CN114351128B - Copper plating solution additive, copper plating solution, copper plated film and preparation method thereof, negative current collector and lithium battery - Google Patents
Copper plating solution additive, copper plating solution, copper plated film and preparation method thereof, negative current collector and lithium battery Download PDFInfo
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- CN114351128B CN114351128B CN202111510908.3A CN202111510908A CN114351128B CN 114351128 B CN114351128 B CN 114351128B CN 202111510908 A CN202111510908 A CN 202111510908A CN 114351128 B CN114351128 B CN 114351128B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- 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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Abstract
The invention relates to the technical field of film metallization, in particular to a copper plating solution additive, a copper plating solution, a copper plated film, a preparation method of the copper plated film, a negative current collector and a lithium battery. The copper plating solution additive comprises the following components in percentage by mass (0.8-1.2): (1.6-2.4): (2.4-3.6) pyrrolidine dithiocarbamic acid sodium salt, benzyl triphenyl phosphonium bromide and 2- (hydroxymethyl) thiophene. The copper plating solution additive can completely improve the defect that a copper plated film is easy to have pinpoint perforation on the basis of not influencing the performance of the original chemical copper plating process, ensures the compactness and continuity of the copper plated film and can play a role in reducing the square resistance of the film surface.
Description
Technical Field
The invention relates to the technical field of film metallization, in particular to a copper plating solution additive, a copper plating solution, a copper plated film, a preparation method of the copper plated film, a negative current collector and a lithium battery.
Background
Magnetic control or evaporation plating and electroplating are common processing technologies for double-sided copper plating on the surface of a plastic film, however, the thickness of copper on the film surface prepared by the magnetic control or evaporation plating and electroplating technologies is insufficient, so that the sheet resistance of the film surface is about 2000m omega, and the sheet resistance is too high. Therefore, in order to reduce the sheet resistance (to 500m Ω), an acid copper electroplating process is generally employed. The process can obtain a copper-plated layer with compact crystals, the sheet resistance of the film surface can meet the requirements, but the uniformity of the thickness of the plated layer is extremely poor, the edge of the film is easy to burn, faults such as edge film layer hole burning, perforation, film breaking and the like occur, and the final qualified rate and efficiency of the plated film are also lower. Meanwhile, if the sheet resistance of the film surface is greatly reduced in the magnetic control or evaporation coating process, the risks of perforation and hole burning of the film surface can be greatly increased. In the subsequent acid copper electroplating process, the electroplating current is small, so that the thickness of the film layer is greatly reduced, and the sheet resistance of the film surface cannot be reduced to the range required by a finished product; when the electroplating current is overlarge, the film burning of the plastic film surface is possible to occur at any time. Therefore, the operation is inconvenient, and the qualification rate of the finished product processed at one time cannot be controlled. In addition, the plastic film tends to be metalized and fragile after being subjected to the acid copper electroplating process, acid copper electroplating can not be repeated for multiple times, the film breaking problem can occur after one (at most two) electroplating, the yield is greatly reduced, and the waste and the cost are high.
Disclosure of Invention
Based on the method, the invention provides a copper plating solution additive, a copper plating solution, a copper plated film, a preparation method of the copper plated film, a negative current collector and a lithium battery, wherein the copper plating solution additive, the copper plating solution and the copper plated film can improve interface binding force and crystallization compactness and can reduce membrane surface sheet resistance.
In one aspect of the invention, the copper plating solution additive comprises the following components in percentage by mass (0.8-1.2): (1.6-2.4): (2.4-3.6) pyrrolidine dithiocarbamic acid sodium salt, benzyl triphenyl phosphonium bromide and 2- (hydroxymethyl) thiophene.
Optionally, as for the copper plating solution additive, the mass ratio of the sodium pyrrolidinodithiocarbamate, the benzyltriphenylphosphonium bromide and the 2- (hydroxymethyl) thiophene is 1.
In one aspect of the invention, a copper plating solution comprising Cu is also provided 2+ Complexing agent, reducing agent, stabilizing agent and the copper plating solution additive.
Optionally, in the copper plating solution described above, the complexing agent is at least one of potassium sodium tartrate, EDTA and α, α -bipyridine; and/or
The reducing agent is at least one of potassium ferrocyanide and formaldehyde; and/or
The stabilizer is sodium hydroxide and/or sodium carbonate.
