WO2011078356A1 - Copper foil for negative electrode current collector for use in non-aqueous solvent secondary battery, process for production of the copper foil, and process for production of non-aqueous solvent secondary battery negative electrode - Google Patents
Copper foil for negative electrode current collector for use in non-aqueous solvent secondary battery, process for production of the copper foil, and process for production of non-aqueous solvent secondary battery negative electrode Download PDFInfo
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- WO2011078356A1 WO2011078356A1 PCT/JP2010/073417 JP2010073417W WO2011078356A1 WO 2011078356 A1 WO2011078356 A1 WO 2011078356A1 JP 2010073417 W JP2010073417 W JP 2010073417W WO 2011078356 A1 WO2011078356 A1 WO 2011078356A1
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- copper foil
- negative electrode
- secondary battery
- solvent secondary
- organic compound
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000011889 copper foil Substances 0.000 title claims abstract description 121
- 239000003125 aqueous solvent Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- -1 triazole compound Chemical class 0.000 claims abstract description 53
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003746 surface roughness Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000011267 electrode slurry Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- PZOIEPPCQPZUAP-UHFFFAOYSA-N 1-aminohexan-2-ol Chemical compound CCCCC(O)CN PZOIEPPCQPZUAP-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- STJQELBRFBLOGV-UHFFFAOYSA-N 2-aminoethanol;2h-tetrazole Chemical compound NCCO.C=1N=NNN=1 STJQELBRFBLOGV-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical group C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- VQQDCCOSSXAFMS-UHFFFAOYSA-N N1N=NN=C1.N(CCO)(CCO)CCO Chemical compound N1N=NN=C1.N(CCO)(CCO)CCO VQQDCCOSSXAFMS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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 copper foil for a negative electrode current collector of a nonaqueous solvent secondary battery and a method for producing the same. More specifically, when the present invention is used as a negative electrode current collector of a Li (lithium) ion secondary battery, the copper foil has excellent adhesion to the negative electrode active material of the battery and can improve charge / discharge characteristics. And a method for producing the copper foil. Moreover, this invention relates to the manufacturing method of a nonaqueous solvent secondary battery negative electrode, and is related with the manufacturing method of the negative electrode which is excellent in the adhesiveness of copper foil and a negative electrode active material especially, and a charging / discharging characteristic improves.
- a secondary battery using a non-aqueous electrolyte (hereinafter referred to as a non-aqueous solvent secondary battery) is characterized by high electromotive force and high energy density.
- a typical example is a Li-ion secondary battery.
- a Li ion secondary battery is a battery can that also serves as a negative electrode terminal with an electrode group formed by interposing a separator having electrical insulation and liquid retention between a positive electrode and a negative electrode.
- the battery can is housed together, and the opening of the battery can is sealed with a sealing plate provided with a positive terminal via an insulating gasket.
- the positive electrode is manufactured as follows. First, as a positive electrode active material, for example, LiCoO 2 powder, a carbon conductive agent, and a binder such as polyvinylidene fluoride are kneaded with a non-aqueous solvent such as N-methylpyrrolidone to obtain a positive electrode slurry having a predetermined composition. Prepare. Next, a predetermined amount of this slurry is applied to both surfaces of an aluminum foil as a positive electrode current collector, dried and press-molded to obtain a positive electrode sheet having a predetermined thickness, and a lead is attached to a predetermined portion of the positive electrode sheet. And
- a positive electrode active material for example, LiCoO 2 powder, a carbon conductive agent, and a binder such as polyvinylidene fluoride are kneaded with a non-aqueous solvent such as N-methylpyrrolidone to obtain a positive electrode slurry having a predetermined composition.
- a predetermined amount of this slurry is
- an aqueous slurry and a solvent slurry are used.
- CMC carboxymethyl cellulose
- SBR styrene butadiene rubber
- a negative electrode slurry is prepared by mixing graphite powder or amorphous carbon powder in N-methylpyrrolidone, which is a solvent, and adding polyvinylidene fluoride as a binder.
- a predetermined amount of either slurry is applied to both sides of a copper foil as a negative electrode current collector, dried and press-molded to form a negative electrode sheet having a predetermined thickness, and a lead is attached to the predetermined portion to form a negative electrode.
- negative electrode slurry As described above, there are two types of negative electrode slurry: a negative electrode slurry using water as a solvent and a negative electrode slurry using an organic solvent as a solvent. Recently, negative electrode slurries using water as a solvent from the viewpoint of environmental problems and explosion-proof properties. Use is becoming mainstream.
- the copper foil is generally adopted as the negative electrode current collector for the following reason.
- Copper foil is excellent in electrical conductivity and has high mechanical strength, so that it can be easily handled during production. Further, there is a property that an alloy is not generated between Li ions entering and exiting in the process of charge and discharge. Further, the copper foil can be made into a thin foil at low cost, and even a wide copper foil necessary for mass production of batteries can be easily manufactured. For the reasons described above, copper foil is used as the negative electrode current collector.
- the charge / discharge cycle life characteristics which are the most important characteristics for a secondary battery, and the battery capacity at the initial stage of charging depend on the surface condition (for example, surface roughness, type of surface film, etc.) of the copper foil as the negative electrode current collector. It has become clear. That is, it has been found that there is a problem in the adhesion of the negative electrode active material provided on the surface of the copper foil depending on the surface state of the copper foil.
- the copper foil as the negative electrode current collector includes an electrolytic copper foil and a rolled copper foil.
- Electrolytic copper foil is manufactured by performing copper plating on a rotating titanium drum with a plating solution containing copper sulfate-sulfuric acid as a main component, and stripping off the copper plating to continuously wind up the copper in the form of a foil.
- a rolled copper foil melts copper, casts an ingot, performs hot rolling, then repeatedly performs cold rolling and intermediate annealing, and performs final cold rolling to produce a copper foil.
- a benzotriazole film or a chromate film is applied to the surface of the copper foil after the foil formation as a rust preventive treatment (see Patent Documents 1 and 2).
- the copper foil covered with the rust preventive film is supplied to the negative electrode slurry application line for applying the negative electrode active material as the negative electrode current collector, and the negative electrode slurry is applied to the surface thereof.
- the adhesiveness with the negative electrode active material differs depending on the kind of the rust preventive film or the generation method, and the better the adhesiveness, the smaller the decrease in capacity after repeating the charge / discharge cycle.
- the copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention has an organic compound film formed on the surface of the copper foil, and the reciprocal (1 / C) of the electric double layer capacity on at least one side of the copper foil is It is characterized by being 0.31-0.9 cm 2 / ⁇ F.
- the organic compound film is preferably a film containing a triazole compound or a film containing a triazole compound and an amine compound.
- a solution containing an organic compound is brought into contact with the surface of the copper foil, and then dried, and at least one surface of the copper foil has an electric double layer capacity.
- a film having an inverse number (1 / C) of 0.31 to 0.9 cm 2 / ⁇ F is formed.
- the organic compound is a film containing a triazole compound or a film containing a triazole compound and an amine compound.
- an organic compound film having an electric double layer capacity reciprocal (1 / C) of 0.31 to 0.9 cm 2 / ⁇ F is formed on at least one surface of a copper foil.
- a negative electrode active material slurry using water as a solvent is applied to the surface of the formed copper foil and dried.
- the copper foil for the negative electrode of the non-aqueous solvent secondary battery of the present invention is excellent in adhesion to the negative electrode active material, and is capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. It has the effect.
- the method for producing a copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention is an excellent non-aqueous solvent secondary battery capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. This is an excellent manufacturing method in which a copper foil for a negative electrode of a battery can be easily provided.
- the method for producing a non-aqueous solvent secondary battery negative electrode of the present invention it is possible to provide a negative electrode having excellent adhesion between a copper foil and a negative electrode active material and improved charge / discharge characteristics.
- the inventors of the present invention have developed a copper foil for a negative electrode current collector of a Li ion secondary battery in which an organic compound film having a certain thickness is formed on the surface of the copper foil to improve adhesion with the negative electrode active material.
- Li ion secondary batteries developed as batteries for electric vehicles have been demanded to further improve performance.
- the thickness of the organic compound film increases the adhesion of the negative electrode active material and has become an important factor for the corrosion resistance of the copper foil surface.
- the reciprocal (1 / C) of the electric double layer capacitance indicating the thickness of the dielectric layer described in Patent Document 1 is 0.1 to 0.3 cm 2 / ⁇ F, the thickness of the organic compound film is small. The effect of increasing the adhesion between the copper foil and the negative electrode active material is not sufficient, and the anticorrosion of the copper foil has become insufficient.
- the 1 / C value is set within the range of 0.31 to 0.9 cm 2 / ⁇ F.
- the adhesion with the active material tends to be low and the corrosion resistance tends to be poor.
- a copper foil having a 1 / C value greater than 0.9 cm 2 / ⁇ F is because even if it is further increased (even if the film is thickened), the adhesiveness is saturated and the improvement effect is lost.
- the material for producing the copper foil may be either an electrolytic copper foil or a rolled copper foil.
- electrolytic copper foil a wide variety can be made at low cost, and it is necessary to increase productivity and mass production. For example, it is suitable for use as a negative electrode current collector of an electric vehicle battery. Yes.
- the surface roughness of the copper foil according to the embodiment of the present invention is preferably 2.5 ⁇ m or less in terms of the 10-point average roughness (Rz) defined by JISB0601-1994.
- Such a copper foil can form an organic compound film with a thin and uniform thickness, and the negative electrode active material carried thereon is also uniform, and has excellent adhesion to the negative electrode active material, and charging / discharging of the battery. Cycle life characteristics and initial battery capacity are improved.
- the thickness of the copper foil is preferably 20 ⁇ m or less even in the case of a small battery for portable electric / electronic devices or a large battery for an electric vehicle.
- the thickness of the copper foil is made too thin, its mechanical strength decreases and pinholes and the like increase, so the lower limit of the thickness of the copper foil that can withstand actual use is about 6 ⁇ m.
- the preferred thickness of the copper foil is 20 to 6 ⁇ m.
- the organic compound film formed on the surface of the copper foil is a film containing a triazole compound.
- it is a film containing a triazole compound and an amine compound.
- the triazole compound, or the triazole compound and the amine compound are dissolved in water or an organic solvent, the solution temperature is kept constant, the copper foil is immersed for a certain time, and then dried to form an organic compound film on the copper foil surface. .
- the concentration of the triazole compound solution, triazole compound and amine compound solution is preferably 10 to 10,000 ppm. If it is less than 10 ppm, the organic compound film thickness is not sufficient to maintain the adhesion to the negative electrode active material, and even if it exceeds 10,000 ppm, the organic compound film thickness is saturated, and the effect of improving adhesion cannot be expected. Because. More preferably, it is 50 to 5,000 ppm. Further, the temperature of the solution may be room temperature, but may be used after heating if necessary.
- the adhesion between the copper foil and the negative electrode active material is further improved as compared to the case of the triazole compound alone, and the corrosion resistance of the copper foil is also improved. More preferred.
