WO2011129633A2 - Copper electrolysis solution for producing electrolytic copper foil, method of producing electrolytic copper foil, and electrolytic copper foil - Google Patents

Copper electrolysis solution for producing electrolytic copper foil, method of producing electrolytic copper foil, and electrolytic copper foil Download PDF

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WO2011129633A2
WO2011129633A2 PCT/KR2011/002670 KR2011002670W WO2011129633A2 WO 2011129633 A2 WO2011129633 A2 WO 2011129633A2 KR 2011002670 W KR2011002670 W KR 2011002670W WO 2011129633 A2 WO2011129633 A2 WO 2011129633A2
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Prior art keywords
copper foil
electrolytic copper
electrolysis solution
tensile strength
temperature
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PCT/KR2011/002670
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French (fr)
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WO2011129633A3 (en
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Duck Young Hwang
Jong Ho Ryu
Ki Deok Song
Chang Yol Yang
Sang Beom Kim
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Iljin Materials Co., Ltd.
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Publication of WO2011129633A2 publication Critical patent/WO2011129633A2/en
Publication of WO2011129633A3 publication Critical patent/WO2011129633A3/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Definitions

  • the present invention relates to a copper electrolysis solution for producing an electrolytic copper foil, a method of producing an electrolytic copper foil, and an electrolytic copper foil, and more particularly, to a copper electrolysis solution including a protein having a predetermined number average molecular weight, and an electrolytic copper foil that is produced by using the copper electrolysis solution and has high thermal stability at high temperature, low roughness, high strength, and high heat resistance.
  • a copper foil is used as a current collector for middle or large sized lithium batteries for use in hybrid electric vehicles (HEV).
  • HEV hybrid electric vehicles
  • a pressed copper foil formed by pressing is often used as a copper foil.
  • the pressed copper foil has high manufacturing costs, and is difficult to be made in a wide width.
  • lubricant oil is used during pressing.
  • an adhesion force between the pressed copper foil and an active material may be reduced due to contamination caused by the lubricant oil, thereby decreasing charge and discharge cycle characteristics.
  • a thin copper foil may have a limited thickness, it has a weak mechanical strength and thus, when a printed interconnection substrate is manufactured, crumpling or bending are likely to occur. Accordingly, a copper foil having a small thickness and high mechanical strength is required.
  • the present invention provides a copper electrolysis solution for producing an electrolytic copper foil.
  • the present invention also provides a method of manufacturing an electrolytic copper foil by using the copper electrolysis solution.
  • the present invention also provides an electrolytic copper foil produced by using the method.
  • a copper electrolysis solution for producing an electrolytic copper foil including a Cl - ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl - ion has a concentration of 0.5 to 1.5 ppm.
  • an electrolytic copper foil produced by using the method.
  • an electrolytic copper foil having low surface roughness, high tensile strength, and high thermal stability may be obtained.
  • FIG. 1 is a scanning electron microscope (SEM) image of a surface of an electrolytic copper foil manufactured according to Example 1.
  • FIG. 2 is a graph of tensile strength with respect to an annealing temperature of electrolytic copper foils manufactured according to Examples 1 and 5 and Comparative Examples 1, 6, and 9.
  • a copper electrolysis solution for producing an electrolytic copper foil includes a Cl - ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl - ion has a concentration of 0.5 to 1.5 ppm.
  • the collagen peptide may be a polypeptide that is prepared by decomposing gelatin extracting from bovine bones and skins, swine bones and skins, etc.
  • a source for the collagen peptide is not limited, and may be any one of collagen peptides that are obtained by decomposing all kinds of proteins.
  • a number average molecular weight of the collagen peptide may be, for example, 4,000 to 10,000.
  • the number average molecular weight of the collagen peptide may be, 5,000 to 8,000.
  • the number average molecular weight of the collagen peptide is less than 4,000, tensile strength and elongation of an electrolytic copper foil at high temperature may be reduced and a shape of grooves formed on a matte side of the electrolytic copper foil may have non-uniformity and thus the electrolytic copper foil has high roughness. If the number average molecular weight of the collagen peptide is greater than 10,000, tensile strength and elongation of an electrolytic copper foil at room temperature may be reduced and a shape of grooves formed on a matte side of the electrolytic copper foil may have non-uniformity and thus the electrolytic copper foil has high roughness.
  • a concentration of the collagen peptide may be, for example, 0.5 to 15 ppm.
  • a concentration of the collagen peptide may be 0.5 to 10 ppm.
  • the concentration of the collagen peptide is less than 0.5 ppm, the concentration of the collagen peptide in a sulfuric acid-copper sulfate electrolysis solution is low and thus an electrolytic copper foil formed using the electrolysis sotluion may have low tensile strength and low thermal stability at high temperature, and also, due to the low thermal stability at high temperature, the tensile strength of the electrolytic copper foil may be easily lowered.