Optionally, the copper plating solution as described above includes the following components in concentration:
0.08 to 0.12g/L of sodium pyrrolidine dithiocarbamate, 0.16 to 0.24g/L of benzyltriphenylphosphonium bromide, 0.24 to 0.36g/L of 2- (hydroxymethyl) thiophene, 10 to 15g/L of copper sulfate, 18 to 24g/L, EDTA8 to 12g/L of sodium potassium tartrate, 0.008 to 0.012g/L of alpha, alpha-bipyridine, 0.02 to 0.03g/L of potassium ferrocyanide and 2.5 to 3.5g/L of formaldehyde.
Optionally, the copper plating solution as described above includes the following components in concentration:
0.08-0.12 g/L of pyrrolidine sodium dithiocarbamate, 0.16-0.24 g/L of benzyltriphenylphosphonium bromide and 0.24-0.36 g/L of 2- (hydroxymethyl) thiophene L, cu 2+ 10 g/L-15 g/L, 18 g/L-24 g/L of sodium potassium tartrate L, EDTA g/L-12 g/L, 0.008 g/L-0.012 g/L of alpha, alpha-bipyridine, 0.02 g/L-0.03 g/L of potassium ferrocyanide, 2.5 g/L-3.5 g/L of formaldehyde, 6 g/L-7 g/L of sodium hydroxide and 3 g/L-6 g/L of sodium carbonate.
The invention also provides a preparation method of the copper-plated film, which comprises the following steps:
providing a plastic film plated with a copper layer; and
and plating the copper plating solution on the surface of the copper layer by adopting an electroless copper plating process.
On one hand, the invention also provides the copper-plated film prepared by the preparation method of the copper-plated film.
In another aspect of the present invention, there is further provided a negative electrode current collector comprising the above copper-plated film.
In another aspect of the present invention, a lithium battery is provided, which includes the above-mentioned negative current collector.
The copper plating solution additive provided by the invention can completely improve the defect that a copper plated film is easy to have pinpoint perforation on the basis of not influencing the original chemical copper plating process performance, ensures the compactness and continuity of the copper plated film and can play a role in reducing the sheet resistance of the film surface. The copper plating additive has the characteristics of environmental protection, no toxicity, low cost and the like, can realize good copper plating effect by adding a small amount of copper plating solution additive with concentration into the copper plating solution, and is suitable for industrial production. In addition, the chemical copper plating process can be used for realizing subsequent repeated copper plating on the plastic film and reducing the film surface sheet resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a metallographic microscope photograph of a copper-plated film obtained in example 1;
FIG. 2 is a metallographic microscope photograph of a copper-plated film obtained in example 2;
FIG. 3 is a metallographic microscope photograph of a copper-plated film obtained in example 3;
FIG. 4 is a metallographic microscope photograph of a copper-plated film obtained in example 4;
FIG. 5 is a metallographic microscope photograph of a copper-plated film obtained in example 5;
FIG. 6 is a metallographic microscope photograph of a copper-plated film obtained in example 6;
FIG. 7 is a metallographic microscope photograph of a copper-plated film obtained in example 7;
FIG. 8 is a metallographic microscope photograph of a copper-plated film obtained in comparative example 1;
FIG. 9 is a metallographic microscope photograph of a copper-plated film obtained in comparative example 2;
FIG. 10 is a metallographic microscopic view of a copper-plated film obtained in comparative example 3;
FIG. 11 is a metallographic microscope photograph of a copper-plated film obtained in comparative example 4;
FIG. 12 is a metallographic microscopic picture of a copper-plated film obtained in comparative example 5;
FIG. 13 is a metallographic microscope photograph of a copper-plated film obtained in comparative example 6;
FIG. 14 is a metallographic microscope photograph of a copper-plated film obtained in comparative example 7.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect of the invention, the copper plating solution additive comprises the following components in percentage by mass (0.8-1.2): (1.6-2.4): (2.4-3.6) pyrrolidine dithiocarbamic acid sodium salt, benzyl triphenyl phosphonium bromide and 2- (hydroxymethyl) thiophene.
