniformly, and then carrying out constant volume with deionized water to obtain the electroforming copper solution.
5. An electroformed copper solution produced by the production method according to claim 4.
6. Use of the electroforming copper solution according to any one of claims 1 to 3 and 5, in electroforming copper electrodes having fine textures.
7. A copper electrode obtained by electroforming a conductive pattern having a fine texture using the electroforming copper solution according to any one of claims 1 to 3 and 5.
8. The copper electrode according to claim 7, wherein the electroforming temperature is 20 to 30 ℃ and the cathode current density is 1 to 2.5A/dm2。
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