  • the concentration of the collagen peptide is higher than 20 ppm, much copper powder may be generated and viscosity of the sulfuric acid-copper sulfate electrolysis solution may be too high, thereby generating bubbles in an electrolysis solution and pores in an electrolytic copper foil and thus tensile strength of the electrolytic copper foil may be lowered.
  • an electrolytic copper foil that is produced by reduction precipitation at a cathode drum that continuously rotates due to an electrochemical reaction in an electrolysis solution
  • high-speed plating is performed using a direct current that is often used to improve productivity.
  • thermal stability of the electrolytic copper foil may be substantially lowered at high temperature.
  • a small concentration of the Cl - ion is added to an electrolysis solution to improve thermal stability of an electrolytic copper foil.
  • the concentration of the Cl - ion is less than 0.5 ppm, the concentration of the Cl - ion in the sulfuric acid-copper sulfate electrolysis solution is low, an electrolytic copper foil formed by using the copper electrolysis solution may have low room-temperature tensile strength and thermal stability at high temperature may be lowered.
  • the concentration of the Cl - ion is higher than 1.5 ppm, a surface roughness of a matte side of the electrolytic copper foil may be increased and thus it is difficult to produce an electrolytic copper foil having low roughness, and the formed electrolytic copper foil may have low room-temperature tensile strength and low thermal stability at high temperature.
  • an electrolytic copper foil produced from a copper electrolysis solution including collagen peptide having the number average molecular weight range and the concentration range may have high mechanical strength and a matte side having low surface roughness and mechanical strength.
  • a copper electrolysis solution for producing an electrolytic copper foil includes a solvent, a Cu 2+ ion, a SO 4 2- ion, a Cl - ion, and a collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl - ion has a concentraton of 0.5 to 1.5 ppm.
  • a copper foil that is generated by electro-plating has two different sides: a shiny side (S side) contacting a cathode drum and a matte side (M side) contacting an electrolysis solution on which crystal granules grow by reduction deposition.
  • surface roughness of the matte side is affected by surface roughness of the shiny side. For example, the lower the surface roughness of the shiny side, the lower the surface roughness of the matte side.
  • a surface roughness (Rz) of a shiny side of an electrolytic copper foil produced by using the copper electrolysis solution may be 1.5 ⁇ m or less.
  • a surface roughness (Rz) of a matte side (M side) of an electrolytic copper foil produced by using the copper electrolysis solution may be 1.5 ⁇ m or less.
  • the surface roughness of the matte side of the electrolytic copper foil may be 0.5 to 1.5 ⁇ m.
  • the surface roughness of the matte side of the electrolytic copper foil may be 0.8 to 1.5 ⁇ m. If the surface roughness of the matte side is higher than 2.0 ⁇ m, a contacting area between the electrolytic copper foil as a current collector for a cathode and an active material may be reduced, and thus, charge and discharge cycle lifetime may be reduced and high electric capacity at initial charging may be difficult to be maintained.
  • a room-temperature tensile strength of the electrolytic copper foil may be 50 to 70 kg/mm 2 .
  • a tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250°C for 1 hour, that is, high-temperature tensile strength of the electrolytic copper foil, may be 70% or more of a room-temperature tensile strength of the electrolytic copper foil.
  • the room-temperature tensile strength refers to a tensile strength of a copper foil obtained at room temperature without performing a high-temperature heat treatment.
  • a concentration of Cu 2+ ion in a sulfuric acid-copper sulfate copper electrolysis solution may be 70 g/L to 150 g/L, but is not limited thereto.
  • the concentration of Cu 2+ ion in the sulfuric acid-copper sulfate copper electrolysis solution may be appropriately controlled as long as the objectives of the present invention are achieved.
  • the concentration of Cu 2+ may be 85 g/L to 100 g/L.
  • a concentration of the free SO 4 2- refers to a concentration of the residual SO 4 2- formed by substracting the concentration of SO 4 2- calculated from conversion of the Cu 2+ concentration in the copper electrolyte solution to CuSO 4 from the total SO 4 2- concentration in the copper electrolyte solution.
  • the concentration of the free SO 4 2- may be 50 g/L to 200 g/L, but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved.
  • the concentration of SO 4 2- may be 80 g/L to 150 g/L.
  • the copper electrolysis solution may be prepared by using any known method.
  • the concentration of the Cu 2+ may be adjusted by controlling a concentration of a copper sulfate
  • the concentration of SO 4 2- ion may be adjusted by controlling a concentration of a sulfuric acid and copper sulfate.
  • the concentration and the number average molecular weight of the collagen polypeptide included in the copper electrolysis solution may be calculated from an amount and a number average molecular weight of collagen polypeptide added to the copper electrolysis solution, or may be obtained by analyzing the collagen polypeptide included in the copper electrolysis solution by any known method, such as column chromatography.