- the blending ratio of the triazole compound and the amine compound is about 0.5 to 2 times that of the amine compound relative to the triazole compound by weight. This is because even if the amine compound is added twice or more, improvement in adhesion and corrosion resistance can no longer be expected, and if it is less than 0.5 times, the effect of adhesion and corrosion resistance is not exhibited.
- the immersion time of the copper foil in the solution is appropriately determined depending on the relationship between the concentration of the triazole compound, the triazole compound and the amine compound, the solution temperature, and the thickness of the organic compound film to be formed, but usually 0.5 to 30 seconds. Any degree is acceptable.
- triazole compound examples include benzotriazole, tolyltriazole, carboxybenzotriazole, chlorobenzotriazole, ethylbenzotriazole, and naphthotriazole.
- Examples of the amine compound include monoamines such as monoalkylamine, dialkylamine, trialkylamine, monocyclohexylamine, dicyclohexylamine, diamines substituted with 1 to 4 alkyl groups, and at least one alkyl group.
- Examples include alkyl monoamines and alkyl diamines having a hydrophilic group such as a hydroxyl group or a polyoxyethylene group.
- monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, monomethylethanolamine, monoethylethanolamine, monobutylethanolamine and the like can be mentioned.
- This organic compound film is generally formed on both sides of the copper foil, but it may be only on one side in relation to the battery manufacturing process, the form as the negative electrode and the purpose of use. However, in the case of a positive electrode and a negative electrode of a normal Li ion secondary battery, both have a structure in which an active material is supported on both surfaces of each current collector. A film layer is preferably formed.
- the copper foil for negative electrode current collectors used for the non-aqueous solvent secondary battery based on the embodiment of the present invention is manufactured by the process shown in FIG. Step 1: For example, a copper foil having a thickness of 6 to 20 ⁇ m and a surface roughness (Rz) of 2.5 ⁇ m or less is manufactured / prepared.
- Step 2 The copper foil is immersed in an aqueous solution containing an organic compound and brought into contact with the aqueous solution.
- Step 3 Dry.
- a copper foil for a negative electrode current collector having a 1 / C of 0.31 to 0.9 cm 2 / ⁇ F is formed.
- Step 4 Apply negative electrode active material slurry.
- Step 5 Dry. Examples based on the embodiments of the present invention will be described below.
- Rz surface roughness
- a CMC aqueous solution having a concentration of 1.0% by mass was obtained by dissolving carboxymethyl cellulose (CMC) [# 1380 manufactured by Daicel Chemical Industries, Ltd.] in deionized water using a homomixer manufactured by PRIMIX.
- CMC carboxymethyl cellulose
- the non-aqueous solvent secondary battery negative electrode copper foils of the embodiments and examples of the present invention have excellent adhesion to the negative electrode active material and oxidation resistance, and are discolored even in high temperature and high humidity environments. Without having such an effect, the charge / discharge cycle life of the nonaqueous solvent secondary battery and the high battery capacity can be maintained.
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- Engineering & Computer Science (AREA)
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- Electrochemistry (AREA)
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Abstract
The charge-discharge cycle life of a non-aqueous solvent secondary battery and the battery capacity of the non-aqueous solvent secondary battery in the initial stage of battery charge are varied depending on the condition of the surface of a copper foil of a negative electrode in the non-aqueous solvent secondary battery. Thus, disclosed are: a copper foil for use in a negative electrode current collector for a non-aqueous solvent secondary battery, which enables the retention of an excellent charge-discharge cycle life and a high battery capacity; and a process for producing the copper foil.
In the copper foil or use in a negative electrode current collector for a non-aqueous solvent secondary battery, an organic compound coating film is formed on the surface of the copper foil, wherein the inverse (1/C) of the electric double layer capacity on at least one surface of the organic compound coating film is 0.31 to 0.9 cm2/μF and the organic compound coating film comprises a triazole compound or both a triazole compound and an amine compound.
Description
本発明は非水溶媒二次電池の負極集電体用銅箔とその製造方法に関する。更に詳しくは、本発明は、Ｌｉ（リチウム）イオン二次電池の負極集電体として用いた場合、当該電池の負極活物質との密着性に優れ、充放電特性を向上させることができる銅箔と該銅箔を製造する方法に関する。
また、本発明は非水溶媒二次電池負極電極の製造方法に関し、特に銅箔と負極活物質との密着性に優れ、充放電特性が向上する負極電極の製造方法に関するものである。 The present invention relates to a copper foil for a negative electrode current collector of a nonaqueous solvent secondary battery and a method for producing the same. More specifically, when the present invention is used as a negative electrode current collector of a Li (lithium) ion secondary battery, the copper foil has excellent adhesion to the negative electrode active material of the battery and can improve charge / discharge characteristics. And a method for producing the copper foil.
Moreover, this invention relates to the manufacturing method of a nonaqueous solvent secondary battery negative electrode, and is related with the manufacturing method of the negative electrode which is excellent in the adhesiveness of copper foil and a negative electrode active material especially, and a charging / discharging characteristic improves.
また、本発明は非水溶媒二次電池負極電極の製造方法に関し、特に銅箔と負極活物質との密着性に優れ、充放電特性が向上する負極電極の製造方法に関するものである。 The present invention relates to a copper foil for a negative electrode current collector of a nonaqueous solvent secondary battery and a method for producing the same. More specifically, when the present invention is used as a negative electrode current collector of a Li (lithium) ion secondary battery, the copper foil has excellent adhesion to the negative electrode active material of the battery and can improve charge / discharge characteristics. And a method for producing the copper foil.
Moreover, this invention relates to the manufacturing method of a nonaqueous solvent secondary battery negative electrode, and is related with the manufacturing method of the negative electrode which is excellent in the adhesiveness of copper foil and a negative electrode active material especially, and a charging / discharging characteristic improves.
各種の電気・電子機器の駆動電源として非水電解液を用いた二次電池が用いられている。非水電解液を用いた二次電池（以後、非水溶媒二次電池という）は、起電力が高く、またエネルギー密度も高いという特徴を備えており、その代表例としてＬｉイオン二次電池が知られている。
Secondary batteries using non-aqueous electrolyte are used as driving power sources for various electric and electronic devices. A secondary battery using a non-aqueous electrolyte (hereinafter referred to as a non-aqueous solvent secondary battery) is characterized by high electromotive force and high energy density. A typical example is a Li-ion secondary battery. Are known.
Ｌｉイオン二次電池は、正極と負極の間に電気絶縁性と保液性を備えたセパレータを介装して成る電極群を負極端子も兼ねる電池缶の中に所定量の非水電解液と一緒に収容し、前記電池缶の開口部を、正極端子を備えた封口板を絶縁性のガスケットを介して密閉した構造になっている。
A Li ion secondary battery is a battery can that also serves as a negative electrode terminal with an electrode group formed by interposing a separator having electrical insulation and liquid retention between a positive electrode and a negative electrode. The battery can is housed together, and the opening of the battery can is sealed with a sealing plate provided with a positive terminal via an insulating gasket.
ここで、正極は、次のようにして製造されている。
まず、正極活物質として、例えば、ＬｉＣｏＯ2粉末と、炭素導電剤と、ポリフッ化ビニリデンのような結着剤とをＮ－メチルピロリドンのような非水溶媒で混練して所定組成の正極スラリーを調製する。
次いで、このスラリーの所定量を、正極集電体であるアルミニウム箔の両面に塗布し、乾燥したのちプレス成形して、所定厚みの正極シートとし、その正極シートの所定箇所にリードを取り付けて正極とする。 Here, the positive electrode is manufactured as follows.
First, as a positive electrode active material, for example, LiCoO 2 powder, a carbon conductive agent, and a binder such as polyvinylidene fluoride are kneaded with a non-aqueous solvent such as N-methylpyrrolidone to obtain a positive electrode slurry having a predetermined composition. Prepare.
Next, a predetermined amount of this slurry is applied to both surfaces of an aluminum foil as a positive electrode current collector, dried and press-molded to obtain a positive electrode sheet having a predetermined thickness, and a lead is attached to a predetermined portion of the positive electrode sheet. And
まず、正極活物質として、例えば、ＬｉＣｏＯ2粉末と、炭素導電剤と、ポリフッ化ビニリデンのような結着剤とをＮ－メチルピロリドンのような非水溶媒で混練して所定組成の正極スラリーを調製する。
次いで、このスラリーの所定量を、正極集電体であるアルミニウム箔の両面に塗布し、乾燥したのちプレス成形して、所定厚みの正極シートとし、その正極シートの所定箇所にリードを取り付けて正極とする。 Here, the positive electrode is manufactured as follows.
First, as a positive electrode active material, for example, LiCoO 2 powder, a carbon conductive agent, and a binder such as polyvinylidene fluoride are kneaded with a non-aqueous solvent such as N-methylpyrrolidone to obtain a positive electrode slurry having a predetermined composition. Prepare.
Next, a predetermined amount of this slurry is applied to both surfaces of an aluminum foil as a positive electrode current collector, dried and press-molded to obtain a positive electrode sheet having a predetermined thickness, and a lead is attached to a predetermined portion of the positive electrode sheet. And
一方、負極の製造には水溶液系スラリーを使う場合と溶剤系スラリーを使う場合が知られている。
水溶液系スラリーを製造する場合は、まず、カルボキシメチルセルロース（ＣＭＣ）の水溶液を作成し、この水溶液中に黒鉛粉末や無定形炭素粉末を混合し、スチレンブタジエンラバー（ＳＢＲ）を追加して、負極スラリーを調製する。
溶剤系スラリーを製造する場合は、溶剤であるＮ－メチルピロリドン中に黒鉛粉末や無定形炭素粉末を混合し、結着剤としてポリフッ化ビニリデンを追加して、負極スラリーを調製する。
次いで、いずれかのスラリーの所定量を負極集電体である銅箔の両面に塗布し、乾燥したのちプレス成形して所定厚みの負極シートとし、その所定箇所にリードを取り付けて負極とする。 On the other hand, in the production of the negative electrode, there are known cases where an aqueous slurry and a solvent slurry are used.
When producing an aqueous slurry, first create an aqueous solution of carboxymethyl cellulose (CMC), mix graphite powder and amorphous carbon powder in this aqueous solution, add styrene butadiene rubber (SBR), To prepare.
When producing a solvent-based slurry, a negative electrode slurry is prepared by mixing graphite powder or amorphous carbon powder in N-methylpyrrolidone, which is a solvent, and adding polyvinylidene fluoride as a binder.
Next, a predetermined amount of either slurry is applied to both sides of a copper foil as a negative electrode current collector, dried and press-molded to form a negative electrode sheet having a predetermined thickness, and a lead is attached to the predetermined portion to form a negative electrode.
