WO2014061983A9 - Feuille de cuivre électrolytique, pièce électrique et batterie comprenant cette feuille de cuivre électrolytique et procédé permettant de fabriquer cette feuille de cuivre électrolytique - Google Patents

Feuille de cuivre électrolytique, pièce électrique et batterie comprenant cette feuille de cuivre électrolytique et procédé permettant de fabriquer cette feuille de cuivre électrolytique Download PDF

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Publication number
WO2014061983A9
WO2014061983A9 PCT/KR2013/009231 KR2013009231W WO2014061983A9 WO 2014061983 A9 WO2014061983 A9 WO 2014061983A9 KR 2013009231 W KR2013009231 W KR 2013009231W WO 2014061983 A9 WO2014061983 A9 WO 2014061983A9
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Prior art keywords
copper foil
electrolytic copper
heat treatment
additive
tensile strength
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Ceased
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PCT/KR2013/009231
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English (en)
Korean (ko)
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WO2014061983A1 (fr
Inventor
이선형
조태진
박슬기
송기덕
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Iljin Materials Co Ltd
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Iljin Materials Co Ltd
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Priority claimed from KR1020130118495A external-priority patent/KR20140050541A/ko
Application filed by Iljin Materials Co Ltd filed Critical Iljin Materials Co Ltd
Publication of WO2014061983A1 publication Critical patent/WO2014061983A1/fr
Publication of WO2014061983A9 publication Critical patent/WO2014061983A9/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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, an electric component and a battery including an electrolytic copper foil, and a method for manufacturing an electrolytic copper foil, and more particularly, to a low roughness, high strength and high elongated electrolytic copper foil having high tensile strength and elongation even after high temperature heat treatment.
  • Copper foil is generally used as an electrical power collector of a secondary battery.
  • the copper foil is mainly used as a rolled copper foil rolled, but the manufacturing cost is expensive and it is difficult to manufacture a wide copper foil.
  • the rolled copper foil must use lubricating oil during rolling, adhesion to the active material may be degraded by contamination of the lubricating oil, and thus, the layer discharge cycle characteristics of the battery may be reduced.
  • Lithium batteries are accompanied by volume change during layer discharge and exothermic phenomenon due to overcharge.
  • the copper foil is effective to improve adhesion to the electrode active material and to prevent the occurrence of wrinkles, breaks, etc. in the copper foil as a current collector by being less affected by the copper base material in relation to the expansion and contraction of the active material layer according to the layer discharge cycle. Should have a low surface roughness. Therefore, high-strength, high-strength and low-light copper foils capable of withstanding volumetric changes and exothermic phenomena of lithium batteries and excellent adhesion to active materials are required.
  • ICs for inner leads disposed in device halls located in the center of the product A plurality of terminals of the chip are directly bonded, and at this time, a current is instantaneously heated by using a bonding device and a constant pressure is applied. Therefore, the inner lead formed by the etching of the electrolytic copper foil is pulled out by the bonding pressure and stretched.
  • One aspect of the present invention is to provide a new electrolytic copper foil.
  • Another aspect of the invention provides an electrical component comprising the electrolytic copper foil. Will be.
  • Another aspect of the invention is to provide a battery comprising the electrolytic copper foil.
  • Another aspect of the present invention is to provide a method for producing the electrolytic copper foil.
  • the surface roughness Rz of the precipitated surface is less than lA, and after heat treatment, an electrolytic copper foil having a tensile strength of 40 kgf / rmn 2 or more and an elongation of 4% or more is presented.
  • an insulating substrate And the electrolytic copper foil attached to one surface of the insulating substrate, and an electric component including a circuit formed by etching the electrolytic copper foil is provided.
  • a battery including the electrolytic copper foil is provided.
  • Additive B is a sulfonic acid or metal salt thereof of a compound containing a sulfur atom, and additive C is a nonionic water soluble polymer;
  • an electrolytic copper foil having low surface roughness and high strength and having high stretch can be obtained.
  • FIG. 1 is an X-ray diffraction (XRD) spectrum of the precipitated surface of the electrolytic copper foil prepared in Example 1.
  • FIG. 1 is an X-ray diffraction (XRD) spectrum of the precipitated surface of the electrolytic copper foil prepared in Example 1.
  • Example 2 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 1;
  • FIG. 3 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 2.
  • FIG. 4 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 3.