  • a method of producing an electrolytic copper foil according to an embodiment of the present invention is performed by using the copper electrolysis solution for producing an electrolytic copper foil.
  • the method of producing an electrolytic copper foil may be the same as a known method, except that the copper electrolysis solution as described above is used.
  • a copper electrolysis solution is supplied between the curved surface of a revolving drum-shaped titanium cathode and an anode to conduct electrolysis, thereby depositing in the form of a deposited foil on the surface of the cathode and continuously taking up the foil.
  • a temperature of the copper electrolysis solution used in the method may be 45 to 65°C, but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved.
  • the temperature of the copper electrolysis solution may be 50 to 60°C.
  • a current density used in the method may be 40 to 100 A/dm 2 , but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved.
  • the current density may be 50 to 80 A/dm 2 .
  • An electrolytic copper foil according to an embodiment of the present invention may be produced by using the method described above.
  • the electrolytic copper foil produced by using the method described above may have a matte side having a surface roughness (Rz) of 1.5 ⁇ m or less.
  • the surface roughness of the electrolytic copper foil may be 0.5 to 1.5 ⁇ m.
  • the surface roughness of the electrolytic copper foil may be 0.8 to 1.5 ⁇ m. If the surface roughness of the electrolytic copper foil is 1.5 ⁇ m or more, a contacting area between the electrolytic copper foil as a current collector for a cathode and an active material may be reduced, and thus, charge and discharge cycle lifetime may be reduced and high electric capacity at initial charging may be difficult to be maintained.
  • a tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250°C for 1 hour may be 70% or more of the room-temperature tensile strength.
  • the room-temperature tensile strength refers to a tensile strength of a copper foil obtained at room temperature without performing a high-temperature heat treatment.
  • FIG. 1 shows a scanning electron microscope (SEM) image of a surface of the electrolytic copper foil.
  • Table 1 shows compositions of electrolysis solutions used in Examples 1-6 and Comparative Examples 1-9.
  • Example 1 Thickness( ⁇ m) Temperature(°C) Current density(A/dm 2 ) Basic composition Collagen peptide Cu(g/L) SO 4 2- (g/L) Cl(ppm) Molecular weight Concentration(ppm)
  • Example 1 18 50 60 87.5 125 1 7,000 1
  • Example 2 18 50 60 87.5 125 1 4,000 1
  • Example 3 18 50 60 87.5 125 1 10,000 1
  • Example 4 18 50 60 87.5 125 1 7,000 0.5
  • Example 5 18 50 60 87.5 125 1 7,000 5
  • Example 6 18 50 60 87.5 125 1 7,000 10
  • Comparative Example 1 18 50 60 87.5 125 1 - - Comparative Example 2 18 50 60 87.5 125 1 3,000 1 Comparative Example 3 18 50 60 87.5 125 1 20,000 1 Comparative Example 4 18 50 60 87.5 125 1 7,000 0.05 Comparative Example 5 18 50 60 87.5 125 1 7,000 30
  • Comparative Example 6 18 50 60 87.5 125 1 7,000 50 Comparative Example 7 18 50 60 8
  • a tensile sample having a width of 12.7 mm and a gage length of 50 mm was collected from each of electrolytic copper foils produced according to Examples 1 to 5 and Comparative Examples 1 to 8, and then a tensile strength test was performed thereon at a crosshead speed of 50.8 mm/min according to IPC-TM-650 2.4.18B criteria.
  • a maximum weight of a tensile strength was referred to as a room-temperature tensile strength, and an elongation when the electrolytic copper foils were broken was referred to as a room-temperature elongation.
  • the room-temperature tensile strengths and the room-temperature elongations evaluated as described above are shown in Table 2 below.
  • Example 1 1.03 1.04 62.43 6.16
  • Example 2 1.07 1.19 59.97 4.02
  • Example 3 1.12 1.44 59.74 4.78
  • Example 4 1.09 1.34 60.15 4.77
  • Example 5 1.17 1.28 61.07 4.26
  • Example 6 1.12 1.27 61.17 4.85 Comparative Example 1 1.85 1.79 50.83 2.59 Comparative Example 2 1.78 1.71 51.55 2.61 Comparative Example 3 1.76 1.74 52.51 3.28 Comparative Example 4 1.89 1.75 51.91 2.59 Comparative Example 5 1.98 1.82 47.15 2.01 Comparative Example 6 2.37 1.83 42.18 1.77 Comparative Example 7 1.15 1.81 50.38 1.77 Comparative Example 8 2.63 1.85 48.42 2.25 Comparative Example 9 3.55 1.93 38.29 1.95
  • the electrolytic copper foils of Examples 1 to 6 have lower surface roughness and higher room-temperature tensile strength and elongation than the electrolytic copper foils of Comparative Examples 1 to 9.
