CN108075098B - Electrolytic copper foil, electrode for secondary battery, and method for producing electrolytic copper foil - Google Patents
Electrolytic copper foil, electrode for secondary battery, and method for producing electrolytic copper foil Download PDFInfo
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
Disclosed are an electrolytic copper foil with minimized curling capable of preventing folding and/or wrinkling during a roll-to-roll (RTR) process, a method of manufacturing the same, an electrode and a secondary battery capable of ensuring high productivity by using the electrolytic copper foil. The electrolytic copper foil has a first surface and a second surface opposite to the first surface. Surface roughness R between first surface and second surfaceaIs less than or equal to 0.3 [ mu ] m, the peak number roughness R between the first surface and the second surfacepcIs less than or equal to 96, the difference in texture coefficient TC (220) of the face (220) between the first surface and the second surface is less than or equal to 0.39, and the difference in the amount of chromium (Cr) coating between the first surface and the second surface is less than or equal to 2.5mg/m2。
Description
This application claims priority and benefit from korean patent application No. 2016-0151713, filed on 15/11/2016, the disclosure of which is hereby incorporated by reference in its entirety.
Technical Field
The present invention relates to an electrodeposited copper foil with minimized curling, an electrode including the same, a secondary battery including the same, and a method of manufacturing the same.
Background
The electrolytic copper foil is used to manufacture various products such as a negative electrode of a secondary battery and a Flexible Printed Circuit Board (FPCB).
In general, an electrolytic copper foil is manufactured by a roll-to-roll (RTR) process, and is also used to manufacture a negative electrode of a secondary battery, an FPCB, and the like by an RTR process.
Since the RTR process allows continuous production, the RTR process is a process known to be suitable for mass production of products. However, in practice, due to the folding and/or wrinkling of the electrolytic copper foil that often occurs in the RTR process, the RTR process equipment must be interrupted and then restarted after these problems are solved. Repeated interruptions and restarts severely reduce productivity.
That is, the folding and/or wrinkling of the electrolytic copper foil occurring during the RTR process makes the product not continuously produced, thus undermining the inherent advantages of the RTR process, resulting in problems of reduced product productivity and reduced yield.
When the electrolytic copper foil has severe curling, the risk of the electrolytic copper foil folding and/or wrinkling during the RTR process will increase. However, factors affecting the curling of the electrolytic copper foil have not been clarified yet.
Disclosure of Invention
Accordingly, the present invention is directed to an electrolytic copper foil, an electrode including the same, a secondary battery including the same, and a method of manufacturing the same that obviate problems due to limitations and disadvantages of the related art.
The present invention provides an electrolytic copper foil having minimized curling while being capable of preventing folding and/or wrinkling in a roll-to-roll (RTR) process.
The present invention also provides an electrode which can ensure high productivity by being produced with an electrolytic copper foil having minimized curling capable of preventing folding and/or wrinkling during an RTR process.
The present invention also provides a secondary battery which can ensure high productivity by being produced with the electrolytic copper foil having minimized curling capable of preventing folding and/or wrinkling during an RTR process.
The present invention also provides a method of manufacturing an electrolytic copper foil having minimized curling while being prevented from being folded and/or wrinkled in a roll-to-roll (RTR) process.
Additional features and advantages of the invention will be set forth in the description which follows, or will be readily apparent to those skilled in the art from the description.
According to an aspect of the present invention, there is provided an electrolytic copper foil having a first surface and a second surface opposite to the first surface, the electrolytic copper foil comprising: a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface; a first protective layer on the matte side; and a second protective layer on the glossy surface, wherein a surface roughness R between the first surface and the second surfaceaIs less than or equal to 0.3 [ mu ] m, the peak number roughness R between the first surface and the second surfacepcA difference in texture coefficient TC (220) of a plane (220) between the first surface and the second surface is less than or equal to 96, a difference in texture coefficient TC (220) of a plane (220) between the first surface and the second surface is less than or equal to 0.39, the first protective layer and the second protective layer contain chromium (Cr), and a difference in chromium (Cr) coating amount between the first surface and the second surface is less than or equal to 2.5mg/m2。
A surface roughness R of each of the first and second surfacesaMay range from 0.1 μm to 0.55 μm.
Peak number roughness R of each of the first and second surfacespcMay range from 3 to 106.
A face (220) of each of the first and second surfaces may have a texture coefficient TC (220) in a range of 0.4 to 1.32.
The electrolytic copper foil may have a yield strength of 21kgf/mm at room temperature of 25 + -15 deg.C2To 55kgf/mm2。
The electrolytic copper foil may have an elongation of 3% or more at room temperature of 25 + -15 deg.C.
According to another aspect of the present invention, there is provided a battery electrode comprising: an electrolytic copper foil having a first surface and a second surface opposite to the first surface; and a first active material layer on the first surface, wherein the electrolytic copper foil includes: a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface; a first protective layer on the matte side; and a second protective layer having a surface roughness R between the first surface and the second surface on the glossy surfaceaIs less than or equal to 0.3 [ mu ] m, the peak number roughness R between the first surface and the second surfacepcA difference in texture coefficient TC (220) of a plane (220) between the first surface and the second surface is less than or equal to 96, a difference in texture coefficient TC (220) of a plane (220) between the first surface and the second surface is less than or equal to 0.39, the first protective layer and the second protective layer contain chromium (Cr), and a difference in chromium (Cr) coating amount between the first surface and the second surface is less than or equal to 2.5mg/m2。
A surface roughness R of each of the first and second surfacesaMay be in a range of 0.1 μm to 0.55 μm, a peak number roughness R of each of the first surface and the second surfacepcExample (A) ofThe circumference may be 3 to 106, and the texture coefficient TC (220) of the face (220) of each of the first and second surfaces may range from 0.4 to 1.32.