  • FIG. 4 is a scanning electron microscope photograph of the surface of the electrolytic copper foil prepared in Example 3.
  • Example 5 is a scanning micrograph photograph of the surface of the electrolytic copper foil prepared in Example 4.
  • Electrolytic copper foil according to an exemplary embodiment of the present invention has a surface roughness Rz of the precipitated surface is ⁇ ⁇ or less, the tensile strength after heat treatment is more than 40 kgf / mm2, the elongation is more than 4%.
  • the electrolytic copper foil has a high roughness of 40 kgi / mm 2 and a high roughness of 40 kgi / mm 2 even though the surface roughness of the low roughness Rz is less than or equal to ⁇ .
  • the electrolytic copper foil has a high elongation of 4% or more even after high temperature.
  • the electrolytic copper foil may be used simultaneously for a printed circuit board (PCB) / FPC (flexible PCB) and a current collector for a battery.
  • PCB printed circuit board
  • FPC flexible PCB
  • the surface roughness Rz of the precipitated surface of the electrolytic copper foil is greater than 1.4, the contact surface of the surface of the electrodeposited copper foil for the negative electrode current collector and the active material may be reduced, so that the lifespan of the layer discharge cycle and the initial capacity of the charge may be lowered.
  • the surface roughness Rz of the precipitation surface exceeds 1.4, it is not easy to form a high density circuit having a fine pitch in the printed wiring board.
  • the electrolytic copper foil has a high strength characteristics of 40kgf / mm 2 to 70kgf / mm 2 tensile strength.
  • the electrolytic copper foil has a tensile strength of 40kgf / mm2 to even after heat treatment 70kgf / mm2.
  • the heat treatment may be carried out at 15 CTC to 22 CTC, for example, and may be performed at 18 CTC in detail.
  • the heat treatment may be carried out over 30 minutes, 1 hour, 2 hours and several hours, but may be carried out for at least 1 hour to maintain a constant tensile strength.
  • the heat treatment is to measure the tensile strength of the electrolytic copper foil, and is a treatment to obtain a tensile strength or elongation maintained at a value which does not change to a certain level when the electrolytic copper foil is stored or put into a subsequent process.
  • the electrolytic copper foil has a tensile strength of less than 40kgf / mm 2 after heat treatment, it may be difficult to handle because the mechanical strength is weak.
  • the electrolytic copper foil has a tensile strength after heat treatment similar to the tensile strength before heat treatment.
  • the tensile strength after the heat treatment of the electrolytic copper foil is preferably 85% to 99% of the anneal strength before the heat treatment. It is easy to handle in the process and the yield is high.
  • the electrolytic copper foil may have an elongation of 2% to 15% before heat treatment.
  • the electrolytic copper foil may have an elongation of 4% to 15% after heat treatment, and the heat treatment may be performed at 18 CTC for 1 hour.
  • the elongation after heat treatment may be 1 to 4.5 times the elongation before heat treatment.
  • the elongation after heat treatment in the electrolytic copper foil is less than 4%, cracks may occur when the subsequent process is a high temperature process.
  • the process of manufacturing the negative electrode current collector is a high temperature process, and cracks may occur due to a volume change of the active material layer during layer discharge. So After elongation, the specified elongation must be maintained.
  • the electrolytic copper foil has a ratio of the intensity of the diffraction peak (1 (200)) to the (200) crystal plane (1 (200)) and the intensity of the diffraction peak (1 (111)) to the (111) crystal plane in the XRD spectrum of the precipitation surface.
  • / 1 (111) may be 0.5 to 1.0.
  • the diffraction angle for the (111) crystal plane is shown at the diffraction angle (2 ⁇ ) 43.0 ° ⁇ 1.0 ° in the XRD spectrum for the precipitation surface, and the diffraction angle (2 ⁇ ) 50.5 ° ⁇ 1.0 It shows a diffraction peak with respect to the (200) crystal plane at °, the intensity ratio 1 (200) / 1 (111) may be 0.5 to 1.0 or more.
  • 1 (200) / 1 (111) may be 0.5 to 0.8 in the electrolytic copper foil.
  • the Bb M (200) / M (lll) of the orientation index obtained from the orientation index (M ( ⁇ )) with respect to the (111) crystal plane may be 1.1 to 1.5.
