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WO2012002526A1 - Feuille de cuivre électrolytique et son procédé de production - Google Patents

Feuille de cuivre électrolytique et son procédé de production Download PDF

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Publication number
WO2012002526A1
WO2012002526A1 PCT/JP2011/065147 JP2011065147W WO2012002526A1 WO 2012002526 A1 WO2012002526 A1 WO 2012002526A1 JP 2011065147 W JP2011065147 W JP 2011065147W WO 2012002526 A1 WO2012002526 A1 WO 2012002526A1
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WIPO (PCT)
Prior art keywords
copper foil
electrolytic copper
negative electrode
tensile strength
iodine
Prior art date
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Ceased
Application number
PCT/JP2011/065147
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English (en)
Japanese (ja)
Inventor
咲子 朝長
慎太郎 稲場
吉岡　淳志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to KR1020127029126A priority Critical patent/KR101385760B1/ko
Priority to CN201180032383.5A priority patent/CN102959135B/zh
Priority to JP2012522711A priority patent/JP5373970B2/ja
Priority to KR1020147000272A priority patent/KR101385761B1/ko
Publication of WO2012002526A1 publication Critical patent/WO2012002526A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolytic copper foil and a method for producing the electrolytic copper foil.
  • the present invention relates to an electrolytic copper foil that has physical properties such as tensile strength and elongation suitable for a current collector application for a lithium ion secondary battery, and that can be used in the production of a copper-clad laminate for producing a printed wiring board. .
  • Lithium-ion secondary batteries have become popular as useful power sources that can be used repeatedly due to the recent increase in environmental protection awareness and the increasing demand for recycling resources. Used in products such as telephones, televisions, and video cameras. Along with the downsizing of these electric products and electronic devices, lithium ion secondary batteries as a power supply source are required to exhibit small size, long life, light weight, and high energy density.
  • Patent Document 1 In the manufacturing process of the negative electrode of this lithium ion secondary battery, as disclosed in Patent Document 1 or Patent Document 2, there is a process in which a high temperature is applied. In that process, high temperature is also applied to the copper foil which is the negative electrode current collector constituting the negative electrode. As a result, when the copper foil is softened, there is a problem that the lithium ion secondary battery is easily affected by deformation stress accompanying expansion and contraction of the negative electrode active material when charging and discharging are repeated.
  • electrolytic copper foil since the electrolytic copper foil hardly recrystallizes due to heating and is difficult to soften, it has been considered that the electrolytic copper foil has a strong resistance to expansion / contraction stress when the above charge / discharge is repeated.
  • electrolytic copper foil is cheaper than rolled copper foil, it becomes possible to increase profitability from the viewpoint of the price of lithium ion secondary batteries in the market, so as an alternative to rolled copper foil.
  • the use of electrolytic copper foil has been actively studied. As a result, at present, an electrolytic copper foil having a low profile surface comparable to that of a rolled copper foil on both sides is widely used for negative electrode current collector applications of lithium ion secondary batteries.
  • Patent Document 4 As a technique related to the electrolytic copper foil having a low profile surface comparable to the rolled copper foil on both sides Inventions have been made in which the electrolytic solution composition, electrolytic solution temperature, current density, etc. of the copper electrolytic solution used for the production of the electrolytic copper foil are controlled.
  • Patent Document 3 for the purpose of producing an electrodeposited copper foil excellent in etching property and impedance controllability useful for the production of a printed circuit board, “(A) flowing an electrolytic solution between an anode and a cathode, And applying an effective amount of voltage between the anode and the cathode such that copper is deposited on the cathode; wherein the electrolytic solution comprises copper ions, sulfate ions and at least one organic additive or derivative thereof.
  • the solution has a chloride ion concentration of up to about 1 ppm; the current density ranges from about 0.1 to about 5 A / cm 2 ; and (B) includes removing the copper foil from the cathode Is used. That is, electrolysis conditions using a copper electrolyte with a controlled chlorine concentration are employed.
  • Patent Document 4 0.05 to 2.0 ppm by weight of thiourea or a derivative thereof; 0.08 to 12 ppm by weight of a high molecular weight polysaccharide; and a molecular weight of 10,000 or less as additives.
  • An electrolysis condition characterized by using an electrolytic solution containing 0.03 to 4.0 weight ppm of glue is employed.
  • an electrolytic copper foil in which the surface roughness of the deposited surface of the electrolytic copper foil is close to the surface roughness level of the rolled copper foil can be produced.