The electrolytic copper foil may have a yield strength in the range of 21kgf/mm at room temperature of 25 + -15 deg.C2To 55kgf/mm2And the electrolytic copper foil may have an elongation of 3% or more.
The battery electrode may further include: a second active material layer on the second surface, wherein the first active material layer and the second active material layer may include carbon; metals such as silicon (Si), germanium (Ge), tin (Sn), lithium (Li), zinc (Zn), magnesium (Mg), cadmium (Cd), cerium (Ce), nickel (Ni), or iron (Fe); an alloy comprising said metal; an oxide of the metal; and one or more active materials selected from the group consisting of a composite of the metal and carbon.
According to still another aspect of the present invention, there is provided a secondary battery including: a positive electrode (cathode); a negative electrode (anode) formed as a battery electrode; an electrolyte configured to provide an environment in which lithium ions are made movable between the positive electrode and the negative electrode; and a separator configured to electrically insulate the positive electrode and the negative electrode.
According to still another aspect of the present invention, there is provided a method of manufacturing an electrolytic copper foil, the method comprising: forming a copper layer; and forming a protective layer on the copper layer, wherein the step of forming the copper layer comprises: preparing an electrolyte solution comprising 70 to 90g/L of copper ions, 80 to 120g/L of sulfuric acid, 10 to 50ppm of bis- (3-sulfopropyl) disulfide (SPS), and 10 to 50ppm of polyethylene glycol (PEG); and flowing an electric current between the electrode plates spaced apart from each other in the electrolyte solution and the rotary electrode drum at 40 to 80A/dm2And while performing the electroplating, maintaining the total carbon amount TC in the electrolyte solution below 0.25g/L or 0.25g/L, and maintaining the silver concentration in the electrolyte solution below 0.2g/L or 0.2 g/L.
The surface of the rotary electrode drum may be polished by using a polishing brush having a particle diameter of #800 to # 3000.
The step of preparing the electrolyte solution may comprise: heat-treating the copper wire at a temperature ranging from 600 ℃ to 900 ℃ for a time ranging from 30 minutes to 60 minutes; pickling the heat-treated copper wire; placing the acid-washed copper wire into sulfuric acid; and adding bis- (3-sulfopropyl) disulfide (SPS) and polyethylene glycol (PEG) to the copper wire-impregnated sulfuric acid.
The step of forming a copper layer may further comprise: when the plating is performed, hydrogen peroxide and air are injected into the electrolyte solution.
The step of forming a copper layer may further comprise: chloride ions capable of precipitating silver (Ag) in the form of AgCl are added to the electrolyte solution to avoid the concentration of silver (Ag) in the electrolyte solution exceeding 0.2 g/L.
The electrolyte solution may further include at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, glycol-based polymers, and thiourea-based compounds.
The step of forming the protective layer may include: the copper layer is immersed in an anti-corrosion solution containing 0.5 to 1.5g/L Cr.
The general description of the invention as set forth above is intended to be illustrative or explanatory of the invention and is not intended to limit the scope of the invention.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent to those skilled in the art by describing in detail exemplary embodiments thereof with reference to the attached drawings, in which:
FIG. 1 is a cross-sectional view of a battery electrode according to an embodiment of the present invention;
FIG. 2 illustrates a surface roughness profile obtained according to ASME B46.1-2009 standard;
FIG. 3 shows an XRD pattern of an electrolytic copper foil;
fig. 4 shows a method of measuring the degree of curling of the electrolytic copper foil.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention. Accordingly, it is intended that the present invention cover all modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
The lithium ion battery includes a positive electrode (cathode), a negative electrode (anode), an electrolyte providing an environment for lithium ions to move between the positive electrode and the negative electrode, and a separator electrically insulating the positive electrode and the negative electrode, thereby preventing unnecessary consumption caused by electrons generated at one electrode from moving to the other electrode inside the battery.
Fig. 1 is a cross-sectional view of a battery electrode according to an embodiment of the present invention.
As shown in fig. 1, a battery electrode 100 according to an embodiment of the present invention includes an electrolytic copper foil 110, a first active material layer 120a, and a second active material layer 120b, the electrolytic copper foil 110 including a first surface S1 and a second surface S2 opposite to the first surface S1, the first active material layer 120a on the first surface S1, and the second active material layer 120b on the second surface S2. Fig. 1 illustrates an example in which the first active material layer 120a and the second active material layer 120b are formed on the first surface S1 and the second surface S2 of the electrolytic copper foil 110, respectively, but the present invention is not limited thereto. The battery electrode 100 of the present invention may include only one of the first and second active material layers 120a and 120b as an active material layer.
Generally, for a lithium ion battery, aluminum foil is used as a positive electrode current collector, which is connected to a positive electrode active material, electrolytic copper foil is used as a negative electrode current collector, which is connected to a negative electrode active material.
According to an embodiment of the present invention, the battery electrode 100 is used as a negative electrode (anode) of a lithium ion battery, the electrolytic copper foil 110 is used as a negative electrode (anode) current collector, and the first active material layer 120a and the second active material layer 120b each contain a negative electrode (anode) active material.
As shown in fig. 1, the electrolytic copper foil 110 includes a copper layer 111, a first protective layer 112a, and a second protective layer 112b, the copper layer 111 including a matte side MS and a glossy side SS, the first protective layer 112a on the matte side MS of the copper layer 111, and the second protective layer 112b on the glossy side SS of the copper layer 111.
The matte side MS is a surface of the copper layer 111 facing the first surface S1 of the electrolytic copper foil 110, and the glossy side SS is a surface of the copper layer 111 facing the second surface S2 of the electrolytic copper foil 110.
