WO2012002418A1 - 負極集電体用銅箔の製造方法 - Google Patents
負極集電体用銅箔の製造方法 Download PDFInfo
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- WO2012002418A1 WO2012002418A1 PCT/JP2011/064888 JP2011064888W WO2012002418A1 WO 2012002418 A1 WO2012002418 A1 WO 2012002418A1 JP 2011064888 W JP2011064888 W JP 2011064888W WO 2012002418 A1 WO2012002418 A1 WO 2012002418A1
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- film
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 a method for producing a copper foil for a negative electrode current collector.
- the present invention relates to a surface treatment method suitable for a copper foil for a negative electrode current collector of a lithium ion secondary battery.
- rolled copper foil or electrolytic copper foil is used for the negative electrode current collector.
- BTA treatment and chromate treatment which are low in production cost, are generally adopted as rust prevention treatments, with emphasis on not causing battery reaction on the surface.
- Patent Document 1 discloses a secondary battery that has a good rust prevention ability and maintains required adhesion even in the presence of an electrolyte, and thus enables a long-term charge / discharge cycle.
- a method of subjecting a copper foil surface to a chromate treatment using an alkaline chromate bath is disclosed as a method for producing a copper foil used for an electrode of a secondary battery.
- an electrolytic copper foil (thickness: 10 ⁇ m; manufactured by Furukawa Circuit Foil Co., Ltd.) is used as an alkaline solution of chromic anhydride (chromic anhydride: 6 g / L; sodium hydroxide: 15 g / L). PH: 12.5; bath temperature: 25 ° C.) for 5 seconds, the glossy side (cathode drum side) is 0.024 mg-Cr / dm 2 , and the rough side (electrolytic bath side) is 0.018 mg- A chromium / dm 2 chromate film is formed.
- the copper foil provided with this chromate film does not cause discoloration under both conditions of holding at 40 ° C.
- Patent Document 2 aims to provide a copper foil for a negative electrode current collector of a Li-ion secondary battery and a method for producing the same, and the reciprocal (1 / C) of the electric double layer capacity at least on one side is 0.00. 1 to 0.3 cm 2 / ⁇ F, and a solution obtained by dissolving at least triazoles in a solvent, chromium trioxide, chromic acid, an electrolytic copper foil washed with water and dried after degreasing rolled copper foil or electrolytic foil
- a technique is disclosed in which at least one selected from the group of salts and dichromates is immersed in an aqueous solution prepared by dissolving in water.
- a copper foil provided with a chromate film or a benzotriazole film satisfying a reciprocal (1 / C) of the electric double layer capacity on one side of 0.1 to 0.3 cm 2 / ⁇ F is collected from the negative electrode
- the non-aqueous solvent secondary battery having a jelly roll type structure used as an electric body is said to have a large charge amount at the first charge and an excellent charge / discharge cycle life.
- Patent Document 2 describes a method for forming an inorganic dielectric film mainly composed of chromium hydrated oxide.
- the pH of the chromate treatment solution is not particularly limited from the acidic region to the alkaline region, and is usually set to 1 to 12. The importance of the pH of the special chromate treatment solution is not pointed out. Since the pH value of the chromate treatment solution is an important factor in producing a chromate-treated copper foil having good discoloration resistance, a secondary battery produced using the method disclosed in the cited document 2 can be used for a long time. If it is used for a long time, the desired battery performance cannot be exhibited due to the above-described reason.
- the acid chromate treatment method When the acid chromate treatment method is adopted as a rust preventive treatment method for copper foil, hexavalent chromium is reduced to trivalent chromium during continuous treatment of the web-like copper foil, and the pH of the chromate treatment solution tends to increase. In such a case, the pH is adjusted to be acidic using chromic anhydride or sulfuric acid. However, when the pH is adjusted using sulfuric acid or the like, a chromate film is hardly formed due to the influence of an anion concentration increase such as a coexisting sulfate group, resulting in a rust preventive film having poor discoloration resistance. That is, considering that the demand for improvement of the charge / discharge cycle life and the like of secondary batteries will continue to increase, a method for producing a copper foil for a negative electrode current collector that is more excellent in discoloration resistance is required.
- the inventors of the present invention have come up with a treatment method for forming a chromate film having better discoloration resistance on the surface of the copper foil, thereby completing the present invention.
- the manufacturing method of the copper foil according to the present invention is a method of manufacturing a copper foil for a negative electrode current collector of a secondary battery by subjecting the copper foil to rust prevention treatment, The foil is treated with a chromate treatment solution having a pH of 3.5 to 7.0 to form a chromate film on the surface of the copper foil.