  • each of electrolytic copper foils produced according to Examples 1 to 6 and Comparative Example s1 to 9 was not heat treated, or annealed at temperatures of 100°C, 150°C, 200°C, and 250°C, each for 1 hour. Then, a tensile test was performed thereon with a crosshead speed of 50.8 mm/min according to IPC-TM-650 2.4.18B criteria, and then, tensile strength was measured at room temperature. The room temperature was 25°C.
  • a tensile strength according to a heat treatment temperature obtained by using the evaluation method is shown in Table 3 and FIG. 2.
  • the tensile test on the electrolytic copper foils of Examples 1-6 that had been annealed at a temperature of 100 to 250°C for 1 hour has the flowing results.
  • a tensile strength after the annealing was performed at a temperature of 250°C was 70% or more of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed.
  • Comparative Examples 1-9 a tensile strength after the annealing was performed at a temperature of 250°C was 60% or less of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed. Accordingly, a decrease in tensile strength of each of the electrolytic copper foils of Examples 1-6 according to increasing temperature was relatively low.
  • a tensile strength after the annealing was performed at a temperature of 250°C was 40% or less of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed.
  • the tensile strength of the electrolytic copper foil of Comparative Example 6 according to a heat treatment temperature increase was significantly decreased. Accordingly, it was confirmed that the electrolytic copper foils of the comparative examples have low thermal stability and thus are not suitable for use as a current collector for a lithium battery.
  • an electrolytic copper foil having low surface roughness, high tensile strength, and high thermal stability may be obtained.

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Abstract

Provided is a copper electrolysis solution for producing an electrolytic copper foil, according to an embodiment of the present invention, includes a Cl- ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl-ion has a concentration of 0.5 to 1.5 ppm. The copper electrolysis solution may provide an electrolytic copper foil having a relatively simple manufacturing process, high thermal stability, low roughness, and high strength. The electrolytic copper foil may be used as a current collector for middle or large-sized lithium ion secondary batteries for use in hybrid electric vehicles and as a semiconductor packing substrate for tape automated bonding (TAB) used in a tape carrier package (TCP).

Description

COPPER ELECTROLYSIS SOLUTION FOR PRODUCING ELECTROLYTIC COPPER FOIL, METHOD OF PRODUCING ELECTROLYTIC COPPER FOIL, AND ELECTROLYTIC COPPER FOIL
The present invention relates to a copper electrolysis solution for producing an electrolytic copper foil, a method of producing an electrolytic copper foil, and an electrolytic copper foil, and more particularly, to a copper electrolysis solution including a protein having a predetermined number average molecular weight, and an electrolytic copper foil that is produced by using the copper electrolysis solution and has high thermal stability at high temperature, low roughness, high strength, and high heat resistance.
In general, a copper foil is used as a current collector for middle or large sized lithium batteries for use in hybrid electric vehicles (HEV). A pressed copper foil formed by pressing is often used as a copper foil. However, the pressed copper foil has high manufacturing costs, and is difficult to be made in a wide width.
Also, during pressing, lubricant oil is used. Thus, an adhesion force between the pressed copper foil and an active material may be reduced due to contamination caused by the lubricant oil, thereby decreasing charge and discharge cycle characteristics.
Lithium batteries undergo a volumetric change during charge and discharge and dissipate heat due to overcharge. Also, in order to improve an adhesive force with the active material, a surface roughness of the copper foil needs to be lowered. Accordingly, there is a need to develop a copper foil that endures the volumetric change and the heat dissipation of a lithium battery, and has a strong adhesion force with the active material, high heat resistance, high strength, and low roughness.
Meanwhile, demand for fine wiring in a semiconductor mount substrate and/or a main board substrate to increase a degree of integration in a relatively small area in response to demand for small, lightweight, and high-performance electronic devices is increasing. If a thick copper foil is used in manufacturing a printed interconnection plate having a fine pattern, an etching time for forming an interconnection circuit may be long and vertical characteristics of a side wall may be degraded. In particular, if a wiring pattern formed by etching has a small line width, the formed wiring can be disconnected. Accordingly, a thinner copper foil is required to obtain a fine pitch circuit. However, since a thin copper foil may have a limited thickness, it has a weak mechanical strength and thus, when a printed interconnection substrate is manufactured, crumpling or bending are likely to occur. Accordingly, a copper foil having a small thickness and high mechanical strength is required.
The present invention provides a copper electrolysis solution for producing an electrolytic copper foil.
The present invention also provides a method of manufacturing an electrolytic copper foil by using the copper electrolysis solution.
The present invention also provides an electrolytic copper foil produced by using the method.
According to an aspect of the present invention, there is provided a copper electrolysis solution for producing an electrolytic copper foil, including a Cl- ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl- ion has a concentration of 0.5 to 1.5 ppm.
According to another aspect of the present invention, there is provided a method of producing an electrolytic copper foil using the copper electrolysis solution described above.