The benzyltriphenylphosphonium bromide in the copper plating solution additive can obviously improve the activity of the copper plating solution, greatly improve the copper deposition speed and shorten the plating time; the sodium pyrrolidine dithiocarbamate can effectively increase the polarization of copper ions in the copper plating solution, and the purpose of refining grains is achieved, so that a crystallized and compact copper plating layer can be obtained; the 2- (hydroxymethyl) thiophene can greatly improve the binding force between the copper plating layer and the plastic film. By regulating the three components in a proper mass ratio range, a copper plating layer with strong binding force and fine and continuous crystallization can be obtained on the plastic film.
In some embodiments, the mass ratio of sodium pyrrolidine dithiocarbamate, benzyltriphenylphosphonium bromide and 2- (hydroxymethyl) thiophene may also be (0.8 to 1.2): (1.6-2.4): (2.4 to 3.6) any ratio in this range may be, for example, 0.8. Preferably 1.
In one aspect of the invention, a copper plating solution comprising Cu is also provided 2+ Complexing agent, reducing agent, stabilizing agent and the copper plating solution additive.
In some embodiments, the complexing agent may be any complexing agent known in the art, including but not limited to sodium potassium tartrate, EDTA, α -bipyridine, and the like. The reducing agent may be a reducing agent commonly used in the art, and may be at least one of potassium ferrocyanide and formaldehyde, for example. The stabilizer may be sodium hydroxide and/or sodium carbonate. Wherein Cu 2+ The source of (b) may be copper salts such as copper sulfate, copper nitrate, copper chloride, etc., preferably copper sulfate.
In some embodiments, the copper plating solution comprises the following concentrations of the components:
0.08 to 0.12g/L of sodium pyrrolidine dithiocarbamate, 0.16 to 0.24g/L of benzyltriphenylphosphonium bromide, 0.24 to 0.36g/L of 2- (hydroxymethyl) thiophene, 10 to 15g/L of copper sulfate, 18 to 24g/L, EDTA8 to 12g/L of sodium potassium tartrate, 0.008 to 0.012g/L of alpha, alpha-bipyridine, 0.02 to 0.03g/L of potassium ferrocyanide and 2.5 to 3.5g/L of formaldehyde.
In some embodiments, the copper plating solution comprises the following concentrations of the components:
0.08-0.12 g/L of pyrrolidine sodium dithiocarbamate, 0.16-0.24 g/L of benzyltriphenylphosphonium bromide and 0.24-0.36 g/L of 2- (hydroxymethyl) thiophene L, cu 2+ 10-15 g/L of potassium sodium tartrate, 18-24 g/L, EDTA-12 g/L of potassium sodium tartrate, 0.008-0.012 g/L of alpha, alpha-bipyridine, 0.02-0.03 g/L of potassium ferrocyanide, 2.5-3.5 g/L of formaldehyde, 6-7 g/L of sodium hydroxide and 3-6 g/L of sodium carbonate.
The invention also provides a preparation method of the copper-plated film, which comprises the following steps:
providing a plastic film plated with a copper layer; and
and plating the copper plating solution on the surface of the copper layer of the plastic film by adopting an electroless copper plating process.
In some embodiments, both sides of the plastic film are plated with a copper layer, and the copper plating solution is plated on the surface of the copper layer.
In some embodiments, the method for plating the copper layer on the surface of the plastic film in advance is not limited, and for example, magnetron sputtering may be used.
In some embodiments, the electroless copper plating is carried out at a temperature of 38 ℃ to 50 ℃ for 1.5min to 20min, and the movement speed of the plastic film relative to the copper plating solution is 1m/min to 15m/min.
In some embodiments, the plastic film may be any plastic film known in the art, including but not limited to PI film, PP film, PET film, and the like.
In some embodiments, the thicknesses of the plastic film and the copper plating layer are not limited to meet practical requirements. The thickness of the copper-plated thin film is preferably 3.2 to 12 μm, and may be 5, 8, 9.5, 10, 11.2 μm or the like.
In one aspect of the invention, the copper-plated film prepared by the preparation method of the copper-plated film is also provided.
In another aspect of the invention, there is further provided a negative electrode current collector comprising the copper-plated film described above.
In another aspect of the present invention, a lithium battery is provided, which includes the above-mentioned negative current collector.