水溶液系スラリーを製造する場合は、まず、カルボキシメチルセルロース（ＣＭＣ）の水溶液を作成し、この水溶液中に黒鉛粉末や無定形炭素粉末を混合し、スチレンブタジエンラバー（ＳＢＲ）を追加して、負極スラリーを調製する。
溶剤系スラリーを製造する場合は、溶剤であるＮ－メチルピロリドン中に黒鉛粉末や無定形炭素粉末を混合し、結着剤としてポリフッ化ビニリデンを追加して、負極スラリーを調製する。
次いで、いずれかのスラリーの所定量を負極集電体である銅箔の両面に塗布し、乾燥したのちプレス成形して所定厚みの負極シートとし、その所定箇所にリードを取り付けて負極とする。 On the other hand, in the production of the negative electrode, there are known cases where an aqueous slurry and a solvent slurry are used.
When producing an aqueous slurry, first create an aqueous solution of carboxymethyl cellulose (CMC), mix graphite powder and amorphous carbon powder in this aqueous solution, add styrene butadiene rubber (SBR), To prepare.
When producing a solvent-based slurry, a negative electrode slurry is prepared by mixing graphite powder or amorphous carbon powder in N-methylpyrrolidone, which is a solvent, and adding polyvinylidene fluoride as a binder.
Next, a predetermined amount of either slurry is applied to both sides of a copper foil as a negative electrode current collector, dried and press-molded to form a negative electrode sheet having a predetermined thickness, and a lead is attached to the predetermined portion to form a negative electrode.
負極スラリーには上述のように、水を溶媒とする負極スラリーと有機溶剤を溶媒とする負極スラリーの二種類があるが、最近では環境問題、防爆性の観点から水を溶媒とする負極スラリーの使用が主流になりつつある。
As described above, there are two types of negative electrode slurry: a negative electrode slurry using water as a solvent and a negative electrode slurry using an organic solvent as a solvent. Recently, negative electrode slurries using water as a solvent from the viewpoint of environmental problems and explosion-proof properties. Use is becoming mainstream.
ここで、負極の集電体として一般に銅箔が採用されるのは次の理由による。
銅箔は導電性が優れており、またその機械的強度も高いので製造時の取り扱いが容易である。
また、充放電の過程で出入りするＬｉイオンとの間で合金を生成しないという性質がある。
更に、銅箔は低コストで薄箔にすることが可能であり、かつ電池の大量生産に必要な広幅な銅箔であっても、容易に製造することができる。
以上のような理由により銅箔が負極集電体として採用されている。 Here, the copper foil is generally adopted as the negative electrode current collector for the following reason.
Copper foil is excellent in electrical conductivity and has high mechanical strength, so that it can be easily handled during production.
Further, there is a property that an alloy is not generated between Li ions entering and exiting in the process of charge and discharge.
Further, the copper foil can be made into a thin foil at low cost, and even a wide copper foil necessary for mass production of batteries can be easily manufactured.
For the reasons described above, copper foil is used as the negative electrode current collector.
銅箔は導電性が優れており、またその機械的強度も高いので製造時の取り扱いが容易である。
また、充放電の過程で出入りするＬｉイオンとの間で合金を生成しないという性質がある。
更に、銅箔は低コストで薄箔にすることが可能であり、かつ電池の大量生産に必要な広幅な銅箔であっても、容易に製造することができる。
以上のような理由により銅箔が負極集電体として採用されている。 Here, the copper foil is generally adopted as the negative electrode current collector for the following reason.
Copper foil is excellent in electrical conductivity and has high mechanical strength, so that it can be easily handled during production.
Further, there is a property that an alloy is not generated between Li ions entering and exiting in the process of charge and discharge.
Further, the copper foil can be made into a thin foil at low cost, and even a wide copper foil necessary for mass production of batteries can be easily manufactured.
For the reasons described above, copper foil is used as the negative electrode current collector.
ところで、Ｌｉイオン二次電池に代表される非水溶媒二次電池に対しても、最近では、更なる高エネルギー密度化と充放電サイクル寿命の長期化への要望が強まり、それに対応すべく研究が進められている。このような動向の中で、負極集電体として銅箔を用いた場合の電池特性に関して、最近、次のような点が指摘されている。
By the way, with respect to non-aqueous solvent secondary batteries represented by Li-ion secondary batteries, recently, the demand for further higher energy density and longer charge / discharge cycle life has been increased, and research is being conducted to respond to them. Is underway. In such a trend, the following points have recently been pointed out regarding battery characteristics when copper foil is used as the negative electrode current collector.
二次電池にとって最も重要な特性である充放電サイクル寿命特性と充電初期の電池容量は、負極集電体である銅箔の表面状態（たとえば、表面粗さ、表面皮膜の種類等）によって左右されることが明らかになってきた。即ち、銅箔の表面状態によって該銅箔の表面に設ける負極活物質の密着性に問題があることが分かった。
The charge / discharge cycle life characteristics, which are the most important characteristics for a secondary battery, and the battery capacity at the initial stage of charging depend on the surface condition (for example, surface roughness, type of surface film, etc.) of the copper foil as the negative electrode current collector. It has become clear. That is, it has been found that there is a problem in the adhesion of the negative electrode active material provided on the surface of the copper foil depending on the surface state of the copper foil.
負極集電体としての銅箔には電解銅箔と圧延銅箔がある。
電解銅箔は回転するチタンドラム上に硫酸銅－硫酸を主成分とするめっき液により銅めっきを行い、この銅めっきを引き剥がして箔状になった銅を連続的に巻き取ることにより製造する。
これに対して圧延銅箔は銅を溶解してインゴットを鋳造し、熱間圧延を行い、その後冷間圧延、中間焼鈍を繰り返し行い、最終冷間圧延を行って銅箔を製造する。 The copper foil as the negative electrode current collector includes an electrolytic copper foil and a rolled copper foil.
Electrolytic copper foil is manufactured by performing copper plating on a rotating titanium drum with a plating solution containing copper sulfate-sulfuric acid as a main component, and stripping off the copper plating to continuously wind up the copper in the form of a foil. .
On the other hand, a rolled copper foil melts copper, casts an ingot, performs hot rolling, then repeatedly performs cold rolling and intermediate annealing, and performs final cold rolling to produce a copper foil.
電解銅箔は回転するチタンドラム上に硫酸銅－硫酸を主成分とするめっき液により銅めっきを行い、この銅めっきを引き剥がして箔状になった銅を連続的に巻き取ることにより製造する。
これに対して圧延銅箔は銅を溶解してインゴットを鋳造し、熱間圧延を行い、その後冷間圧延、中間焼鈍を繰り返し行い、最終冷間圧延を行って銅箔を製造する。 The copper foil as the negative electrode current collector includes an electrolytic copper foil and a rolled copper foil.
Electrolytic copper foil is manufactured by performing copper plating on a rotating titanium drum with a plating solution containing copper sulfate-sulfuric acid as a main component, and stripping off the copper plating to continuously wind up the copper in the form of a foil. .
On the other hand, a rolled copper foil melts copper, casts an ingot, performs hot rolling, then repeatedly performs cold rolling and intermediate annealing, and performs final cold rolling to produce a copper foil.
製箔後の銅箔は、その表面に防錆処理として例えばベンゾトリアゾール皮膜或いはクロメート皮膜等が施される（特許文献１、２参照）。
For example, a benzotriazole film or a chromate film is applied to the surface of the copper foil after the foil formation as a rust preventive treatment (see Patent Documents 1 and 2).
電池の負極製造時に、防錆皮膜に覆われた銅箔が負極集電体として負極活物質を塗布する負極スラリー塗布ラインに供給され、その表面に負極スラリーが塗布される。この防錆皮膜の種類、或いは生成方法により負極活物質との密着性が異なり、密着性の良いものほど充放電サイクルを繰り返した後の容量低下が小さい傾向にある。
At the time of manufacturing the negative electrode of the battery, the copper foil covered with the rust preventive film is supplied to the negative electrode slurry application line for applying the negative electrode active material as the negative electrode current collector, and the negative electrode slurry is applied to the surface thereof. The adhesiveness with the negative electrode active material differs depending on the kind of the rust preventive film or the generation method, and the better the adhesiveness, the smaller the decrease in capacity after repeating the charge / discharge cycle.
負極集電体である銅箔と負極活物質との密着性を高めるための表面処理としては、特許文献1、２に記載されているようにベンゾトリアゾール皮膜或いはクロメート皮膜がある。また、銅箔と溶剤系負極スラリーの濡れ性を高める処理としてカルボニル基を有するアゾール化合物を含有する皮膜が提案されている（特許文献３参照）。
As a surface treatment for enhancing the adhesion between the copper foil as the negative electrode current collector and the negative electrode active material, there is a benzotriazole film or a chromate film as described in Patent Documents 1 and 2. Moreover, the film | membrane containing the azole compound which has a carbonyl group is proposed as a process which improves the wettability of copper foil and a solvent-type negative electrode slurry (refer patent document 3).
上述したように近年、負極活物質用のスラリーは水を溶媒としている。水を溶媒とする負極活物質は特許文献１に記載されている皮膜の種類及び皮膜厚さでは銅箔と負極活物質との密着性が充分とは言えず、また銅箔表面の耐防錆性の点でも問題があった。
また、特許文献３に記載されている皮膜は、有機溶剤を溶媒とする負極スラリーを塗布したとき、銅箔と負極スラリーとの濡れ性は良好であるが、濡れ性が良いことと銅箔と負極活物質との密着性は必ずしも一致するわけではなく、銅箔と負極活物質の密着性に対しては充分とは言えないものであった。 As described above, in recent years, slurries for negative electrode active materials use water as a solvent. The negative electrode active material using water as a solvent cannot be said to have sufficient adhesion between the copper foil and the negative electrode active material with the type and thickness of the film described in Patent Document 1, and rust resistance on the surface of the copper foil. There was also a problem in terms of sex.
In addition, the coating described in Patent Document 3 has good wettability between the copper foil and the negative electrode slurry when a negative electrode slurry using an organic solvent as a solvent is applied, but the good wettability and the copper foil Adhesiveness with the negative electrode active material does not always match, and it cannot be said that the adhesiveness between the copper foil and the negative electrode active material is sufficient.
また、特許文献３に記載されている皮膜は、有機溶剤を溶媒とする負極スラリーを塗布したとき、銅箔と負極スラリーとの濡れ性は良好であるが、濡れ性が良いことと銅箔と負極活物質との密着性は必ずしも一致するわけではなく、銅箔と負極活物質の密着性に対しては充分とは言えないものであった。 As described above, in recent years, slurries for negative electrode active materials use water as a solvent. The negative electrode active material using water as a solvent cannot be said to have sufficient adhesion between the copper foil and the negative electrode active material with the type and thickness of the film described in Patent Document 1, and rust resistance on the surface of the copper foil. There was also a problem in terms of sex.
In addition, the coating described in Patent Document 3 has good wettability between the copper foil and the negative electrode slurry when a negative electrode slurry using an organic solvent as a solvent is applied, but the good wettability and the copper foil Adhesiveness with the negative electrode active material does not always match, and it cannot be said that the adhesiveness between the copper foil and the negative electrode active material is sufficient.