  • the electrolytic copper foil may have an elongation of 10% or more after heat treatment at 180 ° C. for 1 hour. That is, the electrolytic copper foil may have a high elongation of 10% or more after high temperature heat treatment. For example, the electrolytic copper foil may have an elongation of 10% to 20% after high temperature heat treatment. For example, the electrolytic copper foil has an elongation of 10% to 15% after high temperature heat treatment. Can be. For example, the electrolytic copper foil may have an elongation of 10% to 13% after high temperature heat treatment. The electrolytic copper foil may have an elongation of 1% or more before heat treatment. For example, the electrolytic copper foil may have an elongation of 2% to 20% before heat treatment.
  • the electrolytic copper foil may have an elongation of 5% to 20% before heat treatment.
  • the electrolytic copper foil has an elongation of 5% to before heat treatment. May be 15%.
  • the electrolytic copper foil may have an elongation of 5% to 10% before heat treatment.
  • the term “before heat treatment” refers to a temperature of 25 ° C. to 130 ° C. before annealing at a high temperature.
  • the elongation is a value obtained by dividing the stretched distance by the initial length of the electrolytic copper foil immediately before the electrolytic copper foil is broken. to be.
  • the surface roughness Rz of the electrodeposited copper foil may be less than or equal to .Tim.
  • the total thawing foil may be used as both a copper foil for PCB / FPC and a copper foil for negative electrode current collector for secondary batteries by having a low roughness of Rz of 0.7 or less.
  • the electrolytic copper foil may have a precipitation surface and a surface roughness Rz of 0.5 or less.
  • the surface roughness Rz of the precipitation surface of the electrolytic copper foil may be 0.45 / ⁇ or less.
  • the surface roughness Ra of the electrodeposited copper foil may be 0.15 im or less.
  • the electrolytic copper foil may be used as both a copper foil for PCB / FPC and a copper foil for negative electrode current collector for secondary batteries by having a low roughness Ra of 0.15 zm or less.
  • the surface roughness Ra of the precipitation surface of the electrolytic copper foil may be less than or equal to O. Uim.
  • the surface roughness Ra of the deposition surface of the electrolytic copper foil may be less than or equal to O. ll im. * 33:
  • the tensile strength of the electrolytic copper foil may be 85% or more of the tensile strength before the heat treatment.
  • the tensile strength after heat treatment for 1 hour at 18CTC of the electrolytic copper foil may be 90% or more of the tensile strength before heat treatment.
  • the tensile strength before heat treatment is the tensile strength of the copper foil obtained without high temperature thermal treatment.
  • Tensile strength before heat treatment of the electrolytic copper foil may be 40kgf / mm2 to 70kgf / mm2.
  • Glossiness (Gs (60 °)) in the width direction of the precipitation surface in the electrolytic copper foil may be 500 or more.
  • the glossiness (Gs (60 0 )) of the width direction of the precipitation surface in the electrolytic copper foil may be 500 to 1000.
  • the glossiness is a value measured according to JIS Z 871-1997.
  • the thickness of the electrolytic copper foil may be 35 or less.
  • the thickness of the electrolytic copper foil may be 6 to 35 m.
  • the thickness of the electrolytic copper foil may be 6 to 18 pm.
  • the thickness of the electrolytic copper foil may be 2 to 10.
  • An electrical component includes an insulating substrate; And the insulating base It includes; the above-mentioned electrolytic copper foil attached to one surface of, and includes a circuit formed by etching the electrolytic copper foil.
  • the electrical component is, for example, a TAB tape, a printed wiring board (PCB), a flexible printed wiring board (FPC, Flexible PCB), and the like, but not necessarily limited thereto. Anything that can be used in the field is possible.
  • a battery according to an exemplary embodiment includes the electrolytic copper foil.
  • the electrolytic copper foil may be used as a negative electrode straw whole of the battery, but is not necessarily limited thereto and may be used as other components used in the battery.
  • the battery is not particularly limited and includes a primary battery and a secondary battery, and a battery using an electrolytic copper foil as a current collector such as a lithium ion battery, a lithium polymer battery, a lithium air battery, and the like can be used in the art. All is possible.
  • Electrolytic copper foil manufacturing method is an additive A; Additive B; Electrolyzing a copper electrolyte solution comprising the additive C and an additive D; wherein the additive A is at least one selected from the group consisting of a thiourea-based compound and a compound in which a thiol group is connected to a heterocyclic ring containing nitrogen,
  • the additive B is a sulfonic acid or a metal salt thereof of a compound containing a sulfur atom, and the additive C is a nonionic water-soluble polymer;
  • the additive D is a phenazinium compound.