The copper plating solution additive, copper plating solution, copper plated film, and methods for producing the same, negative electrode current collector, and lithium battery according to the present invention will be described in further detail below with reference to specific examples and comparative examples.
Example 1
10g of sodium pyrrolidine dithiocarbamate is weighed and dissolved in 200mL of deionized water to prepare a sodium pyrrolidine dithiocarbamate solution. 30g of 2- (hydroxymethyl) thiophene was weighed and dissolved in 500mL of deionized water to prepare a 2- (hydroxymethyl) thiophene solution. Slowly adding 20g of benzyltriphenylphosphonium bromide into a pyrrolidine sodium dithiocarbamate solution, adding a 2- (hydroxymethyl) thiophene solution after the benzyltriphenylphosphonium bromide is completely dissolved, and fixing the volume to 1L by using deionized water to prepare a copper plating solution additive;
adding 10mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 12.5g/L of copper sulfate, 20g/L, EDTA g/L of sodium potassium tartrate, 0.01g/L of alpha, alpha' -bipyridine, 0.025g/L of potassium ferrocyanide and 3g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 7min at 40 ℃ and a relative movement speed of 7m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The following tests were performed on the copper-plated films:
1) Measuring the sheet resistance of the membrane surface by using an HPS2524/2526 precise square resistance tester to be 402m omega;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in FIG. 1, when the film surface state was observed by a metallographic microscope having an eyepiece of 50 times, the film surface crystal grains were finely continuous and no hole was formed.
Example 2
This example is prepared substantially identically to example 1, except that: the content of each substance and the coating process parameters are different. The method comprises the following specific steps:
8g of pyrrolidine sodium dithiocarbamate is weighed and dissolved in 200mL of deionized water to prepare the pyrrolidine sodium dithiocarbamate solution. 24g of 2- (hydroxymethyl) thiophene was weighed and dissolved in 500mL of deionized water to prepare a 2- (hydroxymethyl) thiophene solution. Slowly adding 16g of benzyltriphenylphosphonium bromide into a pyrrolidine sodium dithiocarbamate solution, adding a 2- (hydroxymethyl) thiophene solution after the benzyltriphenylphosphonium bromide is completely dissolved, and fixing the volume to 1L by using deionized water to prepare a copper plating solution additive;
adding 10mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution comprise 10g/L of copper sulfate, 18g/L, EDTA g/L of potassium sodium tartrate, 0.008g/L of alpha, alpha' -bipyridine, 0.02g/L of potassium ferrocyanide and 2.5g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 8min at the temperature of 38 ℃ and the relative movement speed of 3m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is measured to be 410m omega by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in FIG. 2, the film surface state was observed by using a metallographic microscope having an eyepiece of 50 times, and it was found that the crystal grains were fine and continuous and no pinhole was formed.
Example 3
This example is prepared substantially identically to example 1, except that: the content of each substance and the coating process parameters are different. The method comprises the following specific steps:
12g of sodium pyrrolidine dithiocarbamate is weighed and dissolved in 200mL of deionized water to prepare a sodium pyrrolidine dithiocarbamate solution. 36g of 2- (hydroxymethyl) thiophene is weighed and dissolved in 500mL of deionized water to prepare 2- (hydroxymethyl) thiophene solution. Slowly adding 24g of benzyltriphenylphosphonium bromide into a pyrrolidine sodium dithiocarbamate solution, adding a 2- (hydroxymethyl) thiophene solution after the benzyltriphenylphosphonium bromide is completely dissolved, and fixing the volume to 1L by using deionized water to prepare a copper plating solution additive;
adding 10mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 15g/L of copper sulfate, 24g/L, EDTA g/L of sodium potassium tartrate, 0.012g/L of alpha, alpha' -bipyridine, 0.03g/L of potassium ferrocyanide and 3.5g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 8min at the temperature of 39 ℃ and the relative movement speed of 4m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The copper-plated films were tested as follows:
1) Measuring the sheet resistance of the membrane surface by using an HPS2524/2526 precise square resistance tester to be 352m omega;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in FIG. 3, when the film surface state was observed by a metallographic microscope having an eyepiece of 50 times, the film surface crystal grains were finely continuous and no hole was formed.