したがって、非水溶媒二次電池の負極用として銅箔を用いたときに、電池の充放電サイクル寿命と充電初期の電池容量が銅箔の表面状態によって左右される現象を解決し、優れた充放電サイクル寿命と高い電池容量の保持を可能とする非水溶媒二次電池負極集電体用銅箔とその製造方法が要望されている。
Therefore, when copper foil is used for the negative electrode of a non-aqueous solvent secondary battery, it solves the phenomenon that the charge / discharge cycle life of the battery and the battery capacity at the initial stage of charging are influenced by the surface condition of the copper foil, and has an excellent charge. There is a demand for a copper foil for a negative electrode current collector of a non-aqueous solvent secondary battery that can maintain a discharge cycle life and a high battery capacity, and a method for producing the same.
本発明の非水溶媒二次電池負極集電体用銅箔は、当該銅箔の表面に有機化合物皮膜が形成され、当該銅箔の少なくとも片面における電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦであることを特徴とする。
The copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention has an organic compound film formed on the surface of the copper foil, and the reciprocal (1 / C) of the electric double layer capacity on at least one side of the copper foil is It is characterized by being 0.31-0.9 cm 2 / μF.
前記有機化合物皮膜がトリアゾール化合物を含有する皮膜、あるいは、トリアゾール化合物及びアミン化合物を含有する皮膜であることが好ましい。
The organic compound film is preferably a film containing a triazole compound or a film containing a triazole compound and an amine compound.
本発明の非水溶媒二次電池負極集電体用銅箔の製造方法は、銅箔の表面に有機化合物を含む溶液を接触させ、その後乾燥し、銅箔の少なくとも片面に電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである皮膜を形成することを特徴とする。
In the method for producing a copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention, a solution containing an organic compound is brought into contact with the surface of the copper foil, and then dried, and at least one surface of the copper foil has an electric double layer capacity. A film having an inverse number (1 / C) of 0.31 to 0.9 cm 2 / μF is formed.
前記有機化合物がトリアゾール化合物を含有する皮膜、あるいは、トリアゾール化合物及びアミン化合物を含有する皮膜であることが好ましい。
It is preferable that the organic compound is a film containing a triazole compound or a film containing a triazole compound and an amine compound.
本発明の非水溶媒二次電池負極電極の製造方法は、銅箔の少なくとも片面に電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである有機化合物皮膜が形成された銅箔の表面に、水を溶媒とする負極活物質スラリーを塗布し、乾燥することを特徴とする。
In the method for producing a negative electrode for a non-aqueous solvent secondary battery according to the present invention, an organic compound film having an electric double layer capacity reciprocal (1 / C) of 0.31 to 0.9 cm 2 / μF is formed on at least one surface of a copper foil. A negative electrode active material slurry using water as a solvent is applied to the surface of the formed copper foil and dried.
本発明の非水溶媒二次電池の負極用としての銅箔は、負極活物質との密着性に優れ、非水溶媒二次電池の充放電サイクル寿命と高い電池容量の保持を可能とする優れた効果を有する。
また、本発明の非水溶媒二次電池負極集電体用銅箔の製造方法は、非水溶媒二次電池の充放電サイクル寿命と高い電池容量の保持が可能な優れた非水溶媒二次電池の負極用銅箔を容易に提供できるという優れた製造方法である。
更に、本発明の非水溶媒二次電池負極電極の製造方法によれば、銅箔と負極活物質との密着性に優れ、充放電特性が向上する負極電極を提供することができる。 The copper foil for the negative electrode of the non-aqueous solvent secondary battery of the present invention is excellent in adhesion to the negative electrode active material, and is capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. It has the effect.
In addition, the method for producing a copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention is an excellent non-aqueous solvent secondary battery capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. This is an excellent manufacturing method in which a copper foil for a negative electrode of a battery can be easily provided.
Furthermore, according to the method for producing a non-aqueous solvent secondary battery negative electrode of the present invention, it is possible to provide a negative electrode having excellent adhesion between a copper foil and a negative electrode active material and improved charge / discharge characteristics.
また、本発明の非水溶媒二次電池負極集電体用銅箔の製造方法は、非水溶媒二次電池の充放電サイクル寿命と高い電池容量の保持が可能な優れた非水溶媒二次電池の負極用銅箔を容易に提供できるという優れた製造方法である。
更に、本発明の非水溶媒二次電池負極電極の製造方法によれば、銅箔と負極活物質との密着性に優れ、充放電特性が向上する負極電極を提供することができる。 The copper foil for the negative electrode of the non-aqueous solvent secondary battery of the present invention is excellent in adhesion to the negative electrode active material, and is capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. It has the effect.
In addition, the method for producing a copper foil for a non-aqueous solvent secondary battery negative electrode current collector of the present invention is an excellent non-aqueous solvent secondary battery capable of maintaining the charge / discharge cycle life and high battery capacity of the non-aqueous solvent secondary battery. This is an excellent manufacturing method in which a copper foil for a negative electrode of a battery can be easily provided.
Furthermore, according to the method for producing a non-aqueous solvent secondary battery negative electrode of the present invention, it is possible to provide a negative electrode having excellent adhesion between a copper foil and a negative electrode active material and improved charge / discharge characteristics.
本発明者らは銅箔表面上に一定厚さの有機化合物皮膜を形成し、負極活物質との密着性を高めたＬｉイオン二次電池の負極集電体用銅箔の開発を行った。
The inventors of the present invention have developed a copper foil for a negative electrode current collector of a Li ion secondary battery in which an organic compound film having a certain thickness is formed on the surface of the copper foil to improve adhesion with the negative electrode active material.
近年、例えば、電気自動車用電池として開発されているＬｉイオン二次電池等では更なる性能向上が要望されている。
Ｌｉイオン二次電池等の更なる性能向上には上記有機化合物皮膜の厚さが負極活物質の密着性を高め、銅箔表面の耐食性に対して重要な要因となってきている。
特許文献１に記載されている誘電体層の厚さを示す電気二重層容量の逆数（１／Ｃ）が０．１～０．３ｃｍ２／μＦでは、有機化合物皮膜の厚さが薄いために銅箔と負極活物質との密着性を高める効果が充分ではなく、また銅箔の防錆についても不充分となってきている。特に負極活物質を水を溶媒としたスラリーとして銅箔表面に塗布する製法では両者の密着性、銅箔表面の耐食性が不十分となってきている。
このため、本発明者が特許文献１に記載されている誘電体層の厚さよりさらに厚い誘電体層を皮膜した銅箔につき負極活物質との密着性、銅箔表面の耐食性につき検討した結果、１／Ｃ値にして０.３１～０．９ｃｍ２／μＦの皮膜を有する銅箔が、銅箔と活物質間の密着性を向上し、銅箔の耐食性も向上する、との結論を得た。 In recent years, for example, Li ion secondary batteries developed as batteries for electric vehicles have been demanded to further improve performance.
In order to further improve the performance of Li ion secondary batteries and the like, the thickness of the organic compound film increases the adhesion of the negative electrode active material and has become an important factor for the corrosion resistance of the copper foil surface.
When the reciprocal (1 / C) of the electric double layer capacitance indicating the thickness of the dielectric layer described in Patent Document 1 is 0.1 to 0.3 cm 2 / μF, the thickness of the organic compound film is small. The effect of increasing the adhesion between the copper foil and the negative electrode active material is not sufficient, and the anticorrosion of the copper foil has become insufficient. In particular, in the production method in which the negative electrode active material is applied to the copper foil surface as a slurry using water as a solvent, the adhesion between them and the corrosion resistance of the copper foil surface have become insufficient.
For this reason, as a result of studying the adhesion with the negative electrode active material and the corrosion resistance of the copper foil surface for the copper foil coated with a dielectric layer thicker than the thickness of the dielectric layer described in Patent Document 1, A conclusion was obtained that a copper foil having a 1 / C value of 0.31 to 0.9 cm 2 / μF improves the adhesion between the copper foil and the active material and also improves the corrosion resistance of the copper foil. It was.
Ｌｉイオン二次電池等の更なる性能向上には上記有機化合物皮膜の厚さが負極活物質の密着性を高め、銅箔表面の耐食性に対して重要な要因となってきている。
特許文献１に記載されている誘電体層の厚さを示す電気二重層容量の逆数（１／Ｃ）が０．１～０．３ｃｍ２／μＦでは、有機化合物皮膜の厚さが薄いために銅箔と負極活物質との密着性を高める効果が充分ではなく、また銅箔の防錆についても不充分となってきている。特に負極活物質を水を溶媒としたスラリーとして銅箔表面に塗布する製法では両者の密着性、銅箔表面の耐食性が不十分となってきている。
このため、本発明者が特許文献１に記載されている誘電体層の厚さよりさらに厚い誘電体層を皮膜した銅箔につき負極活物質との密着性、銅箔表面の耐食性につき検討した結果、１／Ｃ値にして０.３１～０．９ｃｍ２／μＦの皮膜を有する銅箔が、銅箔と活物質間の密着性を向上し、銅箔の耐食性も向上する、との結論を得た。 In recent years, for example, Li ion secondary batteries developed as batteries for electric vehicles have been demanded to further improve performance.
In order to further improve the performance of Li ion secondary batteries and the like, the thickness of the organic compound film increases the adhesion of the negative electrode active material and has become an important factor for the corrosion resistance of the copper foil surface.
When the reciprocal (1 / C) of the electric double layer capacitance indicating the thickness of the dielectric layer described in Patent Document 1 is 0.1 to 0.3 cm 2 / μF, the thickness of the organic compound film is small. The effect of increasing the adhesion between the copper foil and the negative electrode active material is not sufficient, and the anticorrosion of the copper foil has become insufficient. In particular, in the production method in which the negative electrode active material is applied to the copper foil surface as a slurry using water as a solvent, the adhesion between them and the corrosion resistance of the copper foil surface have become insufficient.
For this reason, as a result of studying the adhesion with the negative electrode active material and the corrosion resistance of the copper foil surface for the copper foil coated with a dielectric layer thicker than the thickness of the dielectric layer described in Patent Document 1, A conclusion was obtained that a copper foil having a 1 / C value of 0.31 to 0.9 cm 2 / μF improves the adhesion between the copper foil and the active material and also improves the corrosion resistance of the copper foil. It was.
なお、有機化合物皮膜の厚みは、市販の直読式電気二重層容量測定器で銅箔表面の電気二重層容量（キャパシタンス、Ｃ：μF）を測定し、（１）式で示すように、その逆数値（１／Ｃ）として算出した。
１／Ｃ＝Ａ・ｄ＋Ｂ ……（１）
ただし、
ｄは銅箔表面に形成されている電気二重層の厚みであり、Ａ，Ｂは定数である。 The thickness of the organic compound film was measured by measuring the electric double layer capacity (capacitance, C: μF) on the surface of the copper foil with a commercially available direct-reading type electric double layer capacity measuring device. Calculated as a numerical value (1 / C).
1 / C = A · d + B (1)
However,
d is the thickness of the electric double layer formed on the copper foil surface, and A and B are constants.