  • the electrolytic copper foil manufacturing method may include a low thickness copper foil having a thin thickness, high mechanical strength and high stretching by including additives of a new composition.
  • the copper electrolyte may include chlorine (chlorine ion) having a concentration of 1 to 40 ppm.
  • chlorine chlorine ion
  • the presence of a small amount of chlorine ions in the copper electrolyte increases the initial nucleation site during electroplating, resulting in fine grains and the precipitation of CuC12 formed at the grain boundary interface, which inhibits crystal growth when heated to high temperatures, thereby providing thermal stability at high temperatures. Can improve.
  • the concentration of the chlorine ion is less than 1 ppm, the concentration of chlorine ions required in the sulfuric acid-copper sulfate electrolyte may be insufficient, so that the tensile strength before heat treatment may be lowered and thermal stability at high temperature may be lowered.
  • the concentration of chlorine ion is more than 40 ppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture low roughness electrolytic copper foil, low tensile strength before heat treatment, and low thermal stability at high temperature.
  • the content of the additive A is 1 to lOppm
  • the content of the additive B is 10 to 200ppm
  • the content of the additive C is 5 to 40ppm
  • the content of the additive D may be 1 to 100ppm.
  • the additive A may improve the production stability of the electrolytic copper foil and improve the strength of the electrolytic copper foil. If the content of the additive A is less than lppm, the tensile strength of the electrolytic copper foil may be lowered. If the content of the additive A is more than lOppm, the surface roughness of the precipitated surface may increase, making it difficult to manufacture the electrolytic copper foil of low roughness, and the tensile strength may be reduced.
  • Additive B in the copper electrolyte may improve the surface gloss of the electrolytic copper foil.
  • the content of the additive B is less than lOppm, the gloss of the electrolytic copper foil may be lowered.
  • the content of the additive B is more than 200 ppm, the surface roughness of the precipitated surface is increased. It is difficult to manufacture low roughness electrolytic copper foil and the tensile strength of the electrolytic copper foil may be reduced.
  • the additive C may lower the surface roughness of the electrolytic copper foil and improve surface glossiness. If the content of the additive C is less than 5ppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture low-temperature electrolytic copper foil, and the gloss of the electrolytic copper foil may be lowered. It may not be economical.
  • the additive D in the copper electrolyte may serve to improve the flatness of the surface of the electrolytic copper foil. If the content of the additive D is less than lppm, the surface roughness of the precipitated surface is increased, making it difficult to manufacture 3 ⁇ 4 thawed foil of low degree, and the gloss of the electrolytic copper foil may be lowered. It may become unstable and the tensile strength of the electrolytic copper foil may be impaired.
  • the thiourea compound may be a compound represented by Formula 1:
  • R1, R2, R3 and R4 are independently an alkyl group having 1 to 10 carbon atoms, and R2 and R4 may be connected to each other to form a ring.
  • the thiourea-based compound is diethylthiourea, ethylenethiourea, acetylenethiourea, dipropylthiourea, dibutylthiourea, N-trifluoro N-trifluoroacetylthiourea N-ethylthiourea, N-cyanoacetylthiourea, N-allylthiotirea, o_lrylthio Urea (o-tolylthiourea), ⁇ , ⁇ '-butylene thiourea ( ⁇ , ⁇ '-butylene thiourea), thiozolidinethiol, 4-thiazolinethiol, 4-methyl-2-pyri It may be one or more selected from the group consisting of midithiol (4—methyl-2—pyrimidinethiol), 2-thiouracil, but is not necessarily limited to any of the thiourea compounds that can be used as an additive in the art.
