CN108306022B - Electrolytic copper foil, electrode comprising same, secondary battery and method for manufacturing same - Google Patents
Electrolytic copper foil, electrode comprising same, secondary battery and method for manufacturing same Download PDFInfo
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- CN108306022B CN108306022B CN201810035755.3A CN201810035755A CN108306022B CN 108306022 B CN108306022 B CN 108306022B CN 201810035755 A CN201810035755 A CN 201810035755A CN 108306022 B CN108306022 B CN 108306022B
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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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- 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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
Provided are an electrodeposited copper foil substantially free of wrinkle defects, an electrode including the same, a secondary battery including the same, and a method of manufacturing the same. The electrolytic copper foil of the present invention has a first surface and a second surface opposite to the first surface, each of the first surface and the second surface has a Profile Maximum Ratio (PMR) of 4.8 to 16.1, and the electrolytic copper foil has a texture coefficient [ TC (220) ] of a (220) plane of 0.49 to 1.28]、35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
Description
Cross Reference to Related Applications
The present application claims priority and benefit from korean patent application No. 2017-0005857 filed on 13/1/2017, the disclosure of which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to an electrolytic copper foil substantially free from wrinkle defects, an electrode comprising the same, a secondary battery comprising the same, and a method of manufacturing the same.
Background
Electrolytic copper foil is being used to manufacture various products such as a negative electrode of a secondary battery and a Flexible Printed Circuit Board (FPCB).
When the production conditions cannot be precisely controlled in the electrolytic copper foil manufacturing process, the typical wrinkling defect occurring in the manufacture of a film cannot be prevented.
The electrolytic copper foil having the wrinkle defect causes the yield and quality of the secondary battery to be deteriorated. Specifically, the surface of the electrolytic copper foil cannot be uniformly coated with the negative active material due to unevenness of the surface of the electrolytic copper foil having a wrinkle defect. The uneven coating of the negative active material causes short-circuiting of the secondary battery or delamination of the negative active material. Therefore, the wrinkle defect of the electrolytic copper foil is one of the reasons for the return of goods by consumers.
It is known that reducing the weight deviation of the electrolytic copper foil is a method of suppressing the wrinkle defect of the electrolytic copper foil. However, in the case where the thickness of the electrolytic copper foil is 8 μm or less, which increases the use ratio for improving the capacity of the secondary battery, even if the weight deviation thereof is controlled to be very low, the wrinkle defect occurs.
Disclosure of Invention
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 prevent problems due to limitations and disadvantages of the related art.
In addition, the present invention relates to an electrolytic copper foil substantially free from wrinkle defects.
Further, the present invention relates to an electrode capable of securing high productivity by being manufactured with an electrolytic copper foil substantially free from wrinkle defects.
Further, the present invention relates to a secondary battery capable of securing high productivity by being manufactured with an electrolytic copper foil substantially free from wrinkle defects.
Further, the present invention relates to a method for manufacturing an electrolytic copper foil capable of preventing a wrinkle defect.
In addition to, or in addition to, the above aspects of the invention, other features and advantages of the invention are described below or will become apparent to those skilled in the art from the following 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 including: a copper layer comprising a matte surface facing the first surface and a glossy surface facing the second surface; a first protective layer on the matte surface; and a second protective layer on the glossy surface, wherein the first surface and the second surface each have a Profile Maximum Ratio (PMR) of 4.8 to 16.1 (where PMR denotes a maximum height roughness (R)max) And arithmetic mean roughness (R)a) Ratio (R) ofmax/Ra) And the electrolytic copper foil has a texture coefficient [ TC (220) ] of the (220) face of 0.49 to 1.28]、35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
The first surface and the second surface may each have a maximum height roughness (R) of 1.2 μm to 3.7 μmmax) And an arithmetic average roughness (R) of 0.15 μm to 0.45 μma)。
The first protective layer and the second protective layer may each contain chromium (Cr).
The electrolytic copper foil may have a thickness of 4 μm to 30 μm, and preferably may have a thickness of 4 μm to 8 μm.