- a chromate treatment solution having a chromium concentration of 0.3 g / L to 7.2 g / L.
- a chromate treatment solution having a liquid temperature of 15 ° C. to 60 ° C. is used, the copper foil is dipped or electrolyzed, and then drained, and heated air at 30 ° C. to 150 ° C. It is preferable to dry using.
- the immersion treatment is preferably performed by immersing the copper foil in the chromate treatment solution for 0.5 seconds to 10 seconds.
- the electrolytic treatment is performed using a copper foil immersed in a chromate treatment solution as a cathode at a cathode current density of 0.1 A / dm 2 to 25 A / dm 2 for 0.5 seconds to 10 seconds. It is preferable to do.
- a copper foil is treated with a chromate treatment solution having a pH of 3.5 to 7.0, and a chromate film is formed on the surface of the copper foil.
- a chromate treatment solution having a pH of 3.5 to 7.0
- a chromate film is formed on the surface of the copper foil.
- the copper foil is treated with a chromate treatment solution having a pH of 3.5 to 7.0, and a chromate film is formed on the surface of the copper foil.
- a chromate film having good characteristics such as discoloration resistance and small variations can be formed on the surface of the copper foil.
- the pH of the chromate treatment solution falls below 3.5, the concentration of anions such as sulfate ions used for pH adjustment increases, and therefore the reaction of dichromate ions, which are the same anions, is affected.
- the formed chromate film tends to be inferior in discoloration resistance.
- the pH of the chromate treatment solution exceeds 6.2, copper ions contained in a trace amount form a precipitate of copper hydroxide. Then, a tendency that a chromate film is not formed on the surface of the copper foil to which the precipitate has adhered is observed. Therefore, the more preferable pH of the chromate treatment solution is 3.5 to 6.2. Further, from the viewpoint of improving the color fastness, the pH of the chromate treatment solution is more preferably set to 3.5 to 5.9.
- a chromate treatment solution having a chromium concentration of 0.3 g / L to 7.2 g / L is used. If the chromate treatment solution adjusted to such a concentration is used and the copper foil is treated for a predetermined time, a chromate film having good characteristics such as discoloration resistance and small variations can be formed on the copper foil surface. However, if the chromium concentration in the chromate treatment solution is less than 0.3 g / L, no matter how long the chromate treatment time is increased, a good chromate film tends not to be formed.
- the chromium concentration in the chromate treatment solution is more preferably 0.3 g / L to 1.0 g / L.
- a chromate treatment solution having a liquid temperature of 15 ° C. to 60 ° C. is used, the copper foil is dipped or electrolyzed, and then drained, and heated air of 30 ° C. to 150 ° C. is used. Use to dry.
- the electrolytic chromate treatment method is affected by the current density distribution that inevitably occurs on the surface of the copper foil, the in-plane variation of the chromate film obtained by the electrolytic chromate treatment method is slightly increased. is there. However, if the formed chromate film is uniformly adhered at a predetermined level, it is considered that this variation hardly affects the characteristics of the secondary battery when used as a negative electrode current collector.
- the liquid temperature of the chromate treatment solution will be described.
- substitution since substitution is the main reaction, it is considered that the higher the liquid temperature, the better.
- the chromate film formed by the substitution reaction is about a monomolecular film, and the monomolecular film cannot exhibit sufficient discoloration resistance. Therefore, a further adsorbed chromate film is essential for this monomolecular film to exhibit discoloration resistance. Since such an adsorption state can be stably obtained as the temperature becomes lower, it is preferable to employ a liquid temperature on the lower temperature side.
- the temperature of the chromate treatment solution falls below 15 ° C.
- the substitution reaction for uniformly forming a monomolecular film that is essential on the copper foil surface is slowed and the production efficiency is lowered.
- the temperature of the chromate treatment solution exceeds 60 ° C., the thickness of the adsorbed chromate film varies widely, and stable discoloration resistance may not be exhibited.
- the temperature of the chromate treatment solution is also set to 15 ° C. to 60 ° C. as in the case of the immersion treatment, so that the temperature can be controlled in common with the immersion chromate treatment solution. Note that the electrolytic chromate treatment method does not cause the same problems as the immersion chromate treatment method even if the temperature is outside this temperature range.
- the copper foil When the copper foil is immersed, a method of immersing the copper foil in the chromate treatment solution for 0.5 to 10 seconds is employed.