According to another aspect of the present invention, there is provided an electrolytic copper foil produced by using the method.
According to the one or more embodiments of the present invention, due to use of a copper electrolysis solution including a protein having a predetermined molecular weight and a predetermined concentration, an electrolytic copper foil having low surface roughness, high tensile strength, and high thermal stability may be obtained.
FIG. 1 is a scanning electron microscope (SEM) image of a surface of an electrolytic copper foil manufactured according to Example 1.
FIG. 2 is a graph of tensile strength with respect to an annealing temperature of electrolytic copper foils manufactured according to Examples 1 and 5 and Comparative Examples 1, 6, and 9.
Hereinafter, a copper electrolysis solution for producing an electrolytic copper foil, a method of producing an electrolytic copper foil by using the copper electrolysis solution, and an electrolytic copper foil produced by using the method, according to one or more embodiments of the present invention, will be described in detail.
A copper electrolysis solution for producing an electrolytic copper foil, according to an embodiment of the present invention, includes a Cl- ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl- ion has a concentration of 0.5 to 1.5 ppm.
The collagen peptide may be a polypeptide that is prepared by decomposing gelatin extracting from bovine bones and skins, swine bones and skins, etc. A source for the collagen peptide is not limited, and may be any one of collagen peptides that are obtained by decomposing all kinds of proteins. A number average molecular weight of the collagen peptide may be, for example, 4,000 to 10,000. For example, the number average molecular weight of the collagen peptide may be, 5,000 to 8,000.
If the number average molecular weight of the collagen peptide is less than 4,000, tensile strength and elongation of an electrolytic copper foil at high temperature may be reduced and a shape of grooves formed on a matte side of the electrolytic copper foil may have non-uniformity and thus the electrolytic copper foil has high roughness. If the number average molecular weight of the collagen peptide is greater than 10,000, tensile strength and elongation of an electrolytic copper foil at room temperature may be reduced and a shape of grooves formed on a matte side of the electrolytic copper foil may have non-uniformity and thus the electrolytic copper foil has high roughness.
A concentration of the collagen peptide may be, for example, 0.5 to 15 ppm. For example, a concentration of the collagen peptide may be 0.5 to 10 ppm.
If the concentration of the collagen peptide is less than 0.5 ppm, the concentration of the collagen peptide in a sulfuric acid-copper sulfate electrolysis solution is low and thus an electrolytic copper foil formed using the electrolysis sotluion may have low tensile strength and low thermal stability at high temperature, and also, due to the low thermal stability at high temperature, the tensile strength of the electrolytic copper foil may be easily lowered. On the other hand, if the concentration of the collagen peptide is higher than 20 ppm, much copper powder may be generated and viscosity of the sulfuric acid-copper sulfate electrolysis solution may be too high, thereby generating bubbles in an electrolysis solution and pores in an electrolytic copper foil and thus tensile strength of the electrolytic copper foil may be lowered.
Regarding an electrolytic copper foil that is produced by reduction precipitation at a cathode drum that continuously rotates due to an electrochemical reaction in an electrolysis solution, high-speed plating is performed using a direct current that is often used to improve productivity. However, if an electrolytic copper foil is produced by using such a method using high-speed plating, thermal stability of the electrolytic copper foil may be substantially lowered at high temperature. To solve this problem, according to the present invention, a small concentration of the Cl- ion is added to an electrolysis solution to improve thermal stability of an electrolytic copper foil.
If a small concentration of the Cl- ion is included in an electrolysis solution, many initial nucleus generation sites are generated during electrolysis plating and thus, fine crystal grains are generated and precipitates of CuCl2 formed at an intergranular boundary may hinder crystal growth during heated at high temperature, thereby increasing thermal stability at high temperature.
If the concentration of the Cl- ion is less than 0.5 ppm, the concentration of the Cl- ion in the sulfuric acid-copper sulfate electrolysis solution is low, an electrolytic copper foil formed by using the copper electrolysis solution may have low room-temperature tensile strength and thermal stability at high temperature may be lowered. On the other hand, if the concentration of the Cl- ion is higher than 1.5 ppm, a surface roughness of a matte side of the electrolytic copper foil may be increased and thus it is difficult to produce an electrolytic copper foil having low roughness, and the formed electrolytic copper foil may have low room-temperature tensile strength and low thermal stability at high temperature.
That is, an electrolytic copper foil produced from a copper electrolysis solution including collagen peptide having the number average molecular weight range and the concentration range may have high mechanical strength and a matte side having low surface roughness and mechanical strength.
A copper electrolysis solution for producing an electrolytic copper foil, according to another embodiment of the present invention, includes a solvent, a Cu2+ ion, a SO4 2- ion, a Cl- ion, and a collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl- ion has a concentraton of 0.5 to 1.5 ppm.