According to another aspect of the present invention, there is provided a secondary battery electrode including: 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 surface facing the first surface and a glossy surface facing the second surface; a first protective layer on the matte surface; and a second protective layer on the glossy surface, the first surface and the second surface each having a PMR of 4.8 to 16.1 (where PMR denotes a maximum height roughness (R)max) And arithmetic mean roughness (R)a) Ratio (R) ofmax/Ra) And the electrolytic copper foil has a texture coefficient [ TC (220) ] of the (220) face of 0.49 to 1.28]、35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
The first surface and the second surface may each have a maximum height roughness (R) of 1.2 μm to 3.7 μmmax) And an arithmetic average roughness (R) of 0.15 μm to 0.45 μma)。
The first protective layer and the second protective layer may each contain chromium (Cr).
The electrolytic copper foil may have a thickness of 4 μm to 30 μm, and preferably may have a thickness of 4 μm to 8 μm.
The secondary 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 each include at least one active material selected from the group consisting of carbon, a metal such as Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe, an alloy containing the metal, an oxide of the metal, and a composite of the metal and carbon.
According to still another aspect of the present invention, there is provided a secondary battery including: the lithium ion secondary battery includes a cathode, an anode including the secondary battery electrode, an electrolyte configured to provide an environment for lithium ions to move between the cathode and the anode, and a separator configured to electrically insulate the anode from the cathode.
According to still another aspect of the present invention, there is provided a method of manufacturing an electrolytic copper foil including 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 comprising 70 to 90g/L of copper ions, 50 to 150g/L of sulfuric acid, 2 to 20mg/L of N-Allylthiourea (ATU), and 2 to 20mg/L of bis (3-sulfopropyl) -disulfide (SPS); and by making the density 40A/dm2To 80A/dm2The electroplating is performed by flowing a current from the electrode plate to the rotary electrode drum, wherein the surface of the rotary electrode drum is polished using a polishing brush having a grain size (grit) of #800 to #3000, and the concentration of silver (Ag) in the electrolyte is maintained at 50mg/L or less while the electroplating is performed.
The step of preparing the electrolyte may include: heat-treating the copper wire at 600 ℃ to 900 ℃ for 30 minutes to 60 minutes; pickling the heat-treated copper wire; placing the acid-washed copper wire into sulfuric acid; and adding ATU and SPS to the copper wire-embedded sulfuric acid.
When the plating is performed, the electrolyte may be continuously filtered, and when the continuous filtering is performed, the flow rate of the electrolyte may range from 39m3Hr to 46m3/hr。
When the plating is performed, the variation in flow rate may be 5%/sec or less.
The step of forming the copper layer may further include: chloride ions precipitating silver (Ag) as AgCl are added to the electrolyte to prevent the concentration of silver (Ag) in the electrolyte from exceeding 50 mg/L.
The forming of the protective layer may include: the copper layer is immersed in a rust inhibitive solution containing 0.5g/L to 1.5g/L of Cr.
The general description of the invention as set forth above is intended only to illustrate or explain the invention and does not limit the scope of the invention.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing in detail exemplary embodiments thereof with reference to the attached drawings, in which:
fig. 1 is a sectional view of an electrode for a secondary battery according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of an electrolytic copper foil;
FIG. 3 is a photograph of an electrolytic copper foil of comparative example 1 in which a wrinkle defect occurred; and
fig. 4 is a photograph of the electrolytic copper foil of comparative example 4 which was torn in the manufacturing process thereof.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the 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, this invention includes all modifications and alterations insofar as they come within the scope of the invention as defined by the appended claims or the equivalents thereof.
A lithium secondary battery includes a cathode, an anode, an electrolyte providing an environment in which lithium ions can move between the cathode and the anode, and a separator electrically insulating the cathode from the anode to prevent electrons generated at one electrode from being inefficiently consumed by moving to the other electrode through the inside of the secondary battery.
Fig. 1 is a sectional view of an electrode for a secondary battery according to an embodiment of the present invention.
As shown in fig. 1, a secondary battery electrode 100 according to an embodiment of the present invention includes: an electrolytic copper foil 110 having a first surface S1 and a second surface S2 opposite to the first surface S1; a first active material layer 120a formed on the first surface S1; and a second active material layer 120b formed on the second surface S2. In fig. 1, an example of forming the first and second active material layers 120a and 120b on the first and second surfaces S1 and S2 of the electrolytic copper foil 110, respectively, is shown, but the present invention is not limited thereto, and the secondary 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, in a lithium secondary battery, an aluminum foil is used as a positive electrode current collector coupled to a positive electrode active material, and an electrolytic copper foil is used as a negative electrode current collector coupled to a negative electrode active material.