- the surface of the copper foil When the copper foil is subjected to immersion chromate treatment for 0.5 to 10 seconds and then drained, the surface of the copper foil has a mass thickness in terms of metal chromium of 1.0 mg / m 2 to 3.9 mg / m 2.
- the chromate film is formed and exhibits good discoloration resistance.
- the time for immersing the copper foil in the chromate treatment solution is less than 0.5 seconds, there may be an insufficient substitution reaction on the surface of the copper foil, and local discoloration resistance cannot be demonstrated. This is not preferable.
- the chromate film formed by the immersion chromate treatment method is a form in which the chromate layer is adsorbed to a thin film at the monomolecular film level. . Therefore, when mechanical rubbing occurs, the chromate film peels off. Therefore, as a method of draining liquid, a method of uniformly draining without mechanical contact with the copper foil, such as an air blow method using an air knife, or a method that does not rub even when contacting with the copper foil is adopted. .
- the above-mentioned mass thickness in terms of metal chromium is a value when such a liquid draining method is used, but it is clearly stated that even if a water washing step is provided after the chromate treatment step, it does not vary greatly. deep.
- the copper foil immersed in the chromate treatment solution is used as a cathode, and electrolysis is performed with a cathode current density of 0.1 A / dm 2 to 25 A / dm 2 and an electrolysis time of 0.5 seconds to 10 seconds.
- the electrolytic chromate treatment is performed on the copper foil under such conditions, the surface of the copper foil has a mass thickness in terms of metal chromium of 1.0 mg / m 2 to 3.9 mg / m, as in the case of the immersion chromate treatment. 2 chromate film is formed and exhibits good discoloration resistance.
- the time for the electrolytic chromate treatment of the copper foil is less than 0.5 seconds, a uniform electrolytic chromate film may not be formed on the copper foil surface, and the color fastness may not be exhibited locally. It is not preferable.
- the time for the electrolytic chromate treatment of the copper foil exceeds 10 seconds, the effect of forming a uniform chromate film has reached saturation, and the discoloration resistance is not further improved. Therefore, it is not preferable because the productivity of the copper foil is lowered and the manufacturing cost is increased.
- the cathode current density is less than 0.1 A / dm 2 , the surface potential distribution of the copper foil will vary, making it difficult to obtain a uniform chromate film.
- the cathode current density exceeds 25 A / dm 2 , hydrogen is generated from the copper foil surface. In such a case, it is not preferable that hydrogen gas adheres to the surface of the copper foil because formation of a uniform chromate film on the surface of the copper foil is hindered. Therefore, in order to maintain stable production, 0.5 A / dm 2 to 5.0 A / dm 2 is more preferable.
- the copper foil subjected to the chromate treatment using the above-described method is dried using heated air at 30 ° C. to 150 ° C.
- All of the chromate films formed on the surface of the copper foil by the immersion chromate treatment method or the electrolytic chromate treatment method contain hydroxyl groups. Therefore, it is a film that is difficult to exhibit discoloration resistance as it is.
- a chromate film containing a proper amount of hydroxyl groups is decomposed by evaporating the hydroxyl groups contained in the chromate film by drying and evaporating as water, characteristics such as discoloration resistance are improved.
- the discoloration resistance of the chromate-treated copper foil manufactured using the copper foil manufacturing method according to the present invention is evaluated on the drum surface of the electrolytic copper foil. If it is a drum surface, since the microscopic surface shape is stable, comparative evaluation of the chromate film formed on the surface is easy. Specifically, as described in the following examples, the glossiness (Gs (60 °)) before and after the constant temperature and humidity treatment (held in a 50 ° C. and 95% RH atmosphere for 48 hours) is determined by the width of the drum surface.
- ⁇ Gs (gloss difference) indicating the difference between the gloss before the constant temperature and humidity treatment (Gs-A) and the gloss after the constant temperature and humidity treatment (Gs-EH), measured in the direction of If the value is 20 or less, it can be quantitatively determined that the discoloration resistance is good.
- the value of ⁇ Gs (gloss difference) of the chromate-treated copper foil of Comparative Example 4 described later as the chromate-treated copper foil produced in the invention disclosed in Patent Document 1 is 63.7, and the evaluation was carried out. Since the value of ⁇ Gs (gloss degree difference) in the example is 20 or less, it can be determined that the resistance to discoloration is excellent within this range.