  • the sulfonic acid or metal salt thereof of the compound containing the sulfur atom is, for example, a bis- (3-sulfopropyl) -disulfide disodium salt (SPS) represented by the following Chemical Formula 5; 1-propanesulfonic acid (MPS), 3- (N, N-dimethylthiocarbamoyl) -thiopropanesulfonate sodium salt (DPS) represented by the following formula (7), 3- [(amino- Iminomethyl) thio] -1-propanesulfonate sodium salt (UPS), eethyldithiocarbonato-S- (3-sulfopropyl) -ester sodium salt represented by the following formula (9): (10) 3- (benzothiazolyl-2-hammercapto) -propyl-sulfonic acid sodium salt (ZPS), ethylenedithiodipropylsulfonic acid sodium salt, thioglycolic acid, thio
  • the nonionic water-soluble polymer is polyethylene glycol, polyglycerol, hydroxyethyl cellulose, carboxymethyl cellulose (Carboxymethylcellulose), nonylpe Nonylphenol polyglycol ether, Octane diol-bis- (Polyalkylene glycol ether), Octane to polyalkylene glycol ether, Oleic acid poly Glycol ethers (eic acid polyglycol ether), polyethylene propylene glycol, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polyvinyl alcohol, ⁇ -Naph may be one or more selected from the group consisting of ⁇ -naphthol polyglycol ether, stearic acid polyglycol ether, stearyl alcohol polyglycol ether, but Water-soluble which can be used as a scavenger in the art without limitation Any polymer may be used, for example, the polyethylene glycol may have a molecular weight of
  • the phenazinium compound may be a compound represented by Formula 11 below:
  • the phenazinium compound is not a polymer.
  • the phenazinium compound may be at least one selected from the group consisting of safranin-O (Safaranine-O) represented by the following Equation 12, Janus Green BUanus Green B) represented by the following Formula 13, and the like. .
  • the temperature of the copper electrolyte used in the manufacturing method may be 30 to 6CTC, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention.
  • the temperature of the copper electrolyte may be 40 to 50 ° C.
  • the current density used in the manufacturing method may be 20 to 500 A / dm 2, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention.
  • the current density is 30 to 40
  • the copper electrolyte may be sulfuric acid-copper sulfate copper electrolyte.
  • the concentration of Cu 2+ ions in the sulfuric acid-copper sulfate copper electrolyte may be 60 g / L to 180 g / L, but is not necessarily limited to this range and may be appropriately adjusted within a range capable of achieving the object of the present invention.
  • the concentration of Cu 2+ may be 65 g / L to 175 g / L.
  • the copper electrolyte may be prepared by a known method.
  • the concentration of ⁇ Cu2 + ions can be obtained by controlling the iron content of copper ions or copper sulfate, and the concentration of S042 + ions can be obtained by adjusting the amount of sulfuric acid and copper sulfate added.
  • the concentration of the additives included in the copper electrolyte solution may be obtained from the amount and molecular weight of the additives added to the copper electrolyte solution, or may be obtained by analyzing the additives contained in the copper electrolyte solution by a known method such as column chromatography.
  • the electrolytic copper foil may be manufactured by a known method except for using the above-described copper electrolytic backing.
  • the electrolytic copper foil may be prepared by supplying and electrolyzing the copper electrolyte between the curved negative electrode surface of the rotating titanium drum-shaped titanium and the positive electrode to precipitate the electrolytic copper foil on the negative electrode surface and winding it continuously to produce an electrolytic copper foil.
  • electrolytic copper foil In order to manufacture electrolytic copper foil, a 3L electrolytic cell system capable of circulating at 20 L / min was used and the silver conductivity of the copper electrolyte was kept constant at 45 ° C.
  • the anode was a 5mm thick, 10 x 10 cm2 Dimentionally Stable Electrode (DSE) plate, and the cathode was a titanium plate with the same size and thickness as the anode.
  • DSE Dimentionally Stable Electrode
  • plating was performed at a current density of 35 A / dm 2: An electrolytic copper foil having a thickness of 18 ⁇ was prepared.
  • the basic composition of the copper electrolyte is as follows:
  • H2S04 80 ⁇ 150g / L
  • Silver chlorine and additives are added to the additive copper electrolyte, and the composition of the added additives and chloride ions is shown in Table 1 below.
  • ppm is the same concentration as mg / L.
  • the scanning electron micrograph of the prepared electrolytic copper foil precipitation surface (matte surface, M surface) is shown in FIG.
  • PEG polyethylene glycol (canto chemical Cas No. 25322-68-3)
  • the electrolytic copper foils of Examples 1 to 4 had a flat surface and a low roughness compared to those of Comparative Copper Samples 1 to 4.
  • Glossiness was measured about the surface of the precipitation surface of the electrolytic copper foil obtained in Examples 1-4 and Comparative Examples 1-4.
  • Glossiness was measured by irradiating measurement light on the surface of the copper foil along the flow direction (MD direction) of the electrolytic copper foil at an incident angle of 60 °, and measuring the intensity of light reflected at a reflection angle of 60 °. It measured based on 8741-1997.