Example 4
This example is prepared substantially identically to example 1, except that: the content of each substance and the coating process parameters are different. The method comprises the following specific steps:
9g of sodium pyrrolidine dithiocarbamate is weighed and dissolved in 200mL of deionized water to prepare a sodium pyrrolidine dithiocarbamate solution. 27g of 2- (hydroxymethyl) thiophene was weighed and dissolved in 500mL of deionized water to prepare a 2- (hydroxymethyl) thiophene solution. Slowly adding 18g of benzyltriphenylphosphonium bromide into a pyrrolidine sodium dithiocarbamate solution, adding a 2- (hydroxymethyl) thiophene solution after the benzyltriphenylphosphonium bromide is completely dissolved, and fixing the volume to 1L by using deionized water to prepare a copper plating solution additive;
adding 10mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 14g/L of copper sulfate, 22g/L, EDTA g/L of sodium potassium tartrate, 0.012g/L of alpha, alpha' -bipyridine, 0.028g/L of potassium ferrocyanide and 3.0g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive for 7min at 40 ℃ and a relative movement speed of 6m/min, cleaning by using flowing deionized water, and blow-drying to obtain a copper plated film with a thickness of about 5.5 mu m. The copper-plated films were tested as follows:
1) The sheet resistance of the membrane surface is measured to be 410m omega by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 4, the film surface state was observed by a metallographic microscope having an eyepiece of 50 times, and it was found that the film surface crystal grains were fine and continuous and no pinhole was formed.
Example 5
This example is prepared substantially identically to example 1, except that: the content of each substance and the coating process parameters are different. The method comprises the following specific steps:
11g of sodium pyrrolidine dithiocarbamate is weighed and dissolved in 200mL of deionized water to prepare a sodium pyrrolidine dithiocarbamate solution. 33g of 2- (hydroxymethyl) thiophene was weighed and dissolved in 500mL of deionized water to prepare a 2- (hydroxymethyl) thiophene solution. Slowly adding 22g of benzyltriphenylphosphonium bromide into a pyrrolidine sodium dithiocarbamate solution, adding a 2- (hydroxymethyl) thiophene solution after the benzyltriphenylphosphonium bromide is completely dissolved, and fixing the volume to 1L by using deionized water to prepare a copper plating solution additive;
adding 10mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 14g/L of copper sulfate, 20g/L, EDTA g/L of sodium potassium tartrate, 0.012g/L of alpha, alpha' -bipyridine, 0.025g/L of potassium ferrocyanide and 3.0g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 7min at 40 ℃ and a relative movement speed of 6m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 407m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in FIG. 5, when the film surface state was observed by a metallographic microscope having an eyepiece of 50 times, the film surface crystal grains were finely continuous and no hole was formed.
Example 6
This example is substantially the same as example 1 except that: the copper plating solution containing the copper plating solution additive has different copper plating solution additive contents and different coating technological parameters. The method comprises the following specific steps:
adding 8mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 13g/L of copper sulfate, 24g/L, EDTA g/L of potassium sodium tartrate, 0.008g/L of alpha, alpha' -bipyridine, 0.025g/L of potassium ferrocyanide and 3.0g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 6min at 42 ℃ and a relative movement speed of 10m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The copper-plated films were tested as follows:
1) The sheet resistance of the membrane surface is measured to be 401m omega by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 6, when the film surface state was observed by a metallographic microscope having an eyepiece of 50 times, the film surface crystal grains were finely continuous, and no hole was formed.
Example 7
This example is prepared substantially identically to example 1, except that: the copper plating solution containing the copper plating solution additive has different copper plating solution additive contents and different coating technological parameters. The method comprises the following specific steps:
adding 12mL of the copper plating solution additive into 1L of copper plating solution, wherein the rest components in the copper plating solution are 13g/L of copper sulfate, 24g/L, EDTA g/L of sodium potassium tartrate, 0.008g/L of alpha, alpha' -bipyridine, 0.025g/L of potassium ferrocyanide and 3.0g/L of formaldehyde, and preparing the copper plating solution containing the copper plating solution additive;
providing a PP film with a thickness of about 4.5 mu m plated with a copper layer, chemically plating the copper plating solution containing the copper plating solution additive on the PP film for 6min at 42 ℃ and a relative movement speed of 10m/min, cleaning by using flowing deionized water, and blow-drying to obtain the copper plated film with the thickness of about 5.5 mu m. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is measured to be 403 mO by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, and the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 7, the film surface state was observed by using a metallographic microscope having an eyepiece of 50 times, and it was found that the film surface crystal grains were fine and continuous and no pinhole was formed.