１／Ｃ＝Ａ・ｄ＋Ｂ ……（１）
ただし、
ｄは銅箔表面に形成されている電気二重層の厚みであり、Ａ，Ｂは定数である。 The thickness of the organic compound film was measured by measuring the electric double layer capacity (capacitance, C: μF) on the surface of the copper foil with a commercially available direct-reading type electric double layer capacity measuring device. Calculated as a numerical value (1 / C).
1 / C = A · d + B (1)
However,
d is the thickness of the electric double layer formed on the copper foil surface, and A and B are constants.
本発明の実施の形態の銅箔は、１／Ｃ値が０.３１～０．９ｃｍ２／μＦの範囲内に設定される。１／Ｃ値が０.３１ｃｍ２／μＦよりも小さい値として計測される有機皮膜層が形成された銅箔の場合は、活物質との密着性が低くなり、耐食性にも劣る傾向にある。また１／Ｃ値が０．９ｃｍ２／μＦより大きい銅箔は、それ以上高めても（皮膜を厚くしても）密着性は飽和してしまい改善効果がなくなるためである。
In the copper foil according to the embodiment of the present invention, the 1 / C value is set within the range of 0.31 to 0.9 cm 2 / μF. In the case of a copper foil on which an organic film layer is measured with a 1 / C value smaller than 0.31 cm 2 / μF, the adhesion with the active material tends to be low and the corrosion resistance tends to be poor. In addition, a copper foil having a 1 / C value greater than 0.9 cm 2 / μF is because even if it is further increased (even if the film is thickened), the adhesiveness is saturated and the improvement effect is lost.
まず、本発明の実施の形態の銅箔について説明する。
銅箔を製造するための素材は、電解銅箔、圧延銅箔のいずれであってもよい。電解銅箔の場合には、低コストで広幅なものが製箔できるので、生産性を高め大量生産することが必要な、例えば、電気自動車用電池の負極集電体として使用するのに適している。 First, the copper foil of embodiment of this invention is demonstrated.
The material for producing the copper foil may be either an electrolytic copper foil or a rolled copper foil. In the case of electrolytic copper foil, a wide variety can be made at low cost, and it is necessary to increase productivity and mass production. For example, it is suitable for use as a negative electrode current collector of an electric vehicle battery. Yes.
銅箔を製造するための素材は、電解銅箔、圧延銅箔のいずれであってもよい。電解銅箔の場合には、低コストで広幅なものが製箔できるので、生産性を高め大量生産することが必要な、例えば、電気自動車用電池の負極集電体として使用するのに適している。 First, the copper foil of embodiment of this invention is demonstrated.
The material for producing the copper foil may be either an electrolytic copper foil or a rolled copper foil. In the case of electrolytic copper foil, a wide variety can be made at low cost, and it is necessary to increase productivity and mass production. For example, it is suitable for use as a negative electrode current collector of an electric vehicle battery. Yes.
また、本発明の実施の形態の銅箔の表面粗さは、ＪＩＳＢ０６０１－１９９４で規定する１０点平均粗さ（Ｒｚ）で２.５μｍ以下であることが好適である。そのような銅箔は有機化合物皮膜を薄く均一な厚みで形成することができ、しかもその上に担持される負極活物質も均一となって、負極活物質との密着性に優れ電池の充放電サイクル寿命特性と充電初期の電池容量が向上する。
Further, the surface roughness of the copper foil according to the embodiment of the present invention is preferably 2.5 μm or less in terms of the 10-point average roughness (Rz) defined by JISB0601-1994. Such a copper foil can form an organic compound film with a thin and uniform thickness, and the negative electrode active material carried thereon is also uniform, and has excellent adhesion to the negative electrode active material, and charging / discharging of the battery. Cycle life characteristics and initial battery capacity are improved.
銅箔の厚みは薄ければ薄いほど全体としての電極面積が大きくなり、また、表面粗さを小さくできるので、高エネルギー密度化や充放電サイクル寿命特性にとって有利である。例えば、携帯用の電気・電子機器用の小型の電池、あるいは電気自動車用などの大型電池の場合でも銅箔の厚みは２０μｍ以下にすることが好ましい。
しかしながら、銅箔の厚みをあまり薄くすると、その機械的強度が低下し、またピンホールなども多くなってくるので、実使用に耐え得る銅箔としての厚みの下限は、６μｍ程度である。
このように、好ましい銅箔の厚みは、２０～６μｍである。 The thinner the copper foil, the larger the electrode area as a whole, and the lower the surface roughness, which is advantageous for high energy density and charge / discharge cycle life characteristics. For example, the thickness of the copper foil is preferably 20 μm or less even in the case of a small battery for portable electric / electronic devices or a large battery for an electric vehicle.
However, if the thickness of the copper foil is made too thin, its mechanical strength decreases and pinholes and the like increase, so the lower limit of the thickness of the copper foil that can withstand actual use is about 6 μm.
Thus, the preferred thickness of the copper foil is 20 to 6 μm.
しかしながら、銅箔の厚みをあまり薄くすると、その機械的強度が低下し、またピンホールなども多くなってくるので、実使用に耐え得る銅箔としての厚みの下限は、６μｍ程度である。
このように、好ましい銅箔の厚みは、２０～６μｍである。 The thinner the copper foil, the larger the electrode area as a whole, and the lower the surface roughness, which is advantageous for high energy density and charge / discharge cycle life characteristics. For example, the thickness of the copper foil is preferably 20 μm or less even in the case of a small battery for portable electric / electronic devices or a large battery for an electric vehicle.
However, if the thickness of the copper foil is made too thin, its mechanical strength decreases and pinholes and the like increase, so the lower limit of the thickness of the copper foil that can withstand actual use is about 6 μm.
Thus, the preferred thickness of the copper foil is 20 to 6 μm.
この銅箔の表面に形成される有機化合物皮膜は、トリアゾール化合物を含有する皮膜である。あるいはトリアゾール化合物及びアミン化合物を含有する皮膜である。
トリアゾール化合物、あるいはトリアゾール化合物とアミン化合物は、水あるいは有機溶剤に溶解し、溶液温度を一定に保ち、銅箔を一定時間浸漬し、その後乾燥することにより、銅箔表面に有機化合物皮膜を形成させる。 The organic compound film formed on the surface of the copper foil is a film containing a triazole compound. Alternatively, it is a film containing a triazole compound and an amine compound.
The triazole compound, or the triazole compound and the amine compound are dissolved in water or an organic solvent, the solution temperature is kept constant, the copper foil is immersed for a certain time, and then dried to form an organic compound film on the copper foil surface. .
トリアゾール化合物、あるいはトリアゾール化合物とアミン化合物は、水あるいは有機溶剤に溶解し、溶液温度を一定に保ち、銅箔を一定時間浸漬し、その後乾燥することにより、銅箔表面に有機化合物皮膜を形成させる。 The organic compound film formed on the surface of the copper foil is a film containing a triazole compound. Alternatively, it is a film containing a triazole compound and an amine compound.
The triazole compound, or the triazole compound and the amine compound are dissolved in water or an organic solvent, the solution temperature is kept constant, the copper foil is immersed for a certain time, and then dried to form an organic compound film on the copper foil surface. .
トリアゾール化合物溶液、トリアゾール化合物及びアミン化合物溶液の濃度は、１０～１０，０００ｐｐｍが良い。
１０ｐｐｍを下回ると負極活物質との密着性を保持できるほどの有機化合物皮膜厚さとならず、１０，０００ｐｐｍをこえても有機化合物皮膜厚さは飽和してしまい、密着性向上の効果も期待できないからである。
さらに好ましくは５０～５，０００ｐｐｍである。
また、溶液の温度は室温であればよいが、必要に応じては加温して使用してもよい。 The concentration of the triazole compound solution, triazole compound and amine compound solution is preferably 10 to 10,000 ppm.
If it is less than 10 ppm, the organic compound film thickness is not sufficient to maintain the adhesion to the negative electrode active material, and even if it exceeds 10,000 ppm, the organic compound film thickness is saturated, and the effect of improving adhesion cannot be expected. Because.
More preferably, it is 50 to 5,000 ppm.
Further, the temperature of the solution may be room temperature, but may be used after heating if necessary.
１０ｐｐｍを下回ると負極活物質との密着性を保持できるほどの有機化合物皮膜厚さとならず、１０，０００ｐｐｍをこえても有機化合物皮膜厚さは飽和してしまい、密着性向上の効果も期待できないからである。
さらに好ましくは５０～５，０００ｐｐｍである。
また、溶液の温度は室温であればよいが、必要に応じては加温して使用してもよい。 The concentration of the triazole compound solution, triazole compound and amine compound solution is preferably 10 to 10,000 ppm.
If it is less than 10 ppm, the organic compound film thickness is not sufficient to maintain the adhesion to the negative electrode active material, and even if it exceeds 10,000 ppm, the organic compound film thickness is saturated, and the effect of improving adhesion cannot be expected. Because.
More preferably, it is 50 to 5,000 ppm.
Further, the temperature of the solution may be room temperature, but may be used after heating if necessary.
トリアゾール化合物に更にアミン化合物を加えた溶液を銅箔上に塗布すると、トリアゾール化合物単独の場合に比べ銅箔と負極活物質との密着性が更に良好になるとともに、銅箔の耐食性も向上し、より好ましい。
トリアゾール化合物とアミン化合物の配合割合は、重量にしてトリアゾール化合物に対しアミン化合物を約０．５～２倍が有効である。２倍以上アミン化合物を加えても最早密着性、耐食性の向上が望めず、また、０．５倍を下回ると密着性、耐食性の効果が発現しないためである。 When a solution in which an amine compound is further added to a triazole compound is applied on the copper foil, the adhesion between the copper foil and the negative electrode active material is further improved as compared to the case of the triazole compound alone, and the corrosion resistance of the copper foil is also improved. More preferred.
The blending ratio of the triazole compound and the amine compound is about 0.5 to 2 times that of the amine compound relative to the triazole compound by weight. This is because even if the amine compound is added twice or more, improvement in adhesion and corrosion resistance can no longer be expected, and if it is less than 0.5 times, the effect of adhesion and corrosion resistance is not exhibited.
トリアゾール化合物とアミン化合物の配合割合は、重量にしてトリアゾール化合物に対しアミン化合物を約０．５～２倍が有効である。２倍以上アミン化合物を加えても最早密着性、耐食性の向上が望めず、また、０．５倍を下回ると密着性、耐食性の効果が発現しないためである。 When a solution in which an amine compound is further added to a triazole compound is applied on the copper foil, the adhesion between the copper foil and the negative electrode active material is further improved as compared to the case of the triazole compound alone, and the corrosion resistance of the copper foil is also improved. More preferred.
The blending ratio of the triazole compound and the amine compound is about 0.5 to 2 times that of the amine compound relative to the triazole compound by weight. This is because even if the amine compound is added twice or more, improvement in adhesion and corrosion resistance can no longer be expected, and if it is less than 0.5 times, the effect of adhesion and corrosion resistance is not exhibited.