In general, a copper foil that is generated by electro-plating has two different sides: a shiny side (S side) contacting a cathode drum and a matte side (M side) contacting an electrolysis solution on which crystal granules grow by reduction deposition. Also, surface roughness of the matte side is affected by surface roughness of the shiny side. For example, the lower the surface roughness of the shiny side, the lower the surface roughness of the matte side. A surface roughness (Rz) of a shiny side of an electrolytic copper foil produced by using the copper electrolysis solution may be 1.5 ㎛ or less.
A surface roughness (Rz) of a matte side (M side) of an electrolytic copper foil produced by using the copper electrolysis solution may be 1.5 ㎛ or less. For example, the surface roughness of the matte side of the electrolytic copper foil may be 0.5 to 1.5 ㎛. For example, the surface roughness of the matte side of the electrolytic copper foil may be 0.8 to 1.5 ㎛. If the surface roughness of the matte side is higher than 2.0 ㎛, a contacting area between the electrolytic copper foil as a current collector for a cathode and an active material may be reduced, and thus, charge and discharge cycle lifetime may be reduced and high electric capacity at initial charging may be difficult to be maintained.
A room-temperature tensile strength of the electrolytic copper foil may be 50 to 70 kg/mm2. A tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250℃ for 1 hour, that is, high-temperature tensile strength of the electrolytic copper foil, may be 70% or more of a room-temperature tensile strength of the electrolytic copper foil. The room-temperature tensile strength refers to a tensile strength of a copper foil obtained at room temperature without performing a high-temperature heat treatment.
A concentration of Cu2+ ion in a sulfuric acid-copper sulfate copper electrolysis solution may be 70 g/L to 150 g/L, but is not limited thereto. The concentration of Cu2+ ion in the sulfuric acid-copper sulfate copper electrolysis solution may be appropriately controlled as long as the objectives of the present invention are achieved. For example, the concentration of Cu2+ may be 85 g/L to 100 g/L.
A concentration of the free SO4 2- refers to a concentration of the residual SO4 2- formed by substracting the concentration of SO4 2- calculated from conversion of the Cu2+ concentration in the copper electrolyte solution to CuSO4 from the total SO4 2- concentration in the copper electrolyte solution. The concentration of the free SO4 2- may be 50 g/L to 200 g/L, but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved. For example, the concentration of SO4 2- may be 80 g/L to 150 g/L.
The copper electrolysis solution may be prepared by using any known method. For example, the concentration of the Cu2+ may be adjusted by controlling a concentration of a copper sulfate, and the concentration of SO4 2- ion may be adjusted by controlling a concentration of a sulfuric acid and copper sulfate. The concentration and the number average molecular weight of the collagen polypeptide included in the copper electrolysis solution may be calculated from an amount and a number average molecular weight of collagen polypeptide added to the copper electrolysis solution, or may be obtained by analyzing the collagen polypeptide included in the copper electrolysis solution by any known method, such as column chromatography.
A method of producing an electrolytic copper foil according to an embodiment of the present invention is performed by using the copper electrolysis solution for producing an electrolytic copper foil. The method of producing an electrolytic copper foil may be the same as a known method, except that the copper electrolysis solution as described above is used.
An example of the method of producing the electrolytic copper foil will now be described in detail.
A copper electrolysis solution is supplied between the curved surface of a revolving drum-shaped titanium cathode and an anode to conduct electrolysis, thereby depositing in the form of a deposited foil on the surface of the cathode and continuously taking up the foil.
A temperature of the copper electrolysis solution used in the method may be 45 to 65℃, but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved. For example, the temperature of the copper electrolysis solution may be 50 to 60℃.
A current density used in the method may be 40 to 100 A/dm2, but is not limited thereto, and may be appropriately controlled as long as the objectives of the present invention are achieved. For example, the current density may be 50 to 80 A/dm2.
An electrolytic copper foil according to an embodiment of the present invention may be produced by using the method described above.
The electrolytic copper foil produced by using the method described above may have a matte side having a surface roughness (Rz) of 1.5 ㎛ or less. For example, the surface roughness of the electrolytic copper foil may be 0.5 to 1.5 ㎛. For example, the surface roughness of the electrolytic copper foil may be 0.8 to 1.5 ㎛. If the surface roughness of the electrolytic copper foil is 1.5 ㎛ or more, a contacting area between the electrolytic copper foil as a current collector for a cathode and an active material may be reduced, and thus, charge and discharge cycle lifetime may be reduced and high electric capacity at initial charging may be difficult to be maintained.
A tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250℃ for 1 hour may be 70% or more of the room-temperature tensile strength. The room-temperature tensile strength refers to a tensile strength of a copper foil obtained at room temperature without performing a high-temperature heat treatment.
Hereinafter, examples of the present invention will be described in detail, but the present invention is not limited thereto.