According to an embodiment of the present invention, the secondary battery electrode 100 serves as an anode of a lithium secondary battery, the electrolytic copper foil 110 serves as a negative electrode current collector, and the first and second active material layers 120a and 120b each include a negative electrode active material.
As shown in fig. 1, the electrolytic copper foil 110 of the present invention includes a copper layer 111 having a matte surface MS and a glossy surface SS, a first protective layer 112a formed on the matte surface MS of the copper layer 111, and a second protective layer 112b formed on the glossy surface SS of the copper layer 111.
The matte surface MS is a surface of the copper layer 111 facing the first surface S1 of the electrolytic copper foil 110, and the glossy surface 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 the 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 ten-point average roughness (R) lower than the matte surface MSz) However, the present invention is not limited thereto, and the ten-point average roughness (R) of the glossy surface SSz) May be higher than or equal to the ten point average roughness (R) of the matt surface MSz)。
The first protective layer 112a and the second protective layer 112b may be formed to prevent corrosion of the copper layer 111 and improve heat resistance of the copper layer 111, and may contain chromium (Cr).
According to an embodiment of the present invention, an adhesion amount of chromium (Cr) of each of the first and second surfaces S1 and S2 may range from 1mg/m2To 5mg/m2。
As described above, the electrolytic copper foil 110 having the wrinkle defect causes uneven coating of the negative active material, and the uneven coating of the negative active material causes short-circuiting of the secondary battery and delamination of the negative active material. Therefore, the electrolytic copper foil 110 should be manufactured in consideration of all factors causing the wrinkling defect of the electrolytic copper foil 110.
According to the present invention, it was found that factors such as the surface profile of the electrolytic copper foil 110, the crystal structure of the surface, the yield strength, the weight deviation, etc., cause wrinkling defects of the electrolytic copper foil 110. Therefore, in order to minimize the wrinkle defect of the electrolytic copper foil 110, it is necessary to precisely control these important factors.
The surface profile, which is closely related to the grain size, can be determined by the arithmetic mean roughness (R)a) And maximum height roughness (R)max) And the crystal structure of the surface can be represented by the texture coefficient of the (220) plane [ TC (220)]And (4) showing.
According to the present invention, in order to minimize wrinkle defects of the electrolytic copper foil 110, the first surface S1 and the second surface S2 each have a Profile Maximum Ratio (PMR) of 4.8 to 16.1, and the electrolytic copper foil has a texture coefficient [ TC (220) ] of a (220) plane of 0.49 to 1.28]，35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
PMR refers to the maximum height roughness (R)max) And arithmetic mean roughness (R)a) Ratio of (R)max/Ra). In the present invention, arithmetic mean roughness (R)a) And maximum height roughness (R)max) Is measured according to Japanese Industrial Standard (JIS) B0601-2001 standard [ measurement length: 4mm (excluding cut-off parts)]。
When the PMR is greater than 16.1, air may be trapped between the electrolytic copper foils 110 when the electrolytic copper foil 110 manufactured by electrolytic plating is wound on a bobbin (bobbin), thereby causing a wrinkle defect. On the other hand, when the PMR is less than 4.8, the electrolytic copper foil 110 may be locally extended when wound on a reel in a roll-to-roll (RTR) process, thereby causing a wrinkle defect.
According to an embodiment of the present invention, the first surface S1 and the second surface S2 may each have a maximum height roughness (R) of 1.2 μm to 3.7 μmmax) And an arithmetic average roughness (R) of 0.15 μm to 0.45 μma)。
In the present invention, the texture coefficient of the (220) plane of the electrolytic copper foil 110 is measured and calculated as follows.