溶液への銅箔の浸漬時間は、トリアゾール化合物、トリアゾール化合物及びアミン化合物の溶解濃度、溶液温度や形成する有機化合物皮膜の厚みとの関係で適宜に決められるが、通常、０.５～３０秒程度であればよい。
The immersion time of the copper foil in the solution is appropriately determined depending on the relationship between the concentration of the triazole compound, the triazole compound and the amine compound, the solution temperature, and the thickness of the organic compound film to be formed, but usually 0.5 to 30 seconds. Any degree is acceptable.
トリアゾール化合物としては、ベンゾトリアゾール、トリルトリアゾール、カルボキシベンゾトリアゾール、クロロベンゾトリアゾール、エチルベンゾトリアゾール、ナフトトリアゾール等が挙げられる。
Examples of the triazole compound include benzotriazole, tolyltriazole, carboxybenzotriazole, chlorobenzotriazole, ethylbenzotriazole, and naphthotriazole.
また、アミン化合物としては、モノアルキルアミン、ジアルキルアミン、トリアルキルアミン、モノシクロヘキシルアミン、ジシクロヘキシルアミンなどのモノアミン類、１～４個のアルキル基で置換されたジアミン類、アルキル基の少なくとも１個が水酸基やポリオキシエチレン基のような親水性基を有するアルキルモノアミン、アルキルジアミンなどがある。これらのうち、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モノメチルエタノールアミン、モノエチルエタノールアミン、モノブチルエタノールアミン等が挙げられる。
Examples of the amine compound include monoamines such as monoalkylamine, dialkylamine, trialkylamine, monocyclohexylamine, dicyclohexylamine, diamines substituted with 1 to 4 alkyl groups, and at least one alkyl group. Examples include alkyl monoamines and alkyl diamines having a hydrophilic group such as a hydroxyl group or a polyoxyethylene group. Among these, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, monomethylethanolamine, monoethylethanolamine, monobutylethanolamine and the like can be mentioned.
この有機化合物皮膜は、一般に、銅箔の両面に形成するが、電池の製造工程、負極としての形態や使用目的との関係で片面だけであってもよい。しかしながら、通常のＬｉイオン二次電池の正極、負極の場合には、いずれも各集電体の両面に活物質が担持された構造になっているので、銅箔の両面に上記したような有機皮膜層が形成されていることをもって好適とする。
This organic compound film is generally formed on both sides of the copper foil, but it may be only on one side in relation to the battery manufacturing process, the form as the negative electrode and the purpose of use. However, in the case of a positive electrode and a negative electrode of a normal Li ion secondary battery, both have a structure in which an active material is supported on both surfaces of each current collector. A film layer is preferably formed.
本発明の実施の形態に基づく非水溶媒二次電池に用いる負極集電体用銅箔は、図１に示すプロセスで製造される。
ステップ１：たとえば、厚さ６～２０μｍ、表面粗さ（Ｒｚ）２．５μｍ以下の銅箔を製造／準備する。
ステップ２：銅箔を有機化合物を含む水溶液に浸漬させて、水溶液に接触させる。
ステップ３：乾燥させる。
以上により、１／Ｃが０.３１～０．９ｃｍ２／μＦの負極集電体用銅箔が形成される。この負極集電体用銅箔に下記の処理を施すことにより、非水溶媒二次電池用負極電極が形成される。
ステップ４：負極活物質スラリーを塗布する。
ステップ５：乾燥させる。
以下、本発明の実施の形態に基づく、実施例を述べる。 The copper foil for negative electrode current collectors used for the non-aqueous solvent secondary battery based on the embodiment of the present invention is manufactured by the process shown in FIG.
Step 1: For example, a copper foil having a thickness of 6 to 20 μm and a surface roughness (Rz) of 2.5 μm or less is manufactured / prepared.
Step 2: The copper foil is immersed in an aqueous solution containing an organic compound and brought into contact with the aqueous solution.
Step 3: Dry.
Thus, a copper foil for a negative electrode current collector having a 1 / C of 0.31 to 0.9 cm 2 / μF is formed. By subjecting this copper foil for a negative electrode current collector to the following treatment, a negative electrode for a nonaqueous solvent secondary battery is formed.
Step 4: Apply negative electrode active material slurry.
Step 5: Dry.
Examples based on the embodiments of the present invention will be described below.
ステップ１：たとえば、厚さ６～２０μｍ、表面粗さ（Ｒｚ）２．５μｍ以下の銅箔を製造／準備する。
ステップ２：銅箔を有機化合物を含む水溶液に浸漬させて、水溶液に接触させる。
ステップ３：乾燥させる。
以上により、１／Ｃが０.３１～０．９ｃｍ２／μＦの負極集電体用銅箔が形成される。この負極集電体用銅箔に下記の処理を施すことにより、非水溶媒二次電池用負極電極が形成される。
ステップ４：負極活物質スラリーを塗布する。
ステップ５：乾燥させる。
以下、本発明の実施の形態に基づく、実施例を述べる。 The copper foil for negative electrode current collectors used for the non-aqueous solvent secondary battery based on the embodiment of the present invention is manufactured by the process shown in FIG.
Step 1: For example, a copper foil having a thickness of 6 to 20 μm and a surface roughness (Rz) of 2.5 μm or less is manufactured / prepared.
Step 2: The copper foil is immersed in an aqueous solution containing an organic compound and brought into contact with the aqueous solution.
Step 3: Dry.
Thus, a copper foil for a negative electrode current collector having a 1 / C of 0.31 to 0.9 cm 2 / μF is formed. By subjecting this copper foil for a negative electrode current collector to the following treatment, a negative electrode for a nonaqueous solvent secondary battery is formed.
Step 4: Apply negative electrode active material slurry.
Step 5: Dry.
Examples based on the embodiments of the present invention will be described below.
〔銅箔の製造：ステップ１〕
電解液
銅： ７０～１３０ｇ／ｌ
硫酸： ８０～１４０ｇ／ｌ
添加剤： ３－メルカプト１－プロパンスルホン酸ナトリウム＝１～１０ｐｐｍ
ヒドロキシエチルセルロース＝1～１００ｐｐｍ
低分子量膠（分子量３，０００）＝１～５０ｐｐｍ
塩化物イオン濃度＝１０～５０ｐｐｍ
温度： ５０～６０度
この電解液を用いて、アノードには貴金属酸化物被覆チタン電極、カソードにはチタン製回転ドラムを用いて、電流密度＝５０～１００Ａ／ｄｍ２で厚さ６～２０μｍ、両面の表面粗度（Ｒｚ）２．５μｍ以下の電解銅箔を製造した。 [Manufacture of copper foil: Step 1]
Electrolytic copper: 70-130 g / l
Sulfuric acid: 80-140 g / l
Additive: Sodium 3-mercapto 1-propanesulfonate = 1-10 ppm
Hydroxyethyl cellulose = 1-100ppm
Low molecular weight glue (molecular weight 3,000) = 1-50ppm
Chloride ion concentration = 10-50ppm
Temperature: 50 to 60 degrees Using this electrolytic solution, a noble metal oxide-coated titanium electrode for the anode and a titanium rotating drum for the cathode, a current density of 50 to 100 A / dm 2 and a thickness of 6 to 20 μm, An electrolytic copper foil having a surface roughness (Rz) of 2.5 μm or less on both sides was produced.
電解液
銅： ７０～１３０ｇ／ｌ
硫酸： ８０～１４０ｇ／ｌ
添加剤： ３－メルカプト１－プロパンスルホン酸ナトリウム＝１～１０ｐｐｍ
ヒドロキシエチルセルロース＝1～１００ｐｐｍ
低分子量膠（分子量３，０００）＝１～５０ｐｐｍ
塩化物イオン濃度＝１０～５０ｐｐｍ
温度： ５０～６０度
この電解液を用いて、アノードには貴金属酸化物被覆チタン電極、カソードにはチタン製回転ドラムを用いて、電流密度＝５０～１００Ａ／ｄｍ２で厚さ６～２０μｍ、両面の表面粗度（Ｒｚ）２．５μｍ以下の電解銅箔を製造した。 [Manufacture of copper foil: Step 1]
Electrolytic copper: 70-130 g / l
Sulfuric acid: 80-140 g / l
Additive: Sodium 3-mercapto 1-propanesulfonate = 1-10 ppm
Hydroxyethyl cellulose = 1-100ppm
Low molecular weight glue (molecular weight 3,000) = 1-50ppm
Chloride ion concentration = 10-50ppm
Temperature: 50 to 60 degrees Using this electrolytic solution, a noble metal oxide-coated titanium electrode for the anode and a titanium rotating drum for the cathode, a current density of 50 to 100 A / dm 2 and a thickness of 6 to 20 μm, An electrolytic copper foil having a surface roughness (Rz) of 2.5 μm or less on both sides was produced.
〔被膜形成用有機化合物〕
１：トリアゾール化合物（そのうちの一種としてＢＴＡ）
２：トリアゾール化合物（そのうちの一種としてＢＴＡ）+アミン化合物（そのうちの一種としてＴＥＡ）
ＢＴＡ：ベンゾトリアゾール
ＴＥＡ：トリエタノールアミン
テトラゾール：1Ｈ－テトラゾール・モノエタノールアミン塩 [Organic compound for film formation]
1: Triazole compound (BTA as one of them)
2: Triazole compounds (BTA as one of them) + amine compounds (TEA as one of them)
BTA: benzotriazole TEA: triethanolamine tetrazole: 1H-tetrazole monoethanolamine salt
１：トリアゾール化合物（そのうちの一種としてＢＴＡ）
２：トリアゾール化合物（そのうちの一種としてＢＴＡ）+アミン化合物（そのうちの一種としてＴＥＡ）
ＢＴＡ：ベンゾトリアゾール
ＴＥＡ：トリエタノールアミン
テトラゾール：1Ｈ－テトラゾール・モノエタノールアミン塩 [Organic compound for film formation]
1: Triazole compound (BTA as one of them)
2: Triazole compounds (BTA as one of them) + amine compounds (TEA as one of them)
BTA: benzotriazole TEA: triethanolamine tetrazole: 1H-tetrazole monoethanolamine salt
〔クロメート処理〕
ＣｒＯ３＝1～５０ｇ／ｌを溶解した水溶液中に銅箔を浸漬し(ステップ２)、その後乾燥を行った(ステップ３)。 [Chromate treatment]
The copper foil was immersed in an aqueous solution in which CrO 3 = 1 to 50 g / l was dissolved (Step 2), and then dried (Step 3).
ＣｒＯ３＝1～５０ｇ／ｌを溶解した水溶液中に銅箔を浸漬し(ステップ２)、その後乾燥を行った(ステップ３)。 [Chromate treatment]
The copper foil was immersed in an aqueous solution in which CrO 3 = 1 to 50 g / l was dissolved (Step 2), and then dried (Step 3).
上記銅箔に被膜形成用有機化合物、ＣｒＯ３を表１に示す条件で塗布した。
An organic compound for film formation, CrO 3 , was applied to the copper foil under the conditions shown in Table 1.