  • the electrolytic copper foils of Examples 1 to 4 exhibited improved glossiness as compared to the electrolytic copper foils of Comparative Examples 1 to 4.
  • X-ray diffraction (XRD) spectra of the precipitated surfaces of the electrolytic copper foils obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured.
  • XRD for Example 1 The spectrum is shown in FIG.
  • the peak intensity of the (111) crystal plane was the highest, followed by the (200) crystal plane.
  • K200) / I (i n) which is the ratio of the intensity (K20Q) of the diffraction peak with respect to the (200) crystal plane and the intensity (1 (111)) of the diffraction peak with respect to the (111) crystal plane, was 0.605.
  • Orientation indexes are S. Yoshimura, S. Yoshihara, T. Shirakashi, E. Sato, Electrochim. Measurement was performed using the orientation index (M) proposed in Acta 39, 589 (1994).
  • the orientation index XM is calculated as follows.
  • IFR (111) IF (111) / ⁇ IF (111) + IF (200) + IF (220) + IF (311) ⁇
  • IR (111) I (111) / ⁇ I (111) + 1 (200) + 1 (220) + 1 (311) 1
  • IF (lll) is the XRD intensity on JCPDS Cards and 1 (111) is the experimental value. If M (lll) is greater than 1, it has a preferred orientation parallel to the (111) plane, and if M is less than 1, it means that the preferred orientation is reduced. Table 3
  • Precipitation surface and gloss surface roughness Rz and Ra of the electrolytic copper foil obtained in Examples 1-4 and Comparative Examples 1-4 were measured according to JISB 0601- 1994 standard. Surface roughness Rz and Ra obtained by the measuring method are shown in Table 4 below. The lower the value, the lower the roughness.
  • the same electrolytic copper foil used for the measurement of tensile strength and elongation at room temperature was taken out after heat treatment at 180 ° C for 1 hour, and the tensile strength and Elongation was measured and referred to as high temperature tensile strength and high temperature elongation.
  • the electrolytic copper foils of Examples 1 to 4 have a low surface roughness Rz of less than 0.5 / im, a tensile strength of 40 kgf / mm 2 or more after high temperature heat treatment, and an elongation of 10% or more after high temperature heat treatment. High.
  • the electrolytic copper foils of Comparative Examples 1 to 4 have higher surface roughness and lower elongation after high temperature heat treatment than i electrolytic copper foils of Examples 1 to 4, so that they can be used as negative current collectors for secondary batteries and / or low-low copper foils for PDB / FPC. Not suitable for.
  • the invention is not to be limited by the foregoing embodiments and the accompanying drawings, which are to be interpreted by the appended claims.
  • it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible without departing from the technical spirit of the present invention described in the claims with respect to the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

La présente invention se rapporte à une feuille de cuivre électrolytique dont la rugosité de surface d'une surface de précipitation (Rz) est inférieure à 1,4 μm, la résistance à la traction après un traitement thermique est égale à au moins 40 kgf/mm2 et le pourcentage d'élongation est égal à au moins 4 %. La feuille de cuivre électrolytique conserve une faible rugosité et une résistance élevée tout en présentant un pourcentage d'élongation élevé et peut être utilisée dans un collecteur de courant d'une batterie rechargeable au lithium-ion qui présente une taille moyenne jusqu'à une grande taille et dans un boîtier pour permettre un transfert automatique sur bande (TAB pour Tape Automated Bonding) utilisé dans un boîtier de support de bande (TCP pour Tape Carrier Package).
PCT/KR2013/009231 2012-10-18 2013-10-16 Feuille de cuivre électrolytique, pièce électrique et batterie comprenant cette feuille de cuivre électrolytique et procédé permettant de fabriquer cette feuille de cuivre électrolytique Ceased WO2014061983A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20120116073 2012-10-18
KR10-2012-0116073 2012-10-18
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CN112839436B (zh) * 2020-12-30 2022-08-05 广东嘉元科技股份有限公司 一种高频高速印制电路板用电解铜箔及其制备方法
CN113337856B (zh) * 2021-05-24 2024-02-06 中国恩菲工程技术有限公司 一种用于双面光电解铜箔的添加剂以及铜箔的制备方法
CN114182310B (zh) * 2021-12-21 2023-08-22 深圳先进电子材料国际创新研究院 一种用于电解铜箔制造的电解液及其应用
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