First, by performing X-ray diffraction (XRD) [ target: copper K α 1, 2 θ spacing: 0.01 °, 2 θ scan rate: 3 °/min]An XRD pattern having peaks corresponding to n crystal planes (for example, as shown in FIG. 2, XRD patterns having peaks corresponding to (111), (200), (220) and (311) planes) is obtained, and XRD diffraction intensity of each crystal plane (hkl) [ I (hkl) ] is obtained from the XRD pattern]. In addition, XRD Diffraction intensity [ I ] of each of n crystal planes of a standard copper powder specified by Joint Committee on Power Diffraction standards (JCPDS) for powder Diffraction standards was obtained0(hkl)]. Next, I (hkl)/I of n crystal planes is obtained0The arithmetic mean of (hkl) and then the average of (220)/I of (220) plane0(220) The texture coefficient [ TC (220) ] of the (220) plane of the electrolytic copper foil 110 was calculated by dividing the arithmetic mean value]. That is, the texture coefficient [ TC (220) ] of the (220) plane will be calculated based on the following equation 1]。
[ equation 1]
When the texture coefficient [ TC (220) ] of the (220) plane is less than 0.49, the crystal structure of the electrolytic copper foil 110 is not sufficiently dense, and the crystal structure is easily deformed when the electrolytic copper foil 110 is wound around a bobbin, resulting in a wrinkle defect. On the other hand, when the texture coefficient [ TC (220) ] of the (220) plane is more than 1.28, the crystal structure of the electrolytic copper foil 110 becomes too dense to have high brittleness, and as a result, the electrolytic copper foil 110 is torn during the manufacturing process.
In the present invention, the yield strength is a yield strength measured at room temperature of 25 ℃ and measured using a Universal Testing Machine (UTM) [ sample width: 12.7mm, distance between clamps: 50mm, measurement speed: 50 mm/min).
When the yield strength of the electrolytic copper foil 110 is less than 35kgf/mm2When the electrolytic copper foil 110 is wound around a bobbin, plastic deformation is caused, thereby accelerating wrinkle defects. On the other hand, when the yield strength of the electrolytic copper foil 110 is more than 58kgf/mm2When the brittleness of the electrolytic copper foil 110 becomes high to deteriorate the compatibility, and the risk of tearing the electrolytic copper foil 110 during the manufacturing process increases.
In the present invention, the weight deviation means a weight deviation in the width direction, and is measured and calculated as follows.
After sampling 5cm × 5cm from the points on the left, middle, and right sides in the width direction of the electrolytic copper foil 110, each weight of the three samples was measured. The measured values were used to calculate the arithmetic mean weight and standard deviation, and then the ratio (%) of the standard deviation and the arithmetic mean weight (i.e., (standard deviation/arithmetic mean weight) × 100) was calculated.
When the weight deviation of the electrolytic copper foil 110 is more than 3%, the electrolytic copper foil 110 is locally extended when the electrolytic copper foil 110 is wound around a bobbin, causing wrinkles.
The electrolytic copper foil 110 of the present invention has an Elongation (Elongation) of 3% or more at room temperature (25 ℃). When the elongation of the electrolytic copper foil 110 is less than 3%, the electrolytic copper foil 110 is not stretched by a force applied during the process of manufacturing the electrolytic copper foil 110 or during the process of manufacturing the secondary battery electrode 100, increasing the risk of tearing of the electrolytic copper foil 110.
The electrolytic copper foil 110 of the present invention may have a thickness of 4 μm to 30 μm, and preferably, may have a thickness of 4 μm to 8 μm. When the thickness of the electrolytic copper foil 110 is less than 4 μm, the workability (workability) of the process of manufacturing the secondary battery is reduced. On the other hand, when the thickness of the electrolytic copper foil 110 is greater than 30 μm, it may be difficult to secure a sufficient capacity of the secondary battery.
Specifically, since it is difficult to prevent the wrinkle defect of the electrolytic copper foil 110 having a thickness of 8 μm or less (an increase in thickness is required to manufacture a high-capacity secondary battery) by simply reducing the weight deviation of the electrolytic copper foil 110, it is necessary to further apply the technical features of the present invention.
Each of the first and second active material layers 120a and 120b may include a material selected from the group consisting of carbon; metals of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe; an alloy containing the metal; an oxide of the metal; and at least one selected from the group consisting of a composite of the metal and carbon as an anode active material.
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 formed of a mixture containing a predetermined amount of Si.
Hereinafter, a method of manufacturing the electrolytic copper foil 110 according to an embodiment of the present invention 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 containing 70 to 90g/L of copper ions, 50 to 150g/L of sulfuric acid, 2 to 20mg/L of N-Allylthiourea (ATU), and 2 to 20mg/L of bis (3-sulfopropyl) -disulfide (SPS) was prepared.