  • Patent Document 5 the electrolytic copper foils described in Patent Documents 3, 4 and 4 having a refined crystal structure and reduced surface roughness are marketed in terms of charge / discharge cycle life and overcharge characteristics. It is pointed out that the situation is not enough to meet the needs of In this patent document 5, the surface smoothness, room temperature tensile strength, elongation rate, non-recrystallization property, high temperature atmosphere that cannot be expressed by the ten-point average roughness Rz as the characteristics of the copper foil affecting the charge / discharge cycle life and overcharge characteristics. As a result, it was found that the elongation rate of the secondary battery was important and succeeded in obtaining a copper foil having the highest effect in the secondary battery characteristics.
  • Example 1 of Patent Document 5 “Copper sulfate pentahydrate 280 g / L, sulfuric acid 100 g” / L, 7 ppm of low molecular weight gelatin having an average molecular weight of 3000, 3 ppm of hydroxyethyl cellulose, and 1 ppm of sodium 3-mercapto-1-propanesulfonate are added to an acidic copper sulfate sulfuric acid electrolyte containing 35 ppm of chloride ions.
  • An electrolytic copper foil manufactured under the conditions of “° C., flow rate of 0.3 m / min, current density of 50 A / dm 2 ”, etc.
  • the crystal structure is a fine crystal having a 10-point average roughness Rz and smaller than 2.5 ⁇ m, the minimum peak-to-peak distance of the base mountain is 5 ⁇ m or more, the normal temperature tensile strength is 40 kg / mm 2 or less, and An electrolytic copper foil characterized in that the decrease in the normal temperature tensile strength after heat treatment at 130 ° C. for 15 hours is 15% or less and is not heat-softened. ”
  • the electrolytic copper foil used for the negative electrode current collector of the lithium ion secondary battery should improve the characteristics of the copper foil affecting the charge / discharge cycle life and overcharge characteristics, as pointed out in Patent Document 5 above.
  • variations in physical properties such as elongation and tensile strength of the electrolytic copper foil are problematic.
  • chlorine was contained in the copper electrolyte used for the production of the electrolytic copper foil.
  • This chlorine may be intentionally added and controlled, or may be mixed as an unavoidable impurity through a vinyl chloride pipe.
  • chlorine in the electrolytic solution is a component that easily affects product quality even if there is a small amount of fluctuation. Therefore, those skilled in the art have improved the manufacturing method for the purpose of reducing the variation in the original quality of the electrolytic copper foil, but the fluctuation of the chlorine concentration is unavoidable. I thought it was a major factor.
  • the electrolytic copper foil used for the current collector for the lithium ion secondary battery has been required to further stabilize the quality, and even if it is heated more than has been allowed for the conventional electrolytic copper foil.
  • High-level quality such as resistance to softening and resistance to bending, resistance to bending, resistance to bending, and current collector bending performance with a negative electrode active material collector (negative electrode) that actually carries the negative electrode active material It has come to be required to stabilize.
  • the inventors of the present invention as an electrolytic copper foil suitable for use as a constituent material of a current collector for a lithium ion secondary battery and a copper-clad laminate for manufacturing a printed wiring board, I came up with a foil. Further, by adopting the manufacturing method described below, it is possible to efficiently produce the electrolytic copper foil according to the present invention.
  • Electrolytic copper foil according to the present invention is an electrolytic copper foil obtained by electrolyzing a copper electrolyte, and the iodine content in the electrolytic copper foil is 0.003 mass% or more. It is characterized by being.
  • the surface-treated copper foil according to the present invention is characterized in that the surface of the above-described electrolytic copper foil containing iodine is subjected to surface treatment.
  • the manufacturing method of the electrolytic copper foil according to the present invention is a manufacturing method of the above-described electrolytic copper foil containing iodine, and an iodine concentration is 1.5 mg as a copper electrolyte. It is characterized by using a sulfuric acid copper sulfate electrolyte in the range of / L to 15.0 mg / L. And as for this copper electrolyte solution, it is more preferable that chlorine concentration is 1.0 mg / L or less.
  • an electrolytic copper foil it is preferable to perform electrolysis under the electrolytic conditions of a copper electrolytic solution temperature of 40 ° C. to 60 ° C. and a current density of 50 A / dm 2 to 85 A / dm 2 .
  • Negative electrode for a lithium ion secondary battery obtained using the surface-treated copper foil according to the present invention is the negative electrode current collector of the surface-treated copper foil according to the present invention described above. It was used as
  • the electrolytic copper foil according to the present invention contains 0.003% by mass or more of iodine as described above.
  • iodine in the bulk copper of the electrolytic copper foil, even if the chlorine content in the electrolytic copper foil varies, stable physical characteristics are exhibited.