- the discoloration resistance of the chromate-treated copper foil produced using the method for producing a copper foil for a negative electrode current collector according to the present invention is determined by the color tone (L * / a * / b *) of the drum surface before and after the constant temperature and humidity treatment .
- the color difference value which is the square root of the square sum of the difference between the indices shown in the following formula 2, is 2.0 or less, it can be quantitatively determined that the color fastness is good.
- the color difference value of the chromate-treated copper foil of Comparative Example 4 is 18.0, and the color difference value of the example is 2.0 or less. It can be judged that it is excellent.
- Example 1 chromic anhydride was dissolved in ion-exchanged water to prepare a chromic acid solution having a chromium concentration of 0.6 g / L, and a chromate treatment solution having a pH of 5.7 using caustic soda was prepared.
- a chromic acid solution having a chromium concentration of 0.6 g / L
- a chromate treatment solution having a pH of 5.7 using caustic soda was prepared.
- untreated electrolytic copper foil DFF: manufactured by Mitsui Mining & Smelting Co., Ltd.
- the temperature of the chromate treatment solution in the glass beaker is gently stirred at 40 ° C., the copper foil is immersed for 3 seconds, drained, dried with heated air at a temperature of 70 ° C. for 3 seconds, and the chromate treated copper foil.
- the test conditions described above are shown in Table 1 below together with the test conditions of Examples 2 to 9, Comparative Examples 1 to 5 and Reference Examples described below.
- Example 1 [Discoloration resistance evaluation of chromate-treated copper foil]
- the chromate-treated copper foil produced in Example 1 has a gloss Gs (60 °) in the drum surface width direction before and after constant temperature and humidity treatment (held for 48 hours in a constant temperature and humidity tank set at 50 ° C. and 95% RH).
- the color tone L * / a * / b * was measured with a color difference meter (SE-2000: manufactured by Nippon Denshoku Industries Co., Ltd.). Discoloration resistance was evaluated.
- the evaluation results are shown in Table 2 later together with the evaluation results of Examples 2 to 9, Comparative Examples 1 to 5 and Reference Examples described below.
- Example 2 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that the pH of the chromate-treated solution prepared in Example 1 was 4.5, and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Example 3 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that the chromate-treated solution prepared in Example 1 had a pH of 6.2, and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Example 4 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that the chromium concentration of the chromate-treated solution prepared in Example 1 was 0.3 g / L, and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Example 5 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that the temperature of the heated air was 100 ° C., and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Example 6 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that sulfuric acid was added to the chromate-treated solution prepared in Example 3 and the pH was adjusted to 5.7, and the discoloration resistance was improved. evaluated. The evaluation results are shown in Table 2 below.
- Example 7 the chromate treatment solution having a liquid temperature of 40 ° C. prepared in Example 1 was used, and a copper foil was electrolyzed at a cathode current density of 1.0 A / dm 2 for 1.5 seconds using a dimensionally stable anode (DSA) as a counter electrode. Then, it was washed with water, drained, and dried with heated air at a temperature of 70 ° C. for 3 seconds to produce a chromate-treated copper foil.
- DSA dimensionally stable anode
- the chromate-treated copper foil produced in Example 7 was evaluated for discoloration resistance in the same manner as in Example 1. The evaluation results are shown in Table 2 below.
- Example 8 a chromate-treated copper foil was prepared in the same manner as in Example 7 except that the chromate-treated solution having a liquid temperature of 40 ° C. prepared in Example 2 was used. evaluated. The evaluation results are shown in Table 2 below.
- Example 9 a chromate-treated copper foil was prepared in the same manner as in Example 7 except that the chromate-treated solution having a liquid temperature of 40 ° C. prepared in Example 3 was used. evaluated. The evaluation results are shown in Table 2 below.
- Comparative Example 1 a chromate-treated copper foil was produced in the same manner as in Example 1 except that the pH of the chromate-treated solution prepared in Example 1 was 7.2, and the color fastness was evaluated. The evaluation results are shown in Table 2 below.
- Comparative Example 2 was the same as Example 1 except that sulfuric acid was added to a chromate treatment solution prepared to have a chromium concentration of 3.6 g / L and a pH of 6.5 to adjust the pH to 3.2. Thus, a chromate-treated copper foil was prepared and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Comparative Example 3 a chromate-treated copper foil was prepared in the same manner as in Example 1 except that a chromate-treated solution having a chromium concentration of 3.6 g / L and a pH adjusted to 12.5 was used. Evaluated. The evaluation results are shown in Table 2 below.