The yield strength of the electrolytic copper foil 110 can be controlled by adjusting the concentration of ATU. As the concentration of ATU increases, the yield strength of the electrolytic copper foil 110 also substantially increases.
The texture coefficient [ TC (220) ] of the (220) plane of each of the first surface S1 and the second surface S2 of the electrolytic copper foil 110 can be controlled by adjusting the concentration of SPS. The texture coefficient [ TC (220) ] of the (220) side of the electrolytic copper foil 110 also substantially increases with the increase in SPS concentration.
The method includes the steps of heat-treating a high-purity copper wire at 600 to 900 ℃ for 30 to 60 minutes to burn off organic matter, pickling the overheated-treated copper wire, and putting the pickled copper wire into sulfuric acid to prepare an electrolyte containing little or no impurities. Then, an electrolyte can be prepared by adding ATU and SPS.
Subsequently, passing the electrolyte at 50 ℃ to 60 ℃ with a density of 40A/dm2To 80A/dm2Performs electroplating to form a copper layer 111 on the rotating electrode drum, wherein current flows from the electrode plate to the rotating electrode drum spaced apart from the electrode plate.
The current density affects the arithmetic mean roughness (R) of the electrolytic copper foil 110a). Arithmetic mean roughness (R)a) Substantially decreases with increasing current density. In other words, as the current density decreases, the arithmetic mean roughness (R)a) Substantially increased.
The surface of the rotating electrode drum is polished (for example, the surface of copper is precipitated by performing electroplating) using a polishing brush having a particle diameter (grit) of #800 to # 3000. Preferably, the surface of the rotary electrode drum is uniformly polished in the width direction of the surface of the rotary electrode drum by surface polishing the surface of the rotary electrode drum while the water is diffused in the width direction.
The degree of polishing of the surface of the rotary electrode drum (for example, the surface of the copper precipitated by performing electroplating) affects the arithmetic average roughness (R2) of the second surface S78 of the electrolytic copper foil 110a) Maximum height roughness (R)max) And the like.
According to the present invention, the concentration of silver (Ag) in the electrolyte is maintained at 50mg/L or less while the plating is performed. The concentration of silver (Ag) affects the maximum height roughness (R) of the electrolytic copper foil 110max). Maximum height roughness (R) of the electrolytic copper foil 110max) Substantially increases as the concentration of silver (Ag) decreases.
In order to prevent silver (Ag) from being introduced into the electrolyte at the time of plating to make the concentration of silver (Ag) in the electrolyte exceed 50mg/L, a small amount of chloride ions (e.g., 15 to 25mg/L) may be added to the electrolyte, which precipitates the silver (Ag) as AgCl. As a result, the electrolyte may have a silver (Ag) concentration of, for example, 1mg/L to 50 mg/L.
Can be at 39m3Hr to 46m3Continuous (or circulating) filtration is performed at a flow rate of/hr to remove solid impurities from the electrolyte while electroplating is performed. When the flow rate is less than 39m3At/hr, the flow rate is decreased, the overvoltage is increased, and the copper layer 111 is formed unevenly. On the other hand, when the flow rate exceeds 46m3At/hr, the filter is damaged and foreign matter enters the electrolyte. The flow rate of the electrolyte also affects the yield strength of the electrolytic copper foil 110.
In order to manufacture the electrolytic copper foil 110 having a weight deviation of 3% or less, it is preferable to keep the flow rate variation at the time of electroplating at 5%/sec or less. When the flow rate of the electrolytic solution is changed more than 5%/sec, the change of the copper plating efficiency in the width direction of the copper layer 111 is increased, and the weight deviation of the electrolytic copper foil 110 exceeds 3%.
Then, each of the first protective layer 112a and the second protective layer 112b on the copper layer 111 is formed by immersing the copper layer 111 manufactured as described above in an antirust solution (for example, immersion at room temperature for 2 seconds to 20 seconds) containing 0.5g/L to 1.5g/L of Cr and drying the copper layer 111.
The rust inhibitive solution may further include at least one of a silane compound and a nitrogen compound. For example, the rust inhibitive solution may contain 0.5g/L to 1.5g/L of Cr and 0.5g/L to 1.5g/L of a silane compound.
The secondary battery electrode (i.e., anode) of the present invention may be manufactured by coating the electrolytic copper foil 110 of the present invention manufactured as described above with a negative active material.