(Production of Electrolytic Copper Foil)
Examples 1-6 and Comparative Examples 1-9
In order to produce an electrolytic copper foil by an electrochemical system, a 3L-capacity electrolytic cell system that circulates at a rate of 20 L/min was used and a temperature of an electrolysis solution was maintained at 50℃. A dimensionally stable electrode (DSE) plate having a thickness of 5 mm and a size of 10×10 cm2 was used as an anode, and a titanium electrode plate having the same size and thickness was used as a cathode. A copper electrolysis solution used included 87.5 g/L of Cu2+ and 125 g/L of SO4 2- . All examples used a Cl- ion except for Comparative Example 7.
All examples used a collagen peptide (C&A Biotech, Collagen peptide) except for Comparative Example 1.
A distance between the cathode and the anode was maintained at 10 cm, and plating was performed with a current density of 60 A/dm2 so as to allow Cu2+ ions to flow smoothly, and an electrolytic copper foil having a thickness of 18 ㎛ was produced. FIG. 1 shows a scanning electron microscope (SEM) image of a surface of the electrolytic copper foil.
Table 1 shows compositions of electrolysis solutions used in Examples 1-6 and Comparative Examples 1-9.
Table 1
Thickness(㎛) Temperature(℃) Current density(A/dm2) Basic composition Collagen peptide
Cu(g/L) SO4 2- (g/L) Cl(ppm) Molecular weight Concentration(ppm)
Example 1 18 50 60 87.5 125 1 7,000 1
Example 2 18 50 60 87.5 125 1 4,000 1
Example 3 18 50 60 87.5 125 1 10,000 1
Example 4 18 50 60 87.5 125 1 7,000 0.5
Example 5 18 50 60 87.5 125 1 7,000 5
Example 6 18 50 60 87.5 125 1 7,000 10
Comparative Example 1 18 50 60 87.5 125 1 - -
Comparative Example 2 18 50 60 87.5 125 1 3,000 1
Comparative Example 3 18 50 60 87.5 125 1 20,000 1
Comparative Example 4 18 50 60 87.5 125 1 7,000 0.05
Comparative Example 5 18 50 60 87.5 125 1 7,000 30
Comparative Example 6 18 50 60 87.5 125 1 7,000 50
Comparative Example 7 18 50 60 87.5 125 - 7,000 1
Comparative Example 8 18 50 60 87.5 125 2 7,000 1
Comparative Example 9 18 50 60 87.5 125 5 7,000 1
Evaluation Example 1: Evaluation of Surface Roughness (Rz)
Surface roughness (Rz) of a matte side and a shiny side of each of electrolytic copper foils produced according to Examples 1 to 6 and Comparative Examples 1 to 9 was evaluated according to JISB 0601-1994 criteria. The evaluated surface roughness (Rz) values are shown in Table 2 below. The lower the Rz value, the lower a degree of roughness.
Evaluation Example 2: Evaluation of Room-Temperature Tensile Strength and Room-Temperature Elongation
A tensile sample having a width of 12.7 mm and a gage length of 50 mm was collected from each of electrolytic copper foils produced according to Examples 1 to 5 and Comparative Examples 1 to 8, and then a tensile strength test was performed thereon at a crosshead speed of 50.8 mm/min according to IPC-TM-650 2.4.18B criteria. A maximum weight of a tensile strength was referred to as a room-temperature tensile strength, and an elongation when the electrolytic copper foils were broken was referred to as a room-temperature elongation. The room-temperature tensile strengths and the room-temperature elongations evaluated as described above are shown in Table 2 below.
Table 2
Surface roughness Room-temperature tensile strength[kgf/mm2] Room-temperature elongation[%]
Matte side (M side)(Rz)[㎛] Shiny side(S side)(Rz)[㎛]
Example 1 1.03 1.04 62.43 6.16
Example 2 1.07 1.19 59.97 4.02
Example 3 1.12 1.44 59.74 4.78
Example 4 1.09 1.34 60.15 4.77
Example 5 1.17 1.28 61.07 4.26
Example 6 1.12 1.27 61.17 4.85
Comparative Example 1 1.85 1.79 50.83 2.59
Comparative Example 2 1.78 1.71 51.55 2.61
Comparative Example 3 1.76 1.74 52.51 3.28
Comparative Example 4 1.89 1.75 51.91 2.59
Comparative Example 5 1.98 1.82 47.15 2.01
Comparative Example 6 2.37 1.83 42.18 1.77
Comparative Example 7 1.15 1.81 50.38 1.77
Comparative Example 8 2.63 1.85 48.42 2.25
Comparative Example 9 3.55 1.93 38.29 1.95
As shown in Table 2, the electrolytic copper foils of Examples 1 to 6 have lower surface roughness and higher room-temperature tensile strength and elongation than the electrolytic copper foils of Comparative Examples 1 to 9.