  • the electrolytic copper foil according to the present invention for the negative electrode of a lithium ion secondary battery, it is excellent in resistance to expansion and contraction behavior caused by charging and discharging, and a long-life lithium ion secondary battery is marketed at low cost. Can be provided.
  • the electrolytic copper foil according to the present invention the method for producing the surface-treated copper foil, and the negative electrode for a lithium ion secondary battery obtained using the surface-treated copper foil will be described in detail in this order.
  • the electrolytic copper foil according to the present invention is an electrolytic copper foil obtained by electrolyzing a copper electrolyte.
  • This electrolytic copper foil is characterized in that the iodine content in the electrolytic copper foil is in the range of 0.003% by mass or more.
  • the electrolytic copper foil containing iodine is suitable as a current collector for a lithium ion secondary battery, and has a heat resistance softening resistance, a bending resistance property, and a “with a negative electrode active material actually loaded with a negative electrode active material”.
  • the current collector bending performance in the state of “current collector (negative electrode)” is simultaneously improved.
  • the iodine content in the electrolytic copper foil is preferably 0.003% by mass or more.
  • the iodine content in the electrolytic copper foil is 0.003% by mass or more because stable physical characteristics are exhibited even if the chlorine content in the electrolytic copper foil varies. Strictly speaking, however, if the iodine content exceeds 0.03% by mass, none of the above-described characteristics is improved further, rather, the electrolytic copper foil becomes brittle and the bending characteristics deteriorate.
  • the iodine content is preferably 0.03% by mass or less.
  • the chlorine content measured by chemical analysis is preferably in the range of 0.0000 mass% to 0.0018 mass%. That is, when the chlorine content contained in the electrolytic copper foil is 0.0018% by mass or less, the surface roughness of the precipitation surface becomes low, and it is easy to obtain a low profile precipitation surface. It is preferable as a constituent material of a current collector for a secondary battery.
  • the said chlorine content is 0.0006 mass%-0.0018 mass. % Is preferable.
  • the electrolytic copper foil which concerns on this invention is the copper content suitable by the chlorine content measured by the chemical analysis method, and iodine content of the following number 1 (the negative electrode collector use of a lithium ion secondary battery) It is preferable to satisfy the relationship between the chlorine content and the iodine content of the foil. By satisfying such a relationship, even when heated at a temperature of about 350 ° C., extremely high heat-resistant softening resistance is exhibited. This point will be described in detail in the embodiments described later. Hereinafter, a method for analyzing the chlorine content and the iodine content will be described.
  • the chlorine content was measured as follows. After the copper foil is heated and dissolved with nitric acid, a certain amount of silver nitrate solution is added. Next, a certain amount of KBr solution is added to coprecipitate chloride ions together with silver bromide. After standing for 15 minutes in the dark, the precipitate is filtered off and washed. Thereafter, the precipitate is transferred to a beaker, dissolved with a thiourea solution, and left overnight in a dark place. This solution is diluted and constant volume, and subjected to an ion chromatograph (Dionex ICS-2000, electrical conductivity detector, eluent is KOH, column is AS-20), and the chloride ion concentration is measured to determine the chlorine content. Was calculated.
  • Dionex ICS-2000 electrical conductivity detector, eluent is KOH, column is AS-20
  • the iodine content was measured as follows. While heating the copper foil with aqua regia, it was oxidized and dissolved, allowed to cool, and then the volume was measured, and the strength of I: 178 nm (Ar purge) was measured with ICP-AES (Seiko Instruments Inc. SPS3000). The iodine content was calculated.
  • the electrolytic copper foil according to the present invention was measured by gas analysis. As a result, the total main impurity content of each component of carbon, oxygen, sulfur, and nitrogen was 0.01% by mass or less. Is provided. At this stage, it is not clear how these main impurity contents are acting in the electrolytic copper foil used for the negative electrode current collector of the lithium ion secondary battery.
  • the main impurity component mentioned here is an element that is easily segregated at the grain boundary. When the main impurity content is 0.01% by mass or less, the toughness of the electrolytic copper foil is improved, and the elongation rate and tensile strength are increased. Shows a good balance.
  • the inventors of the present invention measured the copper purity of the electrolytic copper foil according to the present invention using a glow discharge mass spectrometer.
  • the copper purity obtained using a glow discharge mass spectrometer was a high purity value of 99.99% by mass or more.
  • this glow The copper purity obtained by using the discharge mass spectrometer is not a consistent value, but it is sufficient to consider it as an error caused by different analysis methods.
  • the surface roughness of the deposited surface of the electrolytic copper foil according to the present invention will be described.
  • the surface roughness of the deposited surface of the electrolytic copper foil according to the present invention has an Rzjis value in the range of 0.70 ⁇ m to 2.0 ⁇ m, and it can be understood that the deposited surface is a low profile.