作成した１４種類の電極上に下記活物質を塗工し(ステップ４)、密着性の評価を行った。
〔負極活物質層の作製〕
先ず、プライミクス製ホモミクサーを用いて、カルボキシメチルセルロース（ＣＭＣ）〔ダイセル化学工業製＃１３８０〕を脱イオン水に溶解させることにより、濃度１．０質量％のＣＭＣ水溶液を得た。
次に、このＣＭＣ水溶液１０００ｇと、人造黒鉛（平均粒径２１μｍ、表面積４．０ｍ２／ｇ）９８０ｇとを秤量し、プライミクス製ホモミクサーを用いて混合した後、スチレンブタジエンラバー（ＳＢＲ）（固形分濃度５０質量％）２０ｇを追加して、負極スラリーを調製した。
なお、人造黒鉛とＣＭＣとＳＢＲとの質量比は、人造黒鉛：ＣＭＣ：ＳＢＲ＝９８．０：１．０：１．０である。
上記負極スラリーを、リバースコート方式を用いて、両面に有機化合物を塗布した銅箔から成る負極集電体の両面に塗工し、更に乾燥、圧延（プレス成形）することにより、負極集電体の両面に負極活物質層を形成した。なお、負極活物質の塗布量は２２６ｍｇ／１０ｃｍ2であり、負極充填密度は１．６０ｇ／ｃｃとした。 The following active materials were applied on the 14 types of electrodes prepared (Step 4), and the adhesion was evaluated.
[Preparation of negative electrode active material layer]
First, a CMC aqueous solution having a concentration of 1.0% by mass was obtained by dissolving carboxymethyl cellulose (CMC) [# 1380 manufactured by Daicel Chemical Industries, Ltd.] in deionized water using a homomixer manufactured by PRIMIX.
Next, 1000 g of this CMC aqueous solution and 980 g of artificial graphite (average particle diameter 21 μm, surface area 4.0 m 2 / g) were weighed and mixed using a homomixer manufactured by PRIMIX, and then styrene butadiene rubber (SBR) (solid content A negative electrode slurry was prepared by adding 20 g of a 50 mass% concentration.
In addition, the mass ratio of artificial graphite, CMC, and SBR is artificial graphite: CMC: SBR = 98.0: 1.0: 1.0.
The negative electrode current collector is coated on both sides of a negative electrode current collector made of a copper foil coated with an organic compound on both sides using a reverse coating method, and further dried and rolled (press-molded). A negative electrode active material layer was formed on both sides of the substrate. The coating amount of the negative electrode active material was 226 mg / 10 cm 2 and the negative electrode filling density was 1.60 g / cc.
〔負極活物質層の作製〕
先ず、プライミクス製ホモミクサーを用いて、カルボキシメチルセルロース（ＣＭＣ）〔ダイセル化学工業製＃１３８０〕を脱イオン水に溶解させることにより、濃度１．０質量％のＣＭＣ水溶液を得た。
次に、このＣＭＣ水溶液１０００ｇと、人造黒鉛（平均粒径２１μｍ、表面積４．０ｍ２／ｇ）９８０ｇとを秤量し、プライミクス製ホモミクサーを用いて混合した後、スチレンブタジエンラバー（ＳＢＲ）（固形分濃度５０質量％）２０ｇを追加して、負極スラリーを調製した。
なお、人造黒鉛とＣＭＣとＳＢＲとの質量比は、人造黒鉛：ＣＭＣ：ＳＢＲ＝９８．０：１．０：１．０である。
上記負極スラリーを、リバースコート方式を用いて、両面に有機化合物を塗布した銅箔から成る負極集電体の両面に塗工し、更に乾燥、圧延（プレス成形）することにより、負極集電体の両面に負極活物質層を形成した。なお、負極活物質の塗布量は２２６ｍｇ／１０ｃｍ2であり、負極充填密度は１．６０ｇ／ｃｃとした。 The following active materials were applied on the 14 types of electrodes prepared (Step 4), and the adhesion was evaluated.
[Preparation of negative electrode active material layer]
First, a CMC aqueous solution having a concentration of 1.0% by mass was obtained by dissolving carboxymethyl cellulose (CMC) [# 1380 manufactured by Daicel Chemical Industries, Ltd.] in deionized water using a homomixer manufactured by PRIMIX.
Next, 1000 g of this CMC aqueous solution and 980 g of artificial graphite (average particle diameter 21 μm, surface area 4.0 m 2 / g) were weighed and mixed using a homomixer manufactured by PRIMIX, and then styrene butadiene rubber (SBR) (solid content A negative electrode slurry was prepared by adding 20 g of a 50 mass% concentration.
In addition, the mass ratio of artificial graphite, CMC, and SBR is artificial graphite: CMC: SBR = 98.0: 1.0: 1.0.
The negative electrode current collector is coated on both sides of a negative electrode current collector made of a copper foil coated with an organic compound on both sides using a reverse coating method, and further dried and rolled (press-molded). A negative electrode active material layer was formed on both sides of the substrate. The coating amount of the negative electrode active material was 226 mg / 10 cm 2 and the negative electrode filling density was 1.60 g / cc.
〔負極活物質密着性の測定〕
集電体と有機化合物皮膜との間の密着強度を、以下のように９０度剥離試験法によって評価した。具体的には、７０ｍｍ×２０ｍｍサイズの両面テープ（ニチバン株式会社社製「ナイスタック ＮＷ－２０」）を用いて１２０ｍｍ×３０ｍｍサイズのアクリル板に負極を貼付し、貼り付けられた負極の端部を日本電産シンポ株式会社社製小型卓上試験機（「ＦＧＳ－ＴＶ」及び「ＦＧＰ－５」）で有機化合物皮膜表面に対して９０度の方向に、一定速度（５０ｍｍ／ｍｉｎ）で上方に５５ｍｍ引っ張り、剥離時の強度を測定した。
この剥離強度測定を３回行い、３回の測定結果を平均した値を９０度剥離強度とし表４に測定結果を示す。
表４から各実施例は標準とした比較例２と略同等の密着性を示している。 [Measurement of adhesion of negative electrode active material]
The adhesion strength between the current collector and the organic compound film was evaluated by a 90-degree peel test method as follows. Specifically, a negative electrode is attached to an acrylic plate having a size of 120 mm × 30 mm using a 70 mm × 20 mm double-sided tape (“Nystack NW-20” manufactured by Nichiban Co., Ltd.), and the end of the attached negative electrode Is moved upward at a constant speed (50 mm / min) in a direction of 90 degrees with respect to the surface of the organic compound film with a small table tester (“FGS-TV” and “FGP-5”) manufactured by Nidec Sympo Corporation. The strength at the time of peeling was measured by 55 mm.
This peel strength measurement was performed three times, and the average of the three measurement results was 90 ° peel strength. Table 4 shows the measurement results.
From Table 4, each example shows substantially the same adhesion as Comparative Example 2 as a standard.
集電体と有機化合物皮膜との間の密着強度を、以下のように９０度剥離試験法によって評価した。具体的には、７０ｍｍ×２０ｍｍサイズの両面テープ（ニチバン株式会社社製「ナイスタック ＮＷ－２０」）を用いて１２０ｍｍ×３０ｍｍサイズのアクリル板に負極を貼付し、貼り付けられた負極の端部を日本電産シンポ株式会社社製小型卓上試験機（「ＦＧＳ－ＴＶ」及び「ＦＧＰ－５」）で有機化合物皮膜表面に対して９０度の方向に、一定速度（５０ｍｍ／ｍｉｎ）で上方に５５ｍｍ引っ張り、剥離時の強度を測定した。
この剥離強度測定を３回行い、３回の測定結果を平均した値を９０度剥離強度とし表４に測定結果を示す。
表４から各実施例は標準とした比較例２と略同等の密着性を示している。 [Measurement of adhesion of negative electrode active material]
The adhesion strength between the current collector and the organic compound film was evaluated by a 90-degree peel test method as follows. Specifically, a negative electrode is attached to an acrylic plate having a size of 120 mm × 30 mm using a 70 mm × 20 mm double-sided tape (“Nystack NW-20” manufactured by Nichiban Co., Ltd.), and the end of the attached negative electrode Is moved upward at a constant speed (50 mm / min) in a direction of 90 degrees with respect to the surface of the organic compound film with a small table tester (“FGS-TV” and “FGP-5”) manufactured by Nidec Sympo Corporation. The strength at the time of peeling was measured by 55 mm.
This peel strength measurement was performed three times, and the average of the three measurement results was 90 ° peel strength. Table 4 shows the measurement results.
From Table 4, each example shows substantially the same adhesion as Comparative Example 2 as a standard.
〔表面に有機化合物被膜を形成した誘電体層の厚み〕
上述したように、表面に有機化合物皮膜を形成した銅箔表面の誘電体層の厚みを、電気二重層容量（Ｃ：μＦ）を測定し、次式に基づいて厚みを確認した。
１／Ｃ＝Ａ・ｄ＋Ｂ ……（１）
ただし、
ｄは銅箔表面に形成されている電気二重層の厚みであり、Ａ，Ｂは定数である。
なお、１／Ｃの測定には日置電機(株)製ケミカルインピーダンスメーター ＨＩＯＫＩ３５３２－８０を用いた。１／Ｃの測定値を表５に示す。
また、クロメート皮膜は１／Ｃでは評価できないのでクロメート付着量を表６に示す。 [Thickness of dielectric layer with organic compound coating on surface]
As described above, the electric double layer capacitance (C: μF) was measured for the thickness of the dielectric layer on the surface of the copper foil having the organic compound film formed on the surface, and the thickness was confirmed based on the following formula.
1 / C = A · d + B (1)
However,
d is the thickness of the electric double layer formed on the copper foil surface, and A and B are constants.
For measurement of 1 / C, a chemical impedance meter HIOKI 3532-80 manufactured by Hioki Electric Co., Ltd. was used. The measured values of 1 / C are shown in Table 5.
Further, since the chromate film cannot be evaluated at 1 / C, the amount of chromate attached is shown in Table 6.
上述したように、表面に有機化合物皮膜を形成した銅箔表面の誘電体層の厚みを、電気二重層容量（Ｃ：μＦ）を測定し、次式に基づいて厚みを確認した。
１／Ｃ＝Ａ・ｄ＋Ｂ ……（１）
ただし、
ｄは銅箔表面に形成されている電気二重層の厚みであり、Ａ，Ｂは定数である。
なお、１／Ｃの測定には日置電機(株)製ケミカルインピーダンスメーター ＨＩＯＫＩ３５３２－８０を用いた。１／Ｃの測定値を表５に示す。
また、クロメート皮膜は１／Ｃでは評価できないのでクロメート付着量を表６に示す。 [Thickness of dielectric layer with organic compound coating on surface]
As described above, the electric double layer capacitance (C: μF) was measured for the thickness of the dielectric layer on the surface of the copper foil having the organic compound film formed on the surface, and the thickness was confirmed based on the following formula.
1 / C = A · d + B (1)
However,
d is the thickness of the electric double layer formed on the copper foil surface, and A and B are constants.