The copper layer 111 of the present invention can be formed on a rotating electrode drum (rotating electrode drum) by electroplating. The glossy surface SS refers to a surface that is in contact with the rotating electrode drum during the plating process, and the matte surface MS refers to a surface opposite to the glossy surface SS.
Generally, the glossy surface SS has a lower surface roughness than the matte surface MS. However, the present invention is not limited thereto, and the surface roughness of the glossy surface SS may be greater than or equal to that of the matte surface MS.
The first protective layer 112a and the second protective layer 112b serve to prevent corrosion of the copper layer 111 and improve heat resistance, and may contain chromium (Cr).
As described above, when the electrolytic copper foil has severe curling, the risk that the electrolytic copper foil will be folded and/or wrinkled during the RTR process increases. Therefore, all factors causing the curling of the electrolytic copper foil 110 should be considered to manufacture the electrolytic copper foil 110.
According to the present invention, it was found that: the difference between the first surface S1 and the second surface S2 of the electrolytic copper foil 110 caused by factors such as the surface shape, the surface profile, the surface crystal structure, and the amount of chromium (Cr) coating causes curling of the electrolytic copper foil 110. That is, the difference between the first surface S1 and the second surface S2 caused by these factors causes a stress difference between the first surface S1 and the second surface S2, which causes curling of the electrolytic copper foil 110. Therefore, in order to minimize the curling of the electrolytic copper foil 110, it is necessary to minimize the difference between the first surface S1 and the second surface S2 caused by the main factor.
The shape and profile of the surface, which is closely related to the grain size, may be characterized by a surface roughness RaAnd peak number roughness RpcAnd the surface crystal structure can be represented by texture coefficient (texture coefficient) TC (220) of the surface (220).
Therefore, according to the present invention, in order to minimize the size of the electrolytic copper foil 110Curl, surface roughness R between first surface S1 and second surface S2aIs less than or equal to 0.3 μm, the peak number roughness R between the first surface S1 and the second surface S2pcIs less than or equal to 96, and the difference in texture coefficient TC (220) of the face (220) between the first surface S1 and the second surface S2 is less than or equal to 0.39.
The surface roughness R can be measured according to JIS (Japanese Industrial Standard) B0601-a(measurement length: 4mm (excluding cut portion)). According to an embodiment of the present invention, the surface roughness R of the first surface S1 and the second surface S2 of the electrolytic copper foil 110aMay range from 0.1 μm to 0.55 μm.
When surface roughness RaLess than 0.1 μm, the active specific surface area (active specific surface area) of the electrolytic copper foil 110 that can contact with the negative active material is small and adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b cannot be secured. On the other hand, when the surface roughness RaAbove 0.55 μm, the first surface S1 and the second surface S2 of the electrolytic copper foil 110 are not flat and may cause a decrease in coating uniformity of the negative active material, and thus may significantly reduce adhesion between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120 b.
Hereinafter, the roughness of the peak number R, which is one of the main factors of the present invention, will be described in detail with reference to FIG. 2pc。
Roughness of peak number RpcCan be measured by measuring the peak number roughness R of any three pointspcAnd calculating an average value of the measured values. Peak number roughness R of these points in the surface roughness profile obtained according to ASME B46.1(2009) StandardpcIs the number of effective peaks P1, P2, P3, and P4 higher than the upper standard line C1 of 0.5 μm per unit sample length of 4 mm. In this case, between adjacent effective peaks among the effective peaks, there is at least one valley lower than the lower standard line C2 of-0.5 μm. When there is no deep valley of the lower standard line C2 below-0.5 μm between adjacent peaks higher than the upper standard line C1, these adjacent peaks may not be "effective peaks" for measuring Peak Density (PD)". Among these peaks, when the number of "effective peaks" is obtained, relatively lower peaks are ignored.
According to an embodiment of the present invention, the peak number roughness R of the first surface S1 and the second surface S2 of the electrolytic copper foil 110pcMay range from 3 to 106.
Roughness at peak number RpcLess than 3, the active specific surface area of the electrolytic copper foil 110 capable of contacting the negative active material is too small to sufficiently secure the adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120 b. On the other hand, the peak number roughness RpcWhen more than 106, the coating uniformity of the negative electrode active material is lowered due to severe surface irregularities, and thus the adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b is remarkably lowered.
The texture coefficient TC (220) of the face (220) is one of the main factors of the present invention, and is measured and calculated as follows.
First, by performing X-ray diffraction (X-ray diffraction) within a diffraction angle of 30 ° to 95 ° [ target: copper K α 1, 2 θ spacing: 0.01 °, 2 θ scan rate: 3 deg./min]An XRD pattern having peaks corresponding to n crystal planes (for example, an XRD pattern in which peaks corresponding to planes (111), (200), (220), and (311) are present) is obtained, and then XRD diffraction intensity i (hkl) of each crystal plane (hkl) is obtained from the pattern. In addition, XRD diffraction intensity I of each of n crystal planes of a standard copper powder specified by Joint Committee for Powder Diffraction Standards (JCPDS) was obtained0(hkl). Next, by obtaining I (hkl)/I of n crystal planes0(hkl) and then by averaging I (220)/I of face (220)0(220) The texture coefficient TC (220) of the surface (220) is calculated by dividing by the arithmetic mean. That is, the texture coefficient TC (220) of the face (220) will be calculated based on equation 1 below.
[ equation 1]
According to the embodiment of the present invention, the texture coefficient TC (220) of the face (220) of each of the first surface S1 and the second surface S2 of the electrolytic copper foil 110 ranges from 0.4 to 1.32.
As the texture coefficient TC (220) of the face (220) increases, the electrolytic copper foil 110 has a more compact crystal structure. Therefore, the texture coefficient TC (220) of the face (220) of each of the first surface S1 and the second surface S2 is preferably greater than or equal to 0.4.