  • Rzjis exceeds 2.0 ⁇ m, it becomes difficult to uniformly carry the negative electrode active material when manufacturing a negative electrode for a lithium ion secondary battery.
  • repeated charge / discharge is not preferable because lithium tends to easily grow in a dendrite shape on the convex portion of the current collector surface.
  • the value of Rzjis is less than 0.7 ⁇ m, the surface state is too smooth, and when used as a negative electrode current collector of a lithium ion secondary battery, it is between the negative electrode active material and the negative electrode current collector. This is not preferable because the adhesion of the resin is lowered. Furthermore, in order to stabilize the characteristics as a lithium ion secondary battery, it is preferable that the difference in the Rzjis values on both sides of the electrolytic copper foil is within 0.6 ⁇ m.
  • the Rzjis (10-point average roughness) referred to here is a value measured with a stylus type surface roughness meter (curvature radius of curvature of 0.2 ⁇ m) based on JIS B 0601.
  • the electrolytic copper foil according to the present invention preferably has a normal elongation (E 0 ) value in the range of 2.0% to 9.0%.
  • E 0 normal elongation
  • the normal elongation becomes 2.0% or more, it becomes suitable for use as a negative electrode current collector of a lithium ion secondary battery.
  • the normal elongation is 9.0% or less, the deformation resistance due to expansion and contraction during charge and discharge when used for the negative electrode current collector of the lithium ion secondary battery is within an appropriate range.
  • the measurement of this elongation rate and the measurement of the tensile strength mentioned later are the values measured by performing a tensile test with respect to the 10-mm-wide electrolytic copper foil sample.
  • the value of the normal tensile strength (F 0 ) is in the range of 48 kgf / mm 2 to 72 kgf / mm 2 .
  • the value of normal tensile strength (F 0 ) is 48 kgf / mm 2 or more, there is a tendency that the deformation resistance against expansion and contraction during charge / discharge when used for a negative electrode current collector of a lithium ion secondary battery is good. is there.
  • the value of the normal tensile strength (F 0 ) is 72 kgf / mm 2 or less, the above-mentioned range of the appropriate normal elongation is stably obtained.
  • the heat treatment as used herein refers to subjecting a normal electrolytic copper foil to a heat treatment at 180 ° C. for 60 minutes in an air atmosphere.
  • the electrolytic copper foil according to the present invention has a post-heat elongation (E a ) value in the range of 4% to 10%.
  • Circuits configured with copper foil in the process of manufacturing a printed wiring board and negative electrode current collectors manufactured with copper foil in the process of manufacturing a negative electrode of a lithium ion secondary battery are exposed to various high-temperature load environments. Therefore, the post-heat physical property of this electrolytic copper foil is a very important factor that affects the product quality. If the value of the elongation after heating (E a ) is 4% or more, the elongation is appropriate for the negative electrode current collector application of the lithium ion secondary battery. On the other hand, when the post-heat elongation is 10% or less, the deformation resistance due to expansion and contraction during charge and discharge when used for the negative electrode current collector of a lithium ion secondary battery is within an appropriate range.
  • the value of the post-heat tensile strength (F a ) after the heat treatment at 180 ° C. ⁇ 60 minutes is in the range of 38 kgf / mm 2 to 72 kgf / mm 2 .
  • the value of tensile strength after heat (F a ) is 38 kgf / mm 2 or more, it is hardly affected by the thermal history in the processing process, and charging / discharging when used as a negative electrode current collector of a lithium ion secondary battery The deformation resistance against the expansion and contraction at the time tends to be good.
  • the value of tensile strength after heat (F a ) is 72 kgf / mm 2 or less, it is preferable because the above-described range of the appropriate normal elongation is easily maintained.
  • electrolytic copper foil according to the present invention as the physical characteristics, the value of the normal tensile strength of above (F 0), the heat after the tensile strength after heat treatment 180 ° C. ⁇ 60 minutes the above (F a It is preferable that the value of
  • this number 2 is that the difference between “normal tensile strength (F 0 )” and “post-heat tensile strength (F a )” is small, and it is difficult to soften even under constant heating. It is.
  • the copper foil is affected by various thermal histories. As a result, when the copper foil is softened, the bending performance required as the negative electrode strength of the lithium ion secondary battery, all the variations in deformation resistance with respect to expansion and contraction during charging and discharging when used for the negative electrode current collector, Since quality stability as a lithium ion secondary battery cannot be secured, it is not preferable. Therefore, a softening resistance against such a level of heating is required.