The anode active material may be selected from the group consisting of carbon; metals such as Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe; an alloy containing the metal; an oxide of the metal; and a composite of the metal and carbon.
For example, 1 to 3 parts by weight of styrene-butadiene rubber (SBR) and 1 to 3 parts by weight of carboxymethyl cellulose (CMC) are mixed in 100 parts by weight of carbon for a negative active material, and then distilled water is used as a solvent to prepare a slurry. Next, the electrolytic copper foil 110 was coated with the slurry to have a thickness of 20 to 100 μm using a doctor blade and 0.5 to 1.5ton cm at a temperature of 110 to 130 ℃2Is pressed under pressure.
The lithium secondary battery may be manufactured using a conventional cathode, electrolyte and separator with the secondary battery electrode (or anode) of the present invention manufactured as described above.
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the following examples are only examples to aid understanding of the present invention, and the scope of the present invention is not limited to these examples.
Examples 1 to 6 and comparative examples 1 to 7
By adjusting the density to 60A/dm in the electrolyte2From the electrode plate to a rotating electrode drum disposed spaced apart from the electrode plate to form a copper layer on the rotating electrode drum. The electrolyte contained 75g/L of copper ions, 100g/L of sulfuric acid, 100g/L of ATU, and 100g/L of SPS, and was maintained at a temperature of 55 ℃. The flow rate of the electrolyte was 42m3And/hr. Variation of ATU concentration, SPS concentration, silver (Ag) concentration, flow rate of electrolyte, and polishing for surface polishing rotary electrode drumThe brush particle size is shown in table 1 below. The copper layer formed by performing electroplating is immersed in an antirust solution and then dried to prepare an electrolytic copper foil.
[ Table 1]
The PMR, the texture coefficient [ TC (220) ] of the (220) plane, the yield strength, and the weight variation of the electrodeposited copper foils of the examples and comparative examples described above were obtained, and the results are shown in table 2. In addition, table 2 shows whether wrinkling and tearing occurred during the manufacturing process of the electrolytic copper foils in the examples and comparative examples.
Maximum ratio of ridge Profile (PMR)
The arithmetic average roughness (R) of the first surface (the surface of the copper layer adjacent to the matte surface) and the second surface (the surface of the copper layer adjacent to the glossy surface) of the electrolytic copper foil was measured using a SJ-310 luminometer manufactured by Mitutoyo corporation in accordance with JIS B0601-2001 standarda) And maximum height roughness (R)max) [ measurement length: 4mm (excluding the truncated part)]. Next, the maximum height roughness (R) is calculatedmax) And arithmetic mean roughness (R)a) Ratio of (R)max/Ra) To obtain a PMR for each of the first and second surfaces.
Texture coefficient of ridge (220) [ TC (220)]
XRD by performing with diffraction angles (2 θ) ranging from 30 ° to 95 ° [ (i) target: copper K α 1, (ii)2 θ spacing: 0.01 °, (iii)2 θ scan rate: 3 °/min]An XRD pattern having peaks corresponding to n crystal planes was obtained, and XRD diffraction intensities for each crystal plane (hkl) [ I (hkl) ]were obtained from the XRD pattern]. In addition, XRD diffraction intensity [ I ] of each of n crystal planes of standard copper powder specified by JCPDS was obtained0(hkl)]. Next, I (hkl)/I of n crystal planes is obtained0The arithmetic mean of (hkl) and then the average of (220)/I of (220) plane0(220) The texture coefficient [ TC (220) ] of the (220) plane of the electrolytic copper foil 110 was calculated by dividing the arithmetic mean value]. That is, the texture coefficient [ TC (220) ] of the (220) plane is calculated based on the following equation 1]。
[ equation 1]
2Yield strength (kgf/mm)
The yield strength of the electrolytic copper foil was measured at room temperature of 25 ℃ using UTM. The width of the sample was 12.7mm, the distance between the grips was 50mm, and the measurement speed was 50 mm/min.
Difference in weight (%)
After taking samples of 5cm × 5cm from points located at the left, middle, and right in the width direction of the electrolytic copper foil, the weights of the three samples were measured, respectively. The arithmetic mean weight and standard deviation were calculated using the measured values, and then the ratio (%) of the standard deviation and arithmetic mean weight (i.e., (standard deviation/arithmetic mean weight) × 100) was calculated.