However, when the texture coefficient TC (220) of the face (220) is greater than 1.32, the crystal structure of the electrolytic copper foil 110 is too close to result in insufficient active sites that can be stably in contact with the negative active material. As a result, sufficient adhesion may not be ensured between the electrolytic copper foil 110 and the negative active material, and the electrolytic copper foil 110 does not expand or contract together with the first active material layer 120a and the second active material layer 120b when the battery is charged and discharged. Therefore, the risk of the first active material layer 120a and the second active material layer 120b being separated from the electrolytic copper foil 110 becomes high.
Further, according to the present invention, in order to minimize curling of the electrolytic copper foil 110, a difference in Cr attachment amount (Cr attachment) between the first surface S1 and the second surface S2 is less than or equal to 2.5mg/m2. The Cr attachment amount can be measured by Atomic Absorption Spectrometry (AAS) analysis.
According to an embodiment of the present invention, the Cr attachment amounts of the first and second surfaces S1 and S2 may range from 1mg/m2To 5mg/m2。
The electrolytic copper foil 110 of the present invention may have a yield strength (yield strength) ranging from 21kgf/mm at room temperature of 25 ℃. + -. 15 ℃. (mm)2To 55kgf/mm2. The yield strength is measured by a Universal Testing Machine (UTM). In this case, the width of the sample was 12.7 mm, the holding distance was 50mm, and the measuring speed was 50 mm/min.
When the yield strength of the electrolytic copper foil 110 is less than 21kgf/mm2There is a risk that the electrolytic copper foil 110 will be folded and/or wrinkled due to the force applied during the process of manufacturing the battery electrode 100 and the battery. On the other hand, when the yield strength of the electrolytic copper foil 110 is more than 55kgf/mm2When it is used, the production process of the secondary battery is reducedThe workability of (1).
The electrolytic copper foil 110 of the present invention has an Elongation (Elongation) of 3% or more at room temperature of 25 ℃. + -. 15 ℃. When the elongation of the electrolytic copper foil 110 is less than 3%, the electrolytic copper foil 110 cannot be extended and the risk of being torn by the force applied during the process of manufacturing the battery electrode 100 and the battery increases.
The thickness of the electrolytic copper foil 110 of the present invention may range from 3 μm to 20 μm.
Independently, the first active material layer 120a and the second active material layer 120b may include, as an anode active material, one or more active materials selected from the group consisting of carbon; metals such as silicon (Si), germanium (Ge), tin (Sn), lithium (Li), zinc (Zn), magnesium (Mg), cadmium (Cd), cerium (Ce), nickel (Ni), or iron (Fe); an alloy comprising a metal; an oxide of the metal; and a composite of the metal and carbon.
In order to increase the charge and discharge capacity of the secondary battery, the first active material layer 120a and the second active material layer 120b may be composed of a mixture including an amount of Si.
Hereinafter, according to an embodiment of the present invention, a method of manufacturing the electrolytic copper foil 110 will be described in detail.
The method of the present invention includes forming a copper layer 111 and forming a first protective layer 112a and a second protective layer 112b on the copper layer 111.
First, an electrolyte solution containing 70 to 90g/L of copper ions, 80 to 120g/L of sulfuric acid, 10 to 50ppm of bis- (3-sulfopropyl) disulfide (SPS), and 10 to 50ppm of polyethylene glycol (PEG) was prepared.
Subsequently, at a temperature of 50 to 60 ℃, flowing an electric current between the electrode plates spaced apart from each other in the electrolyte solution and the rotary electrode drum at 40 to 80A/dm2The electroplating is performed with the current density of (a) to form a copper layer 111 on the rotating electrode drum.
According to the present invention, the electrolyte solution is controlled during the plating process so that the total carbon amount (TC) in the electrolyte solution can be maintained at 0.25g/L or below 0.25 g/L. The total carbon content (TC) may comprise Total Organic Carbon (TOC) and Total Inorganic Carbon (TIC) and may be analyzed by a TC measurement device.
In order to maintain the total carbon amount (TC) of the electrolyte solution at 0.25g/L or less, a high-purity copper wire is heat-treated at a temperature ranging from 600 ℃ to 900 ℃ for 30 minutes to 60 minutes to burn off organic substances, the heat-treated copper wire is acid-washed, the acid-washed copper wire is put into sulfuric acid, thereby preparing an electrolyte solution with little or no impurities, and then bis- (3-sulfopropyl) disulfide (SPS) and polyethylene glycol (PEG) are added to the electrolyte solution.
In order to maintain the total carbon amount (TC) of the electrolyte solution at 0.25g/L or less, the organic substances in the electrolyte solution may be decomposed by ozone treatment, thereby reducing the total carbon amount (TC). Also, the cleanliness of the electrolyte solution can be improved by injecting hydrogen peroxide and air into the electrolyte solution during electroplating.
According to the present invention, the concentration of silver (Ag) in the electrolyte solution is maintained at 0.2g/L or less during electroplating.
In order to prevent the concentration of silver (Ag) in the electrolyte solution from exceeding 0.2g/L due to the inflow of silver into the electrolyte solution during electroplating, a small amount of chloride ions (e.g., 15 to 25ppm) capable of precipitating silver (Ag) in the form of AgCl may be added to the electrolyte solution.
By controlling the total carbon amount (TC) and silver (Ag) concentration of the electrolyte solution at 0.25g/L or less and 0.2g/L or less, respectively, and applying 40 to 80A/dm2Current density of (a), surface roughness R between the first surface S1 and the second surface S2 of the electrolytic copper foil 110aDifference and peak number roughness RpcThe difference of (a) can be controlled to be 0.3 μm or less and 96 or less, respectively.