  • the physical characteristics of the electrolytic copper foil according to the present invention show a high bending performance such that the number of bendings until reaching the fracture in the post-heat bending resistance test after the heat treatment at 180 ° C. ⁇ 60 minutes is 3000 times or more. It is preferable.
  • the number of bendings in the after-heating bending resistance test is 3000 times or more, the deformation resistance against expansion and contraction at the time of charge / discharge when used for the negative electrode current collector of a lithium ion secondary battery is dramatically improved, and the product life Prolongation is also possible.
  • the post-heat bending resistance test referred to here is an important characteristic required even in the case of an electrolytic copper foil for a printed wiring board.
  • the post-heat bending resistance test referred to here is a tester industry stock that conforms to the measurement method of JIS C 5016 after heat-treating a strip-shaped electrolytic copper foil having a width of 10 mm ⁇ length of 10 cm at 180 ° C. ⁇ 60 minutes.
  • the number of times of bending until rupture is measured with a company-made flexible bending tester (bending radius: 1 mm, bending speed: 100 cpm, stroke: 20 mm).
  • the surface-treated copper foil according to the present invention is characterized in that various surface treatments are performed on the surface of the above-described electrolytic copper foil containing iodine.
  • This surface treatment means that one or more of roughening treatment, rust prevention treatment, and silane coupling agent treatment are applied to the surface of the above-described electrolytic copper foil.
  • This surface treatment is performed on the surface of the electrolytic copper foil for the purpose of imparting adhesive strength, chemical resistance, heat resistance and the like in consideration of required characteristics for each application.
  • the silane coupling agent treatment in the case of the electrolytic copper foil used for the negative electrode current collector of the lithium ion secondary battery, it is preferably applied to both surfaces of the electrolytic copper foil. In some cases, it is preferably applied to one side of the electrolytic copper foil.
  • the manufacturing method of the electrolytic copper foil according to the present invention is a manufacturing method of the above-described electrolytic copper foil containing iodine, and the composition of the sulfuric acid-based copper electrolyte used here
  • the copper concentration in the sulfuric acid-based copper electrolyte referred to here is in the range of 50 g / L to 120 g / L, more preferably 50 g / L to 80 g / L.
  • the free sulfuric acid concentration is considered as a standard in the range of 60 g / L to 250 g / L, more preferably 80 g / L to 150 g / L.
  • the iodine concentration in the sulfuric acid copper electrolyte is preferably in the range of 1.5 mg / L to 15.0 mg / L. A range of 2.5 mg / L to 7.0 mg / L is more preferable.
  • the iodine concentration in the sulfuric acid-based copper electrolyte is less than 1.5 mg / L, the amount of iodine taken into the electrolytic copper foil deposited by electrolysis is insufficient, and the obtained electrolytic copper foil is in the above-mentioned proper range. It is not preferable because physical properties such as surface roughness, elongation, and tensile strength cannot be obtained, and various physical properties tend to increase with time.
  • the iodine concentration exceeds 15.0 mg / L, the iodine content in the electrolytic copper foil increases and the above-described disadvantages occur. Moreover, the smoothness of the precipitation surface of electrolytic copper foil and favorable mechanical strength can be made compatible by the said iodine density
  • concentration being 7.0 mg / L or less. In this case, it is preferable to use an iodide such as NaI or KI for the addition of iodine.
  • the chlorine concentration of the copper electrolyte used in the present invention is preferably 1.0 mg / L or less.
  • the said chlorine concentration exceeds 1.0 mg / L, since the obtained electrolytic copper foil becomes easy to embrittle, it is unpreferable.
  • the range of the chlorine concentration contained in the electrolytic copper foil according to the present invention it is preferably in the range of 0.4 mg / L to 0.8 mg / L.
  • the method for producing an electrolytic copper foil according to the present invention it is preferable to perform electrolysis at a temperature of the copper electrolyte of 40 ° C. to 60 ° C. and a current density of 50 A / dm 2 to 85 A / dm 2 .
  • the solution temperature is lower than 40 ° C., the stability of electrolysis is lacking and physical strength such as tensile strength and elongation rate of the obtained electrolytic copper foil tends to increase.
  • the solution temperature exceeds 60 ° C., the evaporation of water in the solution becomes remarkable, and the stability of the solution composition is lacking.
  • Negative electrode for lithium ion secondary battery obtained using the surface-treated copper foil according to the present invention is the above-mentioned surface-treated copper foil. It is used as a negative electrode current collector.
  • a negative electrode for a lithium ion secondary battery is obtained by carrying a negative electrode active material on the surface of a surface-treated copper foil that is a negative electrode current collector to form a negative electrode current collector with a negative electrode active material. It is.