Example 8
A copper-plated PP film having a thickness of about 4.5 μm, a length of about 15cm and a width of about 10cm was provided, and the sheet resistance of the film surface was 150 m.OMEGA.and the surface of the film had fine micropores as measured by using a precision square resistance tester HPS 2524/2526.
The formula of the copper plating solution comprises: 0.1g/L of sodium pyrrolidine dithiocarbamate, 0.2g/L of benzyltriphenylphosphonium bromide, 0.3g/L of 2- (hydroxymethyl) thiophene, 12.5g/L of copper sulfate, 20g/L, EDTA, 0.01g/L of alpha, alpha' -bipyridine, 0.025g/L of potassium ferrocyanide, 3g/L of formaldehyde, 6g/L of sodium hydroxide and 3g/L of sodium carbonate.
And (3) soaking the copper-plated PP film into the copper plating solution at 42 ℃, taking out after 10min, washing by using flowing deionized water and drying by blowing to obtain the copper-plated film with the thickness of about 5.5 mu m. Measuring the average film surface square resistance to be 10m omega by using an HPS2524/2526 precise square resistance tester; the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape, and no hole exists in the film surface.
Example 9
A copper-coated PP film having a thickness of about 4.5 μm, a length of about 15cm and a width of about 10cm was provided, and the sheet resistance of the film surface was 161 m.OMEGA.and the surface had fine micropores as measured by using a precision block resistance tester HPS 2524/2526.
The formula of the copper plating solution is as follows: 0.1g/L of sodium pyrrolidine dithiocarbamate, 0.2g/L of benzyltriphenylphosphonium bromide, 0.3g/L of 2- (hydroxymethyl) thiophene, 12.5g/L of copper sulfate, 20g/L, EDTA, 0.01g/L of alpha, alpha' -bipyridyl, 0.025g/L of potassium ferrocyanide, 3g/L of formaldehyde, 6g/L of sodium hydroxide and 3g/L of sodium carbonate.
And (3) soaking the copper-plated PP film into the copper plating solution at 42 ℃, taking out after 20min, washing by using flowing deionized water and drying by blowing to obtain the copper-plated film with the thickness of about 5.5 mu m. The average film surface sheet resistance measured by an HPS2524/2526 precise square resistance tester was 5.6m Ω; the 3M adhesive tape is used for adhering the copper plating layer of the copper-plated film, the film falling phenomenon does not occur in the process of tearing off the 3M adhesive tape, and no hole exists in the film surface.
The results of the tests of examples 1 to 9 show that the additive for copper plating solutions can prevent the formation of pores on the surface of the film, and can reduce the sheet resistance of the film surface of the copper plated film while maintaining fine and continuous crystallization. The chemical copper plating process can be directly used for plating copper on the film, and can also be used as an auxiliary process of the original film copper plating process, so that holes on the surface of the film can be made up, and the sheet resistance of the film surface can be reduced. The results of the related tests of examples 8 and 9 show that the electroless copper plating process can significantly reduce the sheet resistance of the original film, and has no pores on the surface and excellent binding force.
Comparative example 1
This comparative example was prepared in the same manner as example 1, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 498m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of a copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 8, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
Comparative example 2
This comparative example was prepared in the same manner as example 2 except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 489m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of a copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 9, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
Comparative example 3
This comparative example was prepared in the same manner as example 3, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 468m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of the copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 10, when the film surface state was observed using a metallographic microscope having an eyepiece of 50 times, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
Comparative example 4
This comparative example was prepared in the same manner as example 4, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 453m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of the copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 11, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was rough in crystal grains and discontinuous in film surface, and a large number of perforations were observed.