During electroplating, may be at 31m3Hr to 45m3The flow rate of/hr is subjected to continuous filtration or circulation filtration to remove solid impurities from the electrolyte solution. When the flow rate is less than 31m3At/hr, the flow rate is decreased and the voltage is increased, thereby forming an irregular copper layer 111. On the other hand, when the flow rate is more than 45m3Hr, the filter is damaged, and thus foreign substances are introduced into the electrolyte solution.
As described above, the electrolyte solution includes 10ppm to 50ppm of bis- (3-sulfopropyl) disulfide (SPS) and 10ppm to 50ppm of polyethylene glycol (PEG) as additives. Optionally, the electrolyte solution may further comprise at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, glycol polymers, and thiourea compounds.
When the concentration of SPS in the electrolyte solution exceeds 50ppm, copper plating is activated on the surface of the rotary electrode drum, and thus the glossy surface SS of the copper layer 111 and the surface roughness R of the second surface S2 of the electrolytic copper foil 110aAn excessive increase. As a result, the difference in surface roughness Ra of the first surface S1 and the second surface S2 of the electrolytic copper foil 110 exceeded 0.3. mu.m. Further, the increase in the active specific surface area of the glossy surface SS of the copper layer 111 excessively increases the amount of Cr deposited on the second surface S2 of the electrolytic copper foil 110. As a result, the difference in Cr attachment amount between the first surface S1 and the second surface S2 of the electrolytic copper foil 110 will exceed 2.5mg/m2The risk of (2) increases.
When the concentration of PEG in the electrolyte solution exceeds 50ppm, fine copper plating nuclei are generated on the surface of the rotating electrode drum, and thus the glossy surface SS of the copper layer 111 and the surface roughness R of the second surface S2 of the electrolytic copper foil 110aAnd (4) excessive reduction. As a result, the surface roughness R of the first surface S1 and the second surface S2 of the electrolytic copper foil 110aThe difference of (a) exceeds 0.3 μm. Further, the decrease in the active specific surface area of the glossy surface SS of the copper layer 111 excessively decreases the amount of Cr deposited on the second surface S2 of the electrolytic copper foil 110. As a result, the difference in Cr attachment amount between the first surface S1 and the second surface S2 of the electrolytic copper foil 110 will exceed 2.5mg/m2The risk of (2) increases.
Meanwhile, the degree of the surface of the rotary electrode drum (the surface on which copper is deposited by electroplating) also controls the surface roughness R of the second surface S2 of the electrolytic copper foil 110aPeak number roughness RpcAnd the amount of Cr attached. According to an embodiment of the present invention, the surface of the rotating electrode drum is polished using a polishing brush having a particle size (grit size) of #800 to # 3000.
The difference in the texture coefficient TC (220) of the faces (220) of the first surface S1 and the second surface S2 of the electrolytic copper foil 110 is determined by the current density of electroplating, the polishing conditions of the rotary electrode drum, and the concentration of the additive in the electrolyte solution. In particular, when the SPS concentration in the electrolyte solution exceeds 120ppm, the texture of the second surface S2 of the electrolytic copper foil 110 grows, and thus the difference in texture coefficient TC (220) of the face (220) between the first surface S1 and the second surface S2 exceeds 0.39. And, when the concentration of PEG exceeds 90ppm, the difference of the plane (220) texture coefficients TC (220) of the first surface S1 and the second surface S2 exceeds 0.39.
The first protective layer 112a and the second protective layer 112b are formed on the copper layer 111 by immersing the resulting copper layer 111 in an anticorrosive solution containing 0.5 to 1.5g/L of Cr (for example, at room temperature for a period of 2 seconds to 20 seconds), and then drying the copper layer 111.
The corrosion protection solution may further include at least one of a silane compound and a nitrogen compound. For example, the anti-corrosion solution may contain 0.5 to 1.5g/L of Cr and 0.5 to 1.5g/L of a silane compound.
The battery electrode (i.e., negative electrode) of the present invention can be manufactured by coating a negative active material on the resultant electrolytic copper foil 110 of the present invention.
The negative active material may be selected from the group consisting of carbon; metals such as silicon (Si), germanium (Ge), tin (Sn), lithium (Li), zinc (Zn), magnesium (Mg), cadmium (Cd), cerium (Ce), nickel (Ni), or iron (Fe); an alloy containing the metal; an oxide of the metal; and a composite of the metal and carbon.
For example, a slurry (slurry) is prepared by mixing 1 to 3 parts by weight of styrene-butadiene rubber (SBR) and 1 to 3 parts by weight of carboxymethyl cellulose (CMC) and 100 parts by weight of carbon for a negative electrode active material, and then using distilled water as a solvent. Subsequently, a paste having a thickness ranging from 20 μm to 100 μm is coated on the electrolytic copper foil 110 by using a doctor blade, and then at 0.5 ton/cm at 100 ℃ to 130 ℃2To 1.5 tons/cm2And (3) pressing.
The lithium secondary battery can be manufactured using a conventional positive electrode, an electrolyte and a separator in addition to the secondary battery electrode (negative electrode) manufactured by the above-described method.
Hereinafter, the present invention will be described in detail by examples and comparative examples. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to these examples.
Examples 1 to 3 and comparative examples 1 to 6
A copper layer is formed on the rotating electrode drum by flowing an electric current between the electrode plates spaced apart from each other in the electrolyte solution and the rotating electrode drum. The electrolyte solution contained 75g/L of copper ions, 100g/L of sulfuric acid, 20ppm of chloride ions, 20ppm of SPS, and 20ppm of PEG, and was maintained at 55 ℃. The current density, SPS concentration, PEG concentration, total carbon amount (TC), and silver (Ag) concentration for electroplating, and the particle diameter of the polishing brush for polishing the surface of the rotating electrode drum are shown in table 1 below. The electrolytic copper foil is completed by dipping a copper layer formed by electroplating and then drying the copper layer.