  • the electrolytic copper foil and the surface-treated copper foil according to the present invention are a copper-clad laminate for manufacturing a printed wiring board (in the above and the following, simply “copper-clad laminate”) It is also possible to divert it to manufacture.
  • the above-mentioned surface-treated electrolytic copper foil and an insulating layer constituting material can be laminated to obtain a copper-clad laminate for producing a printed wiring board.
  • the concept of the copper-clad laminate mentioned here includes both a rigid copper-clad laminate and a flexible copper-clad laminate. Since the electrolytic copper foil which concerns on this invention is a low profile, it is suitable for formation of the fine pattern circuit of the level calculated
  • the sulfuric acid-based copper electrolyte As the sulfuric acid-based copper electrolyte, a basic solution having a copper concentration of 80 g / L and a free sulfuric acid concentration of 140 g / L was used and adjusted to have each additive concentration shown in Table 1. . At this time, iodine was added using potassium iodide (KI), and hydrochloric acid was used to adjust the chlorine concentration. Then, using the sulfuric acid-based copper electrolytes having different compositions shown in Table 1, electrolytic copper foils containing 8 kinds of iodine of Sample 1 to Sample 8 were manufactured. In addition, this Example is for clarifying the difference of the general physical property as copper foil by contrasting with a comparative example.
  • KI potassium iodide
  • the electrolytic copper foil was prepared by using a titanium plate electrode whose surface was polished with # 2000 polishing paper as the cathode and DSA as the anode under the conditions of a solution temperature of 50 ° C. and a current density of 75 A / dm 2 . Electrolysis was performed to prepare an electrolytic copper foil containing iodine having a thickness of 18 ⁇ m. The surface roughness (Rzjis) of the glossy surface (surface opposite to the deposition surface) of these electrolytic copper foils was 1.4 ⁇ m.
  • the evaluation results of the characteristics of the obtained electrolytic copper foil are summarized in Table 2 so that they can be compared with the following comparative examples.
  • the comparative sample 1 and the comparative sample 2 use a copper electrolyte having an iodine concentration of 0.5 mg / L or less, and are comparative examples used for comparison with the above-described examples.
  • the comparative sample 3 and the comparative sample 4 use the copper electrolyte solution (copper electrolyte solution which does not contain iodine) whose iodine concentration is 0.0 mg / L.
  • the other production conditions were the same as in Example, and Comparative Sample 1 to Comparative Sample 4 were obtained.
  • the said liquid composition is combined with the liquid composition of an Example, and is shown in following Table 1.
  • Samples 1 to 8 according to the examples are suitable as a copper electrolyte of the present invention, “chlorine concentration is 1.0 mg / L or less, iodine concentration is 1.5 mg / L to 15.0 mg / L
  • the sulfuric acid copper sulfate electrolyte contained in the range of “L” is used.
  • none of Comparative Sample 1 to Comparative Sample 4 uses an acidic copper sulfate electrolyte contained in the range of “iodine concentration of 1.5 mg / L to 15.0 mg / L”. It can be understood that the copper electrolyte containing chlorine and iodine was not used.
  • the copper concentration of the copper electrolyte is “a chlorine concentration of 1.0 mg / L or less, an iodine concentration of 1.5 mg / L to 15
  • a sulfuric acid copper sulfate electrolytic solution that satisfies the condition of “0.0 mg / L”
  • an electrolytic copper foil having an iodine content of 0.005 mass% to 0.063 mass% is obtained.
  • the iodine content of only the electrolytic copper foil of Sample 7 exceeds 0.03% by mass in the examples.
  • the number of times of bending in the post-heat bending resistance test of the sample 7 is 1105 times, and it is noticed that the value is lower than the number of bending times of the other samples. This also supports that when the iodine content in the electrolytic copper foil exceeds 0.03% by mass, the structure of the electrolytic copper foil tends to become brittle.
  • region shown by said Formula 1) above the straight line of FIG. 1 is used for the negative electrode collector application for lithium ion secondary batteries.
  • the heat resistance softening resistance to heating which is a characteristic required as a copper foil, is particularly high, and the heat resistance softening resistance is stabilized, and thus tends to be preferable. That is, the electrolytic copper foil used for the negative electrode current collector application for the lithium ion secondary battery is shown in the formula 1 in consideration of not only the iodine content in the electrolytic copper foil but also the chlorine content in the electrolytic copper foil. It is considered particularly preferable to satisfy the relationship.
  • the iodine content is 0.003% to 0.03% by mass and the chlorine content is 0.0006% by mass? It can be judged that it is 0.0018 mass% and is in the range satisfying the condition shown in Equation 1 with the most preferable characteristics as the negative electrode current collector of the lithium ion secondary battery.