Evaluation Example 3: Evaluation of Tensile Strength according to Heat Treatment Temperature
In order to evaluate thermal stability of an electrolytic copper foil, each of electrolytic copper foils produced according to Examples 1 to 6 and Comparative Example s1 to 9 was not heat treated, or annealed at temperatures of 100℃, 150℃, 200℃, and 250℃, each for 1 hour. Then, a tensile test was performed thereon with a crosshead speed of 50.8 mm/min according to IPC-TM-650 2.4.18B criteria, and then, tensile strength was measured at room temperature. The room temperature was 25℃.
A tensile strength according to a heat treatment temperature obtained by using the evaluation method is shown in Table 3 and FIG. 2.
Table 3
Tensile strength according to heat treatment temperature (kgf/mm2)
No heat treatment 100℃ 150℃ 200℃ 250℃
Example 1 62.43 56.61 53.52 49.57 48.58
Example 2 59.97 55.41 52.78 48.98 46.77
Example 3 59.74 57.01 53.97 48.87 45.14
Example 4 60.15 55.97 52.41 47.57 46.01
Example 5 61.07 56.44 54.35 55.84 51.59
Example 6 61.17 55.74 53.14 49.75 48.98
Comparative Example 1 50.83 48.53 31.78 27.28 26.29
Comparative Example 2 51.55 44.42 39.52 36.14 29.97
Comparative Example 3 50.54 45.99 43.73 30.14 26.71
Comparative Example 4 51.91 50.11 30.05 25.38 22.94
Comparative Example 5 47.15 46.52 38.24 33.14 29.85
Comparative Example 6 42.18 38.45 30.57 28.74 23.04
Comparative Example 7 50.38 49.49 29.95 26.28 24.01
Comparative Example 8 48.42 47.58 41.31 35.76 31.41
Comparative Example 9 38.29 34.51 36.29 32.21 30.85
As shown in Table 2 and FIG. 2, the tensile test on the electrolytic copper foils of Examples 1-6 that had been annealed at a temperature of 100 to 250℃ for 1 hour has the flowing results. A tensile strength after the annealing was performed at a temperature of 250℃ was 70% or more of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed. However, regarding Comparative Examples 1-9, a tensile strength after the annealing was performed at a temperature of 250℃ was 60% or less of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed. Accordingly, a decrease in tensile strength of each of the electrolytic copper foils of Examples 1-6 according to increasing temperature was relatively low.
Also, as shown in FIG. 2, regarding the electrolytic copper foils of Comparative Examples 1, 6, and 9, a tensile strength after the annealing was performed at a temperature of 250℃ was 40% or less of a room-temperature tensile strength of an electrolytic copper foil that had not been annealed. In particular, the tensile strength of the electrolytic copper foil of Comparative Example 6 according to a heat treatment temperature increase was significantly decreased. Accordingly, it was confirmed that the electrolytic copper foils of the comparative examples have low thermal stability and thus are not suitable for use as a current collector for a lithium battery.
According to the one or more embodiments of the present invention, due to use of a copper electrolysis solution including a protein having a predetermined molecular weight and a predetermined concentration, an electrolytic copper foil having low surface roughness, high tensile strength, and high thermal stability may be obtained.

Claims (9)

  1. A copper electrolysis solution for producing an electrolytic copper foil, comprising a Cl- ion, and collagen peptide, wherein the collagen peptide has a number average molecular weight of 4,000 to 10,000 and a concentration of 0.5 to 20 ppm, and the Cl- ion has a concentration of 0.5 to 1.5 ppm.
  2. The copper electrolysis solution of claim 1, wherein the electrolytic copper foil has a matte side having a surface roughness (Rz) is 1.5 ㎛ or less.
  3. The copper electrolysis solution of claim 1, wherein the electrolytic copper foil has a room-temperature tensile strength of 50 to 70 kg/mm2.
  4. The copper electrolysis solution of claim 1, wherein a tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250℃ for 1 hour is 70% or more of a room-temperature tensile strength of the electrolytic copper foil.
  5. A method of producing an electrolytic copper foil using the copper electrolysis solution of any one of claims 1-4.
  6. An electrolytic copper foil produced by using the method of claim 5.
  7. The electrolytic copper foil of claim 6, wherein the electrolytic copper foil has a matte side (M side) and a shiny side (S side), wherein a surface roughness (Rz) of the M side is 1.5 ㎛ or lower and a surface roughness (Rz) of the shiny side (S side) is 1.5㎛ or lower.
  8. The electrolytic copper foil of claim 6, wherein the electrolytic copper foil has a room-temperature tensile strength of 50 to 70 kg/mm2.
  9. The electrolytic copper foil of claim 6, wherein a tensile strength of the electrolytic copper foil after the electrolytic copper foil is annealed at a temperature of 250℃ for 1 hour is 70% or more of a room-temperature tensile strength of the electrolytic copper foil.
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