- Comparative Example 4 a chromate-treated copper foil obtained by tracing Example 1 of Patent Document 1 was produced, and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- Comparative Example 5 In Comparative Example 5, chromate treatment was applied to a plurality of copper foils using the chromate treatment solution prepared in Reference Example shown later, and sulfuric acid was added to a pH of 1.3 when the pH reached 3.0. A chromate-treated copper foil was prepared in the same manner as in Example 1 except that the readjusted chromate-treated solution was used, and the discoloration resistance was evaluated. The evaluation results are shown in Table 2 below.
- a chromate-treated copper foil was prepared in the same manner as in Example 1 except that a chromate-treated solution having a chromium concentration of 3.6 g / L and a pH of 1.3 was used, and the discoloration resistance was evaluated.
- the evaluation results are shown in Table 2 below.
- Examples 1 to 6 are copper foils that have been subjected to immersion chromate treatment, the value of the color difference is good at substantially the same level as Examples 7 to 9 that are copper foils that have been subjected to electrolytic chromate treatment.
- the chromate-treated copper foil produced in the reference example has a ⁇ Gs (gloss difference) value of 0.6 and a color difference value of 1.79, which is the same level of discoloration resistance as the chromate-treated copper foil produced in the example. It has.
- the chromate-treated copper foil produced in Comparative Example 5 has a ⁇ Gs (gloss difference) value of 52.7 and a color difference value of 15.4, which is clearly inferior in color fastness. It has become.
- the chromate treatment solution used in Comparative Example 5 was readjusted to 1.3 using sulfuric acid after the pH of the chromate treatment solution used in Reference Example was raised by repeated chromate treatment. That is, the chromate treatment solution used in Comparative Example 5 contains more sulfate ions used for pH adjustment than the chromate treatment solution used in the Reference Example. Accordingly, it was confirmed that sulfate ions present at a predetermined level inhibit the formation of a stable chromate film.
- the discoloration resistance in the high-temperature and high-humidity atmosphere of the chromate-treated copper foil of the example is clearly good at a different level compared to the chromate-treated copper foil produced by the technique described in Patent Document 1 produced in Comparative Example 4. It was confirmed that. Moreover, when Example 2 using the chromate treatment solution on the low pH side is compared with Comparative Example 2, the discoloration resistance is greatly inferior when the pH of the chromate treatment solution is changed from 4.5 to 3.2. . On the other hand, when Example 3 using the chromate treatment solution on the high pH side is compared with Comparative Example 1, the discoloration resistance is greatly inferior only when the pH of the chromate treatment solution is changed from 6.2 to 7.2. .
- the pH of the chromate treatment solution is in the range of 1 to 12 disclosed in Patent Document 2, and the chromate having good discoloration resistance is set to 3.5 to 7.0. It was confirmed that this was an important factor for producing the treated copper foil. In the region where the pH is below 3.5, it was confirmed that sulfate ions coexisting at a predetermined concentration inhibit the formation of a good chromate film.
- a chromate-treated copper foil having excellent discoloration resistance can be produced even if the chromium concentration of the chromate-treated solution is low. Therefore, the amount of hexavalent chromium required for the production of chromate-treated copper foil can be reduced, and it will be easier to manage harmful substances that will become stricter in the future. It can be applied to the surface treatment of copper foil in a wide range of applications.