  • Table 3 shows the relationship between “normal tensile strength (F 0 )” and “post-heating tensile strength after heating at 350 ° C. (F b )”. Here, it is the result of having performed the tension test using the strip-shaped sample of length 10cm x width 10mm, after heating 350 degreeC x 60 minutes with respect to copper foil.
  • the electrolytic copper foil used for the negative electrode current collector application for the lithium ion secondary battery is not only the iodine content in the electrolytic copper foil but also the chlorine content in the electrolytic copper foil, and the above formula 1 It is clear that satisfying the relationship shown in FIG.
  • the electrolytic copper foil must contain iodine and chlorine in a well-balanced manner.
  • the electrolytic copper foils of Sample 1 and Sample 2 classified as such electrolytic copper foils have a large softening resistance due to heating, and even when used for the production of a negative electrode for a lithium ion secondary battery, On the other hand, it can be understood that sufficient deformation resistance is exhibited.
  • Heat-resistant bending tensile test procedure 1. A strip-shaped copper foil sample of 1 cm ⁇ 10 cm for a tensile test is subjected to a heat treatment for 60 minutes at a predetermined heating temperature (a heating temperature of a special method of 350 ° C., other 180 ° C.) in an air atmosphere and left to cool. 2. Thereafter, the sample is bent, and a bending portion is formed by applying a 180 ° bending stress for 1 minute under a load of 15 kg, and the original strip shape is restored. 3. Using a tensile tester, the tensile strength and elongation are measured in a room temperature atmosphere. 4). Evaluation item ⁇ Heat-resistant tensile strength (those in which heat-resistant bending tensile test procedure (2) is omitted) ⁇ Heat-resistant bending tensile strength
  • the examples are relatively in comparison with Comparative Sample 1 also in the bending tensile strength after heating at 180 ° C. ⁇ 60 minutes. I understand that it is expensive. From this, it is understood that the electrolytic copper foil containing iodine according to the present invention has a characteristic that it is difficult to soften even when subjected to high temperature heating, and there is little decrease in tensile strength even when bent, and it is difficult to break. it can.
  • sample S-2 is sample 1 in the example
  • sample S-5 is sample 2 in the example
  • sample C-1 is comparative sample 1 in the comparative example
  • sample C-2 is Note that comparative sample 2 and sample C-4 in the comparative example are comparative sample 4 in the comparative example.
  • the “S series” has higher tensile strength after the heat treatment at 350 ° C. for 60 minutes than the “C series”. That is, to see the tendency of tensile strength, the “S series” produced by using an acidic copper sulfate electrolyte containing a predetermined amount of iodine is resistant to severe heating of 350 ° C. ⁇ 60 minutes. It can be seen that the film shows a sufficient softening resistance of 27 kgf / mm 2 or more. Moreover, the “S series” shows a high tensile strength of 28 kgf / mm 2 or more even when it is bent.
  • the preferable mode when viewed in the “S series” is that Samples S-1 to S-6 that showed high tensile strengths of 30 kgf / mm 2 or more in both the heat-resistant tensile strength and the heat-resistant bending tensile strength. Is applicable. Further, as a more preferable embodiment, Sample S-1 to Sample S-3 which show high tensile strength of 40 kgf / mm 2 or more in both heat resistant tensile strength and heat resistant bending tensile strength are applicable.
  • the voltage loss due to the electrical resistance of the negative electrode current collector is made as small as possible, and electrons are supplied or collected evenly to the negative electrode active material in the battery. It is necessary to let Regarding this required characteristic, it is considered that the physical properties of the electrolytic copper foil used as the negative electrode current collector after heat treatment at 350 ° C. for 60 minutes are greatly affected.
  • the electrolytic copper foil containing iodine according to the present application has a high tensile strength of 30 kgf / mm 2 or more at 350 ° C. ⁇ 60 minutes after heat treatment, It can be seen that both the normal state and the heated state show a stable high conductivity. On the other hand, although the electrolytic copper foil which does not contain iodine has high electrical conductivity, the tensile strength is greatly reduced by heating. Therefore, it can be judged that the electrolytic copper foil containing no iodine cannot withstand the expansion and contraction behavior that the negative electrode current collector receives during charging and discharging of the lithium ion secondary battery.
  • Corson alloy foil and rolled copper alloy foil are shown for comparison.
  • Corson alloy foil has very good tensile strength after heating, but its conductivity is low due to the alloy composition. For this reason, when it is used as a negative electrode current collector, it is difficult to cause a reaction to uniformly supply electrons to the whole negative electrode and collect lithium evenly in the negative electrode active material, which is not preferable. .