Comparative example 5
This comparative example was prepared in the same manner as example 5, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The square resistance of the membrane surface is measured to be 461 mO by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of a copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 12, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
Comparative example 6
This comparative example was prepared in the same manner as example 6, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 441 mO measured by an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of a copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 13, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
Comparative example 7
This comparative example was prepared in the same manner as example 7, except that: the copper plating solution is not added with copper plating solution additives. The following tests were performed on the copper-plated films:
1) The sheet resistance of the membrane surface is 438m omega measured by using an HPS2524/2526 precise square resistance tester;
2) And (3) testing the binding force: a 3M adhesive tape is used for adhering a copper plating layer of the copper-plated film, and a small amount of film falling phenomenon occurs in the process of tearing off the 3M adhesive tape;
3) As shown in fig. 14, when the film surface state was observed by a metallographic microscope having a 50-fold eyepiece, the film surface was found to have coarse crystal grains and discontinuous film surface, and a large number of perforations were formed.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The copper plating solution additive is characterized by comprising sodium pyrrolidine dithiocarbamate, benzyltriphenylphosphonium bromide and 2- (hydroxymethyl) thiophene; in 1L of the copper plating solution additive, the addition amount of the sodium pyrrolidine dithiocarbamate is 8g, 9g, 10g, 11g or 12g, and the mass ratio of the sodium pyrrolidine dithiocarbamate to the benzyltriphenylphosphonium bromide to the 2- (hydroxymethyl) thiophene is 1.
2. A copper plating solution is characterized by comprising Cu 2+ Complexing agent, reducing agent, stabilizing agent and copper plating solution additive as defined in claim 1.
3. The copper plating solution according to claim 2, wherein the complexing agent is at least one of potassium sodium tartrate, EDTA, and α, α -bipyridine.
4. The copper plating solution according to claim 2, wherein the reducing agent is at least one of potassium ferrocyanide and formaldehyde; and/or
The stabilizer is sodium hydroxide and/or sodium carbonate.
5. The copper plating solution according to any one of claims 2 to 4, characterized by comprising the following components in concentrations:
0.08-0.12 g/L of pyrrolidine sodium dithiocarbamate, 0.16-0.24 g/L of benzyltriphenylphosphonium bromide and 0.24-0.36 g/L of 2- (hydroxymethyl) thiophene L, cu 2+ 10 g/L-15 g/L, 18 g/L-24 g/L, EDTA g/L-12 g/L of potassium sodium tartrate, 0.008 g/L-0.012 g/L of alpha, alpha-bipyridine, and ferrous iron0.02-0.03 g/L of potassium cyanide and 2.5-3.5 g/L of formaldehyde.
6. The copper plating solution according to any one of claims 2 to 4, characterized by comprising the following components in concentrations:
0.08-0.12 g/L of sodium pyrrolidine dithiocarbamate, 0.16-0.24 g/L of benzyltriphenyl phosphonium bromide and 0.24-0.36 g/L of 2- (hydroxymethyl) thiophene L, cu 2+ 10 g/L-15 g/L, 18 g/L-24 g/L of sodium potassium tartrate L, EDTA g/L-12 g/L, 0.008 g/L-0.012 g/L of alpha, alpha-bipyridine, 0.02 g/L-0.03 g/L of potassium ferrocyanide, 2.5 g/L-3.5 g/L of formaldehyde, 6 g/L-7 g/L of sodium hydroxide and 3 g/L-6 g/L of sodium carbonate.
7. The preparation method of the copper-plated film is characterized by comprising the following steps:
providing a plastic film plated with a copper layer; and
plating the copper plating solution according to any one of claims 2 to 6 on the surface of the copper layer by an electroless copper plating process.
8. A copper-plated film obtained by the method for producing a copper-plated film according to claim 7.
9. A negative electrode current collector comprising the copper-coated film according to claim 8.
10. A lithium battery comprising the negative electrode current collector of claim 9.
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| CN202111510908.3A CN114351128B (en) | 2021-12-10 | 2021-12-10 | Copper plating solution additive, copper plating solution, copper plated film and preparation method thereof, negative current collector and lithium battery |
| PCT/CN2022/094617 WO2023103293A1 (en) | 2021-12-10 | 2022-05-24 | Additive for copper plating solution, copper plating solution, copper-plated thin film and preparation method therefor, negative electrode current collector, and lithium battery |
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