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Abstract
Description
実施例1では、無水クロム酸をイオン交換水に溶解し、クロム濃度0.6g/Lのクロム酸溶液を作製し、苛性ソーダを用いてpHを5.7としたクロメート処理溶液を調製した。クロメート処理を施す銅箔には、8μm厚さの未処理電解銅箔(DFF:三井金属鉱業(株)製)を用い、硫酸100g/L水溶液に30秒間浸漬して酸洗いし、その後、イオン交換水に30秒間浸漬して水洗した。クロメート処理では、ガラスビーカー内のクロメート処理溶液の液温を40℃として緩やかに撹拌し、銅箔を3秒間浸漬後液切りし、温度70℃の加熱空気で3秒間乾燥し、クロメート処理銅箔を作製した。上述した試験条件を、以下に記載する実施例2~9と比較例1~5及び参考例の試験条件と併せて後の表1に示す。
実施例1で作製したクロメート処理銅箔は、恒温恒湿処理(50℃95%RHに設定した恒温恒湿槽で48時間保持)前後におけるドラム面幅方向の光沢度Gs(60°)を光沢度計(VG-2000:日本電色工業(株)製)で測定し、色調L*/a*/b*を色差計(SE-2000:日本電色工業(株)製)で測定し、耐変色性を評価した。評価結果を、以下に記載する実施例2~9と比較例1~5及び参考例の評価結果と併せて後の表2に示す。
比較例1では、実施例1で調製したクロメート処理溶液のpHを7.2とした以外は、実施例1と同様にしてクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
比較例2では、クロム濃度を3.6g/Lとし、pHが6.5になるよう調製したクロメート処理溶液に硫酸を添加してpHを3.2とした以外は、実施例1と同様にしてクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
比較例3では、クロム濃度を3.6g/Lとし、pHを12.5に調整したクロメート処理溶液を用いた以外は、実施例1と同様にしてクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
比較例4では、特許文献1の実施例1をトレースしたクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
比較例5では、後に示す参考例で調製したクロメート処理溶液を用いて複数枚の銅箔にクロメート処理を施し、pHが3.0になった段階で硫酸を添加してpHを1.3に再調整したクロメート処理溶液を用いた以外は、実施例1と同様にしてクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
参考例では、クロム濃度が3.6g/LでpHが1.3のクロメート処理溶液を用いた以外は、実施例1と同様にしてクロメート処理銅箔を作製し、耐変色性を評価した。評価結果を後の表2に示す。
ΔGs(光沢度差): 実施例1~6と比較例1~5とを対比すると、実施例のクロメート処理銅箔におけるΔGs(光沢度差)の値は0.3~4.6であり、比較例の21.6~67.1と対比すると、1/10のレベルである。なお、実施例1~6は、浸漬クロメート処理した銅箔であるが、ΔGs(光沢度差)の値が、電解クロメート処理した銅箔である実施例7~9とほぼ同レベルで良好である。
参考例で作製したクロメート処理銅箔では、ΔGs(光沢度差)の値が0.6、色差の値が1.79であり、実施例で作製したクロメート処理銅箔と同等レベルの耐変色性を備えている。これに対し、比較例5で作製したクロメート処理銅箔では、ΔGs(光沢度差)の値が52.7、色差の値が15.4であり、明らかに耐変色性に劣るクロメート処理銅箔となっている。
Claims (5)
- 銅箔に防錆処理を施して二次電池の負極集電体用銅箔を製造する方法であって、
前記銅箔をpHが3.5~7.0のクロメート処理溶液を用いて処理し、当該銅箔の表面にクロメート皮膜を形成することを特徴とする銅箔の製造方法。 - クロム濃度が0.3g/L~7.2g/Lの前記クロメート処理溶液を用いる請求項1に記載の銅箔の製造方法。
- 液温を15℃~60℃とした前記クロメート処理溶液を用い、前記銅箔を浸漬処理又は電解処理した後に液切りし、30℃~150℃の加熱空気を用いて乾燥させる請求項1又は請求項2に記載の銅箔の製造方法。
- 前記浸漬処理は、前記クロメート処理溶液に0.5秒間~10秒間銅箔を浸漬する請求項3に記載の銅箔の製造方法。
- 前記電解処理は、前記クロメート処理溶液に浸漬した銅箔を陰極として、陰極電流密度0.1A/dm2~25A/dm2で0.5秒間~10秒間電解する請求項3に記載の銅箔の製造方法。
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CN201180027665.6A CN102933746B (zh) | 2010-06-30 | 2011-06-29 | 负极集电体用铜箔的制造方法 |
US13/807,091 US20130306486A1 (en) | 2010-06-30 | 2011-06-29 | Method for manufacturing copper foil for negative electrode current collector |
JP2012522651A JP5898616B2 (ja) | 2010-06-30 | 2011-06-29 | 負極集電体用銅箔の製造方法 |
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JP2015030917A (ja) * | 2013-08-01 | 2015-02-16 | 長春石油化學股▲分▼有限公司 | 洗浄液組成物及び電解銅箔の洗浄方法 |
KR101833590B1 (ko) | 2014-05-28 | 2018-02-28 | 제이엑스금속주식회사 | 표면 처리 동박, 캐리어 부착 동박, 적층체, 프린트 배선판, 전자 기기, 표면 처리 동박의 제조 방법 및 프린트 배선판의 제조 방법 |
JP2019210520A (ja) * | 2018-06-05 | 2019-12-12 | Jx金属株式会社 | 表面処理銅箔、銅張積層板及びプリント配線板 |
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TWI530586B (zh) | 2016-04-21 |
US20130306486A1 (en) | 2013-11-21 |
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