  • the electrolytic copper foil containing iodine according to the present invention is used as a negative electrode current collector of a lithium ion secondary battery even when compared with a comparative sample, a Corson alloy foil, and a rolled copper alloy foil of a comparative example. It can be understood that this is suitable.
  • the electrolytic copper foil containing iodine corresponding to the examples described above has a property that it is difficult to break even when bent. Therefore, when such an electrolytic copper foil is used as a current collector material of a wound battery employed in a lithium ion secondary battery, softening due to a thermal history loaded in the manufacturing process of the battery is less likely to occur, and It is difficult to be affected by heat generation during charging / discharging, and also has excellent resistance to deformation against expansion / contraction behavior during charging / discharging. Therefore, it can be said that the electrolytic copper foil containing iodine according to the present invention is a copper foil suitable as a current collector material employed in a lithium ion secondary battery.
  • the electrolytic copper foil according to the present invention contains 0.003% by mass or more of iodine which is not included in the conventional electrolytic copper foil.
  • This electrolytic copper foil containing iodine exhibits stable characteristics even when the chlorine content varies.
  • the physical properties of the electrolytic copper foil are not easily softened even when heated, and have both good heat resistance softening resistance and bending resistance required for a current collector of a lithium ion secondary battery. Therefore, if this electrolytic copper foil is employed as a current collector, a high quality and long-life lithium ion secondary battery can be supplied to the market.

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Abstract

L'invention concerne une feuille de cuivre électrolytique qui peut présenter diverses propriétés de façon stable, même quand la teneur en chlore y varie. Une feuille de cuivre électrolytique spécifiquement décrite est produite en électrolysant une solution électrolytique de cuivre. De préférence, la teneur en iode y est d'au moins 0,003 % en masse, mieux de 0,003 à 0,03 % en masse, et la teneur en chlore n'y dépasse pas 0,0018 % en masse.
PCT/JP2011/065147 2010-07-01 2011-07-01 Feuille de cuivre électrolytique et son procédé de production Ceased WO2012002526A1 (fr)

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KR1020127029126A KR101385760B1 (ko) 2010-07-01 2011-07-01 전해 동박 및 그 제조 방법
CN201180032383.5A CN102959135B (zh) 2010-07-01 2011-07-01 电解铜箔以及其制造方法
JP2012522711A JP5373970B2 (ja) 2010-07-01 2011-07-01 電解銅箔及びその製造方法
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JP2016537514A (ja) * 2013-11-08 2016-12-01 イルジン マテリアルズ カンパニー リミテッドＩｌｊｉｎ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． 電解銅箔、並びにこれを含む電気部品及び電池
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KR102473557B1 (ko) * 2015-09-24 2022-12-01 에스케이넥실리스 주식회사 전해동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조방법
JP6190980B2 (ja) * 2015-09-25 2017-08-30 古河電気工業株式会社 電解銅箔、その電解銅箔を用いた各種製品
KR102109379B1 (ko) * 2016-08-19 2020-05-12 케이씨에프테크놀로지스 주식회사 전해 동박과, 이 전해 동박을 포함하는 리튬 이차전지용 집전체 및 리튬 이차전지
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JPWO2015080052A1 (ja) * 2013-11-27 2017-03-16 三井金属鉱業株式会社 キャリア箔付銅箔及び銅張積層板
JP2019178431A (ja) * 2013-11-27 2019-10-17 三井金属鉱業株式会社 キャリア箔付銅箔及び銅張積層板
JP2018141230A (ja) * 2017-02-24 2018-09-13 南亞塑膠工業股▲分▼有限公司 電解液、電解銅箔及びその製造方法
WO2021153257A1 (fr) * 2020-01-30 2021-08-05 三井金属鉱業株式会社 Feuille de cuivre électrolytique
JPWO2021153257A1 (fr) * 2020-01-30 2021-08-05
JP7656555B2 (ja) 2020-01-30 2025-04-03 三井金属鉱業株式会社 電解銅箔
US12344953B2 (en) 2020-01-30 2025-07-01 Mitsui Mining & Smelting Co., Ltd. Electrolytic copper foil

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CN105386088B (zh) 2018-06-29
JPWO2012002526A1 (ja) 2013-08-29
KR20140007507A (ko) 2014-01-17
KR20130006504A (ko) 2013-01-16
CN102959135B (zh) 2016-03-09
CN102959135A (zh) 2013-03-06
KR101385760B1 (ko) 2014-04-17
KR101385761B1 (ko) 2014-04-17
CN105386088A (zh) 2016-03-09
JP5373970B2 (ja) 2013-12-18

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