[ Table 1]
In the obtained electrolytic copper foils of examples 1 to 3 and comparative examples 1 to 6, surface roughness R of a first surface (a surface adjacent to the matte surface of the copper layer) and a second surface opposite to the first surface was measuredaPeak number roughness RpcThe texture coefficient TC (220) of the side (220) and the amount of chromium (Cr) coating, and the degree of curling of the electrolytic copper foil was measured, and the results are shown in table 2 below.
aSurface roughness R (mum)
The surface roughness R of the first and second surfaces of the electrolytic copper foil was measured by using Marsurf M300 of Mahr company in accordance with JIS B0601-a(measurement length: 4mm (excluding cut portion)).
pcPeak number roughness R (EA)
Using MaMarsurf M300 of hr corporation to measure the peak number roughness R of the first and second surfaces of the electrolytic copper foilpc. As described above, the peak number roughness RpcIs the peak number roughness R of any three pointspcAnd the peak number roughness R of these points in the surface roughness profile obtained according to ASME B46.1(2009) standardpcIs the number of effective peaks per unit sample length of 4mm higher than the upper standard line of 0.5 μm. When there are no deep valleys of the lower standard line below-0.5 μm between adjacent peaks higher than the upper standard line, the relatively lower peak among the peaks is ignored in looking for the number of "effective peaks".
Texture coefficient of face (220) TC (220)
An XRD pattern having peaks corresponding to n crystal planes is obtained by X-ray diffraction (XRD) performed in a range of diffraction angles 2 theta of 30 DEG to 95 deg ((i) target: copper K.alpha.1, (ii)2 theta interval: 0.01 DEG, (iii)2 theta scan rate: 3 DEG/min), and then XRD diffraction intensity I (hkl) of each crystal plane (hkl) is obtained from the pattern. In addition, XRD diffraction intensity I of each of n crystal planes of standard copper powder specified by Joint Committee for Powder Diffraction Standards (JCPDS) was obtained0(hkl). Next, I (hkl)/I of n crystal planes is obtained0(hkl) and then by averaging I (220)/I of face (220)0(220) The texture coefficient TC (220) of the surface (220) is calculated by dividing by the arithmetic mean. That is, the texture coefficient TC (220) of the face (220) will be calculated based on equation 1 below.
[ equation 1]
Anticorrosive material (chromium) coating
By covering the second surface of the electrolytic copper foil with tape and cutting the electrolytic copper foil, a sample of 10cm × 10cm was obtained. Subsequently, the first surface of the electrolytic copper foil was dissolved in an aqueous nitric acid solution (a mixture of commercial nitric acid and water in a ratio of 1: 1). The resulting solution was diluted with water to give 50mL of diluted solution. Subsequently, the diluted solution was analyzed at 25 ℃ to measure the chromium coating amount by Atomic Absorption Spectroscopy (AAS). Subsequently, the chromium coating amount of the second surface of the electrolytic copper foil was measured in the same manner.
Crimp degree (mm) of electrolytic copper foil
As shown in fig. 4, the electrolytic copper foil was cut along a cross-shaped line (8cm × 8cm) at an arbitrary point of the first surface of the electrolytic copper foil, and then the curling degree of four pieces formed by the cutting was measured using a ruler, and the arithmetic average of the measured values was calculated.
[ Table 2]
As can be seen from Table 2, the surface roughness R between the first surface and the second surface of the electrodeposited copper foilaWhen the difference exceeds 0.3. mu.m (comparative example 1); roughness at peak number RpcWhen the difference of (A) exceeds 96 (comparative example 2), when the texture coefficient TC (220) of the face (220) exceeds 0.39 (comparative examples 3 and 4), and when the difference of chromium adhesion amounts exceeds 2.5mg/m2When (comparative examples 5 and 6), the curl of the electrolytic copper foil exceeded 10mm and was very severe.
According to the present invention, by manufacturing intermediate products and end products such as a Flexible Printed Circuit Board (FPCB) and a secondary battery by an RTR process using an electrodeposited copper foil with minimized curling, the electrodeposited copper foil can be prevented from being folded or wrinkled during the RTR process, thereby improving the productivity of the end products and the intermediate products.
Therefore, the embodiments and drawings of the present invention should be considered as illustrative rather than limiting the present invention and not limiting the technical scope of the present invention. The scope of the present invention should be construed by the appended claims, and all technical ideas within the scope of equivalents thereof should be construed as being included in the scope of the present invention.
Claims (13)
1. An electrolytic copper foil having a first surface and a second surface opposite to the first surface, the electrolytic copper foil comprising:
a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface;
a first protective layer on the matte side; and
a second protective layer on the glossy surface, wherein,
surface roughness R between first surface and second surfaceaThe difference of (a) is less than or equal to 0.3 μm;
peak number roughness R between first surface and second surfacepcIs less than or equal to 96;
the difference in texture coefficient TC (220) of the face 220 between the first surface and the second surface is less than or equal to 0.39;
the first protective layer and the second protective layer contain chromium Cr; and
the difference in the amount of Cr coating between the first surface and the second surface is less than or equal to 2.5mg/m2，
Wherein the surface roughness R of each of the first and second surfacesaIn the range of 0.1 μm to 0.55. mu.m,
peak number roughness R of each of the first and second surfacespcIn the range of from 3 to 106,
the texture coefficient TC (220) of the face 220 of each of the first and second surfaces ranges from 0.4 to 1.32.
2. The electrolytic copper foil as claimed in claim 1, wherein the electrolytic copper foil has a yield strength in the range of 21kgf/mm at room temperature of 25 ± 15 ℃2To 55kgf/mm2。
3. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has an elongation of 3% or more at room temperature of 25 ± 15 ℃.