[ Table 2]
Referring to table 2 above, in the case where the electrolytic copper foil includes a surface having a PMR of less than 4.8 (in comparative example 1), and in the case where the electrolytic copper foil includes a surface having a PMR of more than 16.1 (in comparative example 2), the texture coefficient [ TC (220)) of the (220) side of the electrolytic copper foil is included]In the case of a surface of less than 0.49 (in comparative example 6), the surface of the electrolytic copper foil included a yield strength of less than 35kgf/mm2In the case of the surface of (in comparative example 3), and in the case of the electrolytic copper foil including heavy metalIn the case of the surface having the amount deviation of more than 3% (in comparative example 5), wrinkles occurred in the manufacturing process of the electrolytic copper foil. FIG. 3 is a photograph of an electrodeposited copper foil with wrinkling defects of comparative example 1.
In addition, the electrolytic copper foil includes a yield strength of more than 58kgf/mm2In the case of (1) (comparative example 4), the electrolytic copper foil was torn. FIG. 4 is a photograph showing the electrolytic copper foil torn in the production process of comparative example 4.
Specifically, in the case where the electrolytic copper foil includes a surface having a texture coefficient [ TC (220) ] of the (220) plane of more than 1.28 (in comparative example 7), wrinkling and tearing occur.
According to the present invention, an electrolytic copper foil substantially free from wrinkle defects can be manufactured, and as a result, the electrolytic copper foil can be uniformly coated with a negative electrode active material when manufacturing a negative electrode for a secondary battery. Therefore, according to the present invention, short circuits of the secondary battery and delamination of the anode active material due to uneven coating of the anode active material can be prevented. As a result, according to the present invention, the life and capacity retention rate of the secondary battery can be improved.
Claims (14)
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 surface facing the first surface and a glossy surface facing the second surface;
a first protective layer on the matte surface; and
a second protective layer, on the glossy surface,
wherein the first surface and the second surface each have a profile maximum ratio PMR of 4.8 to 16.1, wherein the profile maximum ratio represents a maximum height roughness RmaxAnd arithmetic mean roughness RaRatio R ofmax/RaAnd an
The electrolytic copper foil has a texture coefficient [ TC (220) ] of the (220) face of 0.49 to 1.28]、35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
2. The electrolytic copper foil of claim 1, wherein the first surface and the second surface each have a maximum height roughness R of 1.2 μm to 3.7 μmmaxAnd an arithmetic average roughness R of 0.15 μm to 0.45 μma。
3. The electrolytic copper foil of claim 1, wherein the first protective layer and the second protective layer each contain chromium Cr.
4. The electrolytic copper foil of claim 1, wherein the electrolytic copper foil has a thickness of 4 μm to 30 μm.
5. A secondary 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 formed on the first surface,
wherein the electrolytic copper foil includes:
a copper layer comprising a matte surface facing the first surface and a glossy surface facing the second surface;
a first protective layer on the matte surface; and
a second protective layer, on the glossy surface,
wherein the first surface and the second surface each have a profile maximum ratio PMR of 4.8 to 16.1, wherein the profile maximum ratio represents a maximum height roughness RmaxAnd arithmetic mean roughness RaRatio R ofmax/RaAnd an
The electrolytic copper foil has a texture coefficient [ TC (220) ] of the (220) face of 0.49 to 1.28]、35kgf/mm2To 58kgf/mm2And a weight deviation of 3% or less.
6. The secondary battery electrode according to claim 5, wherein the first surface and the second surface each have a maximum height roughness R of 1.2 μm to 3.7 μmmaxAnd an arithmetic average roughness R of 0.15 μm to 0.45 μma。
7. The secondary battery electrode as claimed in claim 5, wherein the first protective layer and the second protective layer each contain chromium Cr.
8. The electrode for a secondary battery according to claim 5, wherein the electrolytic copper foil has a thickness of 4 μm to 30 μm.
9. The secondary battery electrode according to claim 5, further comprising: a second active material layer disposed on the second surface,
wherein the first active material layer and the second active material layer each include at least one active material selected from the group consisting of carbon, Si, a metal including Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe, an alloy containing the metal, an oxide of the metal, and a composite of the metal and carbon.