4. A battery electrode, comprising:
an electrolytic copper foil having a first surface and a second surface opposite to the first surface; and
a first active material layer on the first surface, wherein,
the electrolytic copper foil comprises:
a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface;
a first protective layer on the matte side; and
a second protective layer, on the glossy surface,
surface roughness R between first surface and second surfaceaThe difference of (a) is less than or equal to 0.3 μm;
peak number roughness R between first surface and second surfacepcIs less than or equal to 96;
the difference in texture coefficient TC (220) of the face 220 between the first surface and the second surface is less than or equal to 0.39;
the first protective layer and the second protective layer contain chromium Cr; and
the difference in the amount of Cr coating between the first surface and the second surface is less than or equal to 2.5mg/m2，
Wherein the surface roughness R of each of the first and second surfacesaIn the range of 0.1 μm to 0.55. mu.m,
peak number roughness R of each of the first and second surfacespcIn the range of from 3 to 106,
the texture coefficient TC (220) of the face 220 of each of the first and second surfaces ranges from 0.4 to 1.32.
5. The battery electrode as set forth in claim 4, wherein the electrolytic copper foil has a yield strength ranging from 21kgf/mm at room temperature of 25 ± 15 ℃2To 55kgf/mm2And the electrolytic copper foil has an elongation of 3% or more.
6. The battery electrode of claim 4, further comprising: a second active material layer on the second surface, wherein,
the first active material layer and the second active material layer contain carbon; metals including silicon Si, germanium Ge, tin Sn, lithium Li, zinc Zn, magnesium Mg, cadmium Cd, cerium Ce, nickel Ni, or iron Fe; an alloy comprising said metal; an oxide of the metal; and one or more active materials selected from the group consisting of a composite of the metal and carbon.
7. A battery, comprising:
a positive electrode;
a negative electrode formed as a battery electrode according to any one of claims 4 to 6;
an electrolyte configured to provide an environment in which lithium ions are made movable between the positive electrode and the negative electrode; and
a separator configured to electrically insulate the positive electrode and the negative electrode.
8. A method for manufacturing an electrolytic copper foil according to claim 1, the method comprising:
forming a copper layer; and
forming a protective layer on the copper layer, wherein,
the step of forming the copper layer includes:
preparing an electrolyte solution comprising 70 to 90g/L of copper ions, 80 to 120g/L of sulfuric acid, 10 to 50ppm of bis- (3-sulfopropyl) disulfide SPS, and 10 to 50ppm of polyethylene glycol PEG;
by causing current to flow between electrode plates spaced apart from each other in an electrolyte solution and a rotary electrode drum at 40 to 80A/dm2Performing electroplating with the current density of (a); and
when the plating is performed, the total carbon amount TC in the electrolyte solution is maintained below 0.25g/L or 0.25g/L, and the silver concentration in the electrolyte solution is maintained below 0.2g/L or 0.2g/L,
wherein the surface of the rotary electrode drum is polished by using a polishing brush having a particle diameter of #800 to #3000,
wherein the step of forming the protective layer comprises: the copper layer is immersed in an anti-corrosion solution containing 0.5 to 1.5g/L Cr.
9. The method of manufacturing an electrolytic copper foil according to claim 8, wherein the step of preparing an electrolyte solution comprises:
heat-treating the copper wire at a temperature ranging from 600 ℃ to 900 ℃ for a time ranging from 30 minutes to 60 minutes;
pickling the heat-treated copper wire;
placing the acid-washed copper wire into sulfuric acid; and
to the copper wire-impregnated sulfuric acid was added bis- (3-sulfopropyl) disulfide SPS and polyethylene glycol PEG.
10. The method of manufacturing an electrolytic copper foil according to claim 8, wherein the step of forming a copper layer further comprises: when the plating is performed, hydrogen peroxide and air are injected into the electrolyte solution.
11. The method of manufacturing an electrolytic copper foil according to claim 8, wherein the step of forming a copper layer further comprises: chloride ions capable of precipitating silver Ag in the form of AgCl are added to the electrolyte solution to avoid the concentration of silver Ag in the electrolyte solution exceeding 0.2 g/L.
12. The method for producing an electrolytic copper foil according to claim 8, wherein the electrolyte solution further contains at least one organic additive selected from the group consisting of hydroxyethyl cellulose HEC, organic sulfides, organic nitrides and glycol-based polymers.
13. The method of manufacturing an electrolytic copper foil according to claim 8, wherein the electrolytic solution further contains a thiourea-based compound.