10. A secondary battery comprising:
a cathode;
an anode comprising the secondary battery electrode according to any one of claims 5to 9;
an electrolyte configured to provide an environment for lithium ions to move between the cathode and the anode; and
a separator configured to electrically insulate the anode from the cathode.
11. 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 comprising 70 to 90g/L of copper ions, 50 to 150g/L of sulfuric acid, 2 to 20mg/L of N-allylthiourea ATU, and 2 to 20mg/L of bis (3-sulfopropyl) -disulfide SPS; and
by making the density 40A/dm2To 80A/dm2From the electrode plate to the rotating electrode drumSo as to carry out the electroplating process,
wherein the surface of the rotary electrode drum is polished using a polishing brush having a particle size grid of #800 to #3000, and
the concentration of silver Ag in the electrolyte is maintained at 50mg/L or less when the plating is performed,
wherein:
when the electroplating is performed, the electrolyte is continuously filtered,
when continuous filtration is performed, the flow rate of the electrolyte ranges from 39m3Hr to 46m3/hr，
When the plating is performed, the variation in flow rate is 5%/sec or less.
12. The method of claim 11, wherein the step of preparing the electrolyte comprises:
heat-treating the copper wire at 600 ℃ to 900 ℃ for 30 minutes to 60 minutes;
pickling the heat-treated copper wire;
placing the acid-washed copper wire into sulfuric acid; and
ATU and SPS were added to the sulfuric acid charged with copper wire.
13. The method of claim 11, wherein the step of forming a copper layer further comprises: chloride ions that precipitate silver Ag as AgCl are added to the electrolyte to prevent the concentration of silver Ag in the electrolyte from exceeding 50 mg/L.
14. The method of claim 11, wherein the forming a protective layer comprises: the copper layer is immersed in a rust inhibitive solution containing 0.5g/L to 1.5g/L of Cr.
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| KR10-2017-0005857 | 2017-01-13 | ||
| KR1020170005857A KR20180083515A (en) | 2017-01-13 | 2017-01-13 | Electrolytic Copper Foil Substantially Free Of Wrinkle Problem, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
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| JP (1) | JP6545300B2 (en) |
| KR (1) | KR20180083515A (en) |
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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 |
| 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 |
| JP7087760B2 (en) * | 2018-07-18 | 2022-06-21 | 住友金属鉱山株式会社 | Copper-clad laminate |
| HUE058062T2 (en) * | 2018-08-08 | 2022-06-28 | Sk Nexilis Co Ltd | Copper foil with minimized bagginess and tear, electrode comprising 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 |
| HUE056946T2 (en) * | 2018-08-10 | 2022-04-28 | 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 |
| TWI679311B (en) * | 2018-08-10 | 2019-12-11 | 南韓商Ｋｃｆ科技有限公司 | Copper foil with minimized bagginess, wrinkle or tear, electrode including the same, secondary battery including the same and method for manufacturing the same |
| JP6767441B2 (en) * | 2018-08-16 | 2020-10-14 | 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 minimized sagging, wrinkles and tearing, electrodes containing it, secondary batteries containing it, and methods for manufacturing them. |
| TWI669032B (en) * | 2018-09-26 | 2019-08-11 | 金居開發股份有限公司 | Micro-rough electrolytic copper foil and copper foil substrate |
| US10581081B1 (en) * | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
| TWI700393B (en) * | 2019-08-27 | 2020-08-01 | 長春石油化學股份有限公司 | Electrolytic copper foil and electrode and lithium ion cell comprising the same |
| CN110699715A (en) * | 2019-10-21 | 2020-01-17 | 湖北中科铜箔科技有限公司 | Composite additive composition for preparing electrolytic copper foil and preparation method thereof |
| KR20210056073A (en) * | 2019-11-08 | 2021-05-18 | 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 |
| KR20210062204A (en) * | 2019-11-21 | 2021-05-31 | 에스케이넥실리스 주식회사 | Copper foil free from generation of wrinkle, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| 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 |
| US20220102730A1 (en) * | 2020-09-28 | 2022-03-31 | Industrial Technology Research Institute | Electrolytic copper foil and negative current collector of lithium secondary battery |
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| TWI659827B (en) | 2019-05-21 |
| JP6545300B2 (en) | 2019-07-17 |
| CN108306022A (en) | 2018-07-20 |
| TW201825285A (en) | 2018-07-16 |
| KR20180083515A (en) | 2018-07-23 |
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