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| KR10-2016-0151713 | 2016-11-15 | ||
| KR1020160151713A KR20180054985A (en) | 2016-11-15 | 2016-11-15 | Electrolytic Copper Foil with Minimized Curl, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
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| KR102639965B1 (en) | 2022-06-28 | 2024-02-22 | 장 춘 페트로케미컬 컴퍼니 리미티드 | Electrolytic copper foil, electrode and lithium-ion cell comprising the same |
Families Citing this family (12)
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| KR101992840B1 (en) | 2017-06-20 | 2019-06-27 | 케이씨에프테크놀로지스 주식회사 | Copper foil with minimized bagginess and tear, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| KR102180926B1 (en) | 2017-06-28 | 2020-11-19 | 에스케이넥실리스 주식회사 | Copper foil having improved workability and charge discharge characteristics, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| KR101992841B1 (en) | 2017-07-13 | 2019-06-27 | 케이씨에프테크놀로지스 주식회사 | Copper foil with minimized bagginess, wrinkle and tear, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| KR102439621B1 (en) | 2017-09-01 | 2022-09-01 | 에스케이넥실리스 주식회사 | Copper Film, Manufacturing Methods Thereof, And Anode For Li Secondary Battery Comprising The Same |
| KR102518398B1 (en) * | 2018-06-20 | 2023-04-04 | 에스케이넥실리스 주식회사 | Copper foil with high stability, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| JP6700347B2 (en) * | 2018-08-09 | 2020-05-27 | ケイシーエフ テクノロジース カンパニー リミテッド | Copper foil with minimal sagging and tearing, electrode including the same, secondary battery including the same, and manufacturing method thereof |
| EP3608447B1 (en) * | 2018-08-10 | 2021-10-06 | SK Nexilis Co., Ltd. | Copper foil with minimized bagginess, wrinkle and tear, electrode including the same, secondary battery including the same and method for manufacturing the same |
| EP3608446B1 (en) * | 2018-08-10 | 2022-09-14 | SK Nexilis Co., Ltd. | Copper foil having workability and charge/discharge characteristics, electrode including the same, secondary battery including the same and method for manufacturing the same |
| JP7075332B2 (en) * | 2018-11-30 | 2022-05-25 | 三洋電機株式会社 | Secondary battery and its manufacturing method |
| KR20210062369A (en) * | 2019-11-21 | 2021-05-31 | 에스케이넥실리스 주식회사 | Electrolytic Copper Foil Capable of Preventing Defects of Tear or Wrinkle Thereof, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| CN112981474B (en) * | 2021-02-05 | 2021-12-07 | 广东嘉元科技股份有限公司 | High-strength copper foil and preparation method thereof |
| TWI800419B (en) * | 2022-06-28 | 2023-04-21 | 長春石油化學股份有限公司 | Electrolytic copper foil, electrode and lithium ion battery comprising the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358409A (en) * | 2000-01-28 | 2002-07-10 | 三井金属鉱业株式会社 | Surface treated copper foil and method for preparing the same and copper-clad laminate using the same |
| CN102933746A (en) * | 2010-06-30 | 2013-02-13 | 三井金属矿业株式会社 | Process for production of copper foil for negative electrode current collector |
| CN104928726A (en) * | 2014-03-21 | 2015-09-23 | 长春石油化学股份有限公司 | Electrolytic copper foil |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07107181B2 (en) * | 1987-08-27 | 1995-11-15 | 日鉱金属株式会社 | Copper material for superconductivity |
| JP2754157B2 (en) * | 1994-03-31 | 1998-05-20 | 三井金属鉱業株式会社 | Manufacturing method of electrolytic copper foil for printed wiring board |
| JP3608840B2 (en) * | 1995-04-07 | 2005-01-12 | 古河サーキットフォイル株式会社 | Electrolytic copper foil for flexible wiring boards |
| JP3943214B2 (en) * | 1997-11-14 | 2007-07-11 | 日鉱金属株式会社 | Electrolytic copper foil containing silver |
| JP3850155B2 (en) * | 1998-12-11 | 2006-11-29 | 日本電解株式会社 | Electrolytic copper foil, copper foil for current collector of secondary battery and secondary battery |
| JP4349690B2 (en) * | 1999-06-29 | 2009-10-21 | 日本電解株式会社 | Method for producing electrolytic copper foil |
| JP4712759B2 (en) * | 2006-06-07 | 2011-06-29 | 古河電気工業株式会社 | Surface-treated electrolytic copper foil, method for producing the same, and circuit board |
| WO2008132987A1 (en) * | 2007-04-20 | 2008-11-06 | Nippon Mining & Metals Co., Ltd. | Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil |
| JP4948654B2 (en) * | 2010-03-01 | 2012-06-06 | 古河電気工業株式会社 | Copper foil for negative electrode current collector of lithium ion secondary battery, manufacturing method thereof, negative electrode of lithium ion secondary battery, manufacturing method thereof |
| JP2012172198A (en) * | 2011-02-22 | 2012-09-10 | Jx Nippon Mining & Metals Corp | Electrolytic copper foil and method for manufacturing the same |
| JP5822928B2 (en) * | 2011-07-13 | 2015-11-25 | Jx日鉱日石金属株式会社 | Electrolytic copper foil having high strength and low warpage and method for producing the same |
| JP5730742B2 (en) * | 2011-10-25 | 2015-06-10 | 古河電気工業株式会社 | Electrolytic copper foil for lithium ion secondary battery and method for producing the same |
| TWI539033B (en) * | 2013-01-07 | 2016-06-21 | Chang Chun Petrochemical Co | Electrolytic copper foil and its preparation method |
| TWI533496B (en) * | 2013-07-23 | 2016-05-11 | Chang Chun Petrochemical Co | Electrolytic copper foil |
| KR101449342B1 (en) * | 2013-11-08 | 2014-10-13 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil |
| US9287566B1 (en) * | 2015-04-17 | 2016-03-15 | Chang Chun Petrochemical Co., Ltd. | Anti-curl copper foil |
-
2016
- 2016-11-15 KR KR1020160151713A patent/KR20180054985A/en not_active Application Discontinuation
-
2017
- 2017-10-26 JP JP2017206962A patent/JP6533267B2/en active Active
- 2017-11-15 CN CN201711130543.5A patent/CN108075098B/en active Active
- 2017-11-15 TW TW106139484A patent/TWI651436B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358409A (en) * | 2000-01-28 | 2002-07-10 | 三井金属鉱业株式会社 | Surface treated copper foil and method for preparing the same and copper-clad laminate using the same |
| CN102933746A (en) * | 2010-06-30 | 2013-02-13 | 三井金属矿业株式会社 | Process for production of copper foil for negative electrode current collector |
| CN104928726A (en) * | 2014-03-21 | 2015-09-23 | 长春石油化学股份有限公司 | Electrolytic copper foil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102639965B1 (en) | 2022-06-28 | 2024-02-22 | 장 춘 페트로케미컬 컴퍼니 리미티드 | Electrolytic copper foil, electrode and lithium-ion cell comprising the same |
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| JP6533267B2 (en) | 2019-06-19 |
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