For measurement of 1 / C, a chemical impedance meter HIOKI 3532-80 manufactured by Hioki Electric Co., Ltd. was used. The measured values of 1 / C are shown in Table 5.
Further, since the chromate film cannot be evaluated at 1 / C, the amount of chromate attached is shown in Table 6.
〔耐酸化性比較〕
Ｌｉイオン二次電池の電極製造工程に於いては乾燥が重要となる(ステップ５)。この乾燥が不十分であり水分がＬｉイオン二次電池に持ち込まれた場合、電池のサイクル特性及び充放電容量に大きな影響を与える。
このため銅箔にはこの乾燥工程に於いて酸化し難い事が要求される。そこでトリアゾール系化合物で処理した銅箔とクロメート防錆で処理した銅箔の耐酸化性を測定した。
なお、測定は銅箔を大気オーブン中で１５０℃×１Ｈｒ加熱した後カソード還元法を用いて測定した。測定結果を表７に示す。 [Oxidation resistance comparison]
In the Li ion secondary battery electrode manufacturing process, drying is important (step 5). When this drying is insufficient and moisture is brought into the Li ion secondary battery, the battery cycle characteristics and charge / discharge capacity are greatly affected.
For this reason, the copper foil is required to be difficult to oxidize in this drying process. Therefore, the oxidation resistance of the copper foil treated with the triazole compound and the copper foil treated with chromate rust was measured.
The measurement was performed using a cathode reduction method after heating the copper foil in an atmospheric oven at 150 ° C. × 1 Hr. Table 7 shows the measurement results.
Ｌｉイオン二次電池の電極製造工程に於いては乾燥が重要となる(ステップ５)。この乾燥が不十分であり水分がＬｉイオン二次電池に持ち込まれた場合、電池のサイクル特性及び充放電容量に大きな影響を与える。
このため銅箔にはこの乾燥工程に於いて酸化し難い事が要求される。そこでトリアゾール系化合物で処理した銅箔とクロメート防錆で処理した銅箔の耐酸化性を測定した。
なお、測定は銅箔を大気オーブン中で１５０℃×１Ｈｒ加熱した後カソード還元法を用いて測定した。測定結果を表７に示す。 [Oxidation resistance comparison]
In the Li ion secondary battery electrode manufacturing process, drying is important (step 5). When this drying is insufficient and moisture is brought into the Li ion secondary battery, the battery cycle characteristics and charge / discharge capacity are greatly affected.
For this reason, the copper foil is required to be difficult to oxidize in this drying process. Therefore, the oxidation resistance of the copper foil treated with the triazole compound and the copper foil treated with chromate rust was measured.
The measurement was performed using a cathode reduction method after heating the copper foil in an atmospheric oven at 150 ° C. × 1 Hr. Table 7 shows the measurement results.
このデータよりトリアゾール化合物含有皮膜及びトリアゾール化合物及びアミン化合物含有皮膜がクロメート防錆よりも耐酸化性に優れていることが明らかである。
From this data, it is clear that the triazole compound-containing film and the triazole compound and amine compound-containing film have better oxidation resistance than chromate rust prevention.
〔恒温恒湿試験とその結果〕
６０℃×９０％の環境下での恒温恒湿評価を行った。評価結果を表８に示す。
評価は５段階で行い３以下は茶点及び変色にて電池としての使用は困難である、と評価した。 [Constant temperature and humidity test and results]
The constant temperature and humidity evaluation in an environment of 60 ° C. × 90% was performed. The evaluation results are shown in Table 8.
Evaluation was carried out in 5 stages, and 3 or less were evaluated as being difficult to use as a battery due to brown point and discoloration.
６０℃×９０％の環境下での恒温恒湿評価を行った。評価結果を表８に示す。
評価は５段階で行い３以下は茶点及び変色にて電池としての使用は困難である、と評価した。 [Constant temperature and humidity test and results]
The constant temperature and humidity evaluation in an environment of 60 ° C. × 90% was performed. The evaluation results are shown in Table 8.
Evaluation was carried out in 5 stages, and 3 or less were evaluated as being difficult to use as a battery due to brown point and discoloration.
比較例２（Ｎｏ．１４）のＭ面は９日目で茶点に変色して電池としての使用は困難な状態となったが、本発明に基づく各実施例はほとんど変色がなく、電池用銅箔として十分に使用できることが明らかとなった。
The M surface of Comparative Example 2 (No. 14) turned brown on the 9th day, making it difficult to use as a battery. However, each of the examples based on the present invention had almost no discoloration, and the copper for the battery. It became clear that it can be used sufficiently as a foil.
〔酸化量を測定〕
また、この時の酸化量を測定した。測定結果を表９に示す。 (Measure the amount of oxidation)
Further, the amount of oxidation at this time was measured. Table 9 shows the measurement results.
また、この時の酸化量を測定した。測定結果を表９に示す。 (Measure the amount of oxidation)
Further, the amount of oxidation at this time was measured. Table 9 shows the measurement results.
各実施例の酸化する速度は比較例２（Ｎｏ．１４）と比較して明らかに緩やかで、電池用電極として十分に使用可能であることが明らかになった。
The oxidation rate of each example was clearly moderate as compared with Comparative Example 2 (No. 14), and it was revealed that it could be used satisfactorily as a battery electrode.
上述したように、本発明の実施形態並びに実施例の非水溶媒二次電池負極用銅箔は、負極活物質との密着性、耐酸化性に優れ、高温、高湿の環境下においても変色せず、非水溶媒二次電池の充放電サイクル寿命と高い電池容量の保持を可能とする優れた効果を有するものである。
As described above, the non-aqueous solvent secondary battery negative electrode copper foils of the embodiments and examples of the present invention have excellent adhesion to the negative electrode active material and oxidation resistance, and are discolored even in high temperature and high humidity environments. Without having such an effect, the charge / discharge cycle life of the nonaqueous solvent secondary battery and the high battery capacity can be maintained.
Claims (15)
- 銅箔の表面に有機化合物を含む溶液を接触させ、その後乾燥し、前記銅箔の少なくとも片面に電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである皮膜を形成する
非水溶媒二次電池に用いる負極集電体用銅箔を製造する方法。 A film in which a solution containing an organic compound is brought into contact with the surface of the copper foil, and then dried, and at least one surface of the copper foil has a reciprocal (1 / C) of electric double layer capacity of 0.31 to 0.9 cm 2 / μF. A method of producing a copper foil for a negative electrode current collector used in a nonaqueous solvent secondary battery. - 前記有機化合物を含む溶液がトリアゾール化合物を含有する溶液である
請求項１記載の製造方法。 The manufacturing method according to claim 1, wherein the solution containing the organic compound is a solution containing a triazole compound. - 前記有機化合物を含む溶液がトリアゾール化合物及びアミン化合物を含有する溶液である
請求項１記載の製造方法。 The manufacturing method according to claim 1, wherein the solution containing the organic compound is a solution containing a triazole compound and an amine compound. - 前記トリアゾール化合物と前記アミン化合物を含有する溶液の濃度は、１０～１０，０００ｐｐｍである、
請求項３記載の方法。 The concentration of the solution containing the triazole compound and the amine compound is 10 to 10,000 ppm.
The method of claim 3. - 前記トリアゾール化合物と前記アミン化合物の配合割合は、重量にして、１：０．５～２である
請求項３記載の方法。 The method according to claim 3, wherein a mixing ratio of the triazole compound and the amine compound is 1: 0.5 to 2 by weight. - 前記溶液に前記銅箔を接触させる時間は、前記トリアゾール化合物および前記アミン化合物の溶解濃度、溶液温度によって処理される、
請求項３記載の方法。 The time for which the copper foil is brought into contact with the solution is treated according to the dissolution concentration of the triazole compound and the amine compound, and the solution temperature.
The method of claim 3. - 前記銅箔の厚さは、６～２０μｍである、
請求項１記載の方法。 The copper foil has a thickness of 6 to 20 μm.
The method of claim 1. - 前記銅箔の表面粗さ（Ｒｚ）は２．５μｍ以下である、
請求項１記載の方法。 The surface roughness (Rz) of the copper foil is 2.5 μm or less.
The method of claim 1. - 請求項１～８のいずれか記載の方法によって形成された、少なくとも片面に電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである有機化合物皮膜が形成された銅箔の表面に、水を溶媒とする負極活物質スラリーを塗布し、
その後乾燥させて、
非水溶媒二次電池の負極電極を製造する方法。 An organic compound film formed by the method according to any one of claims 1 to 8 and having an electric double layer capacity reciprocal (1 / C) of 0.31 to 0.9 cm 2 / μF is formed on at least one side. Apply the negative electrode active material slurry using water as a solvent to the surface of the copper foil,
Then let it dry,
A method for producing a negative electrode of a nonaqueous solvent secondary battery. - 少なくとも片面に電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである有機化合物皮膜が形成された銅箔の表面に、水を溶媒とする負極活物質スラリーを塗布し、
その後乾燥する
非水溶媒二次電池に用いる負極電極を製造する方法。 A negative electrode active material slurry using water as a solvent is formed on the surface of a copper foil on which an organic compound film having an electric double layer capacity reciprocal (1 / C) of 0.31 to 0.9 cm 2 / μF is formed on at least one surface. Apply,
The method of manufacturing the negative electrode used for the nonaqueous solvent secondary battery dried after that. - 表面に有機化合物皮膜が形成された銅箔の少なくとも片面における電気二重層容量の逆数（１／Ｃ）が０.３１～０．９ｃｍ２／μＦである
非水溶媒二次電池に用いる負極集電体用銅箔。 Negative electrode current collector used for non-aqueous solvent secondary batteries in which the reciprocal (1 / C) of the electric double layer capacity on at least one surface of a copper foil having an organic compound film formed on the surface is 0.31 to 0.9 cm 2 / μF Copper foil for body. - 前記有機化合物皮膜がトリアゾール化合物を含有する皮膜である
請求項１１記載の負極集電体用銅箔。 The copper foil for a negative electrode current collector according to claim 11, wherein the organic compound film is a film containing a triazole compound. - 前記有機化合物皮膜がトリアゾール化合物及びアミン化合物を含有する皮膜である
請求項１１記載の負極集電体用銅箔。 The copper foil for a negative electrode current collector according to claim 11, wherein the organic compound film is a film containing a triazole compound and an amine compound. - 前記銅箔の厚さは、６～２０μｍである、
請求項１１記載の非水溶媒二次電池に用いる負極集電体用銅箔。 The copper foil has a thickness of 6 to 20 μm.
The copper foil for negative electrode collectors used for the nonaqueous solvent secondary battery of Claim 11. - 前記銅箔の表面粗さ（Ｒｚ）は２．５μｍ以下である、
請求項１１記載の非水溶媒二次電池に用いる負極集電体用銅箔。 The surface roughness (Rz) of the copper foil is 2.5 μm or less.
The copper foil for negative electrode collectors used for the nonaqueous solvent secondary battery of Claim 11.
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| JP2009294318A JP2011134651A (en) | 2009-12-25 | 2009-12-25 | Copper foil for nonaqueous solvent secondary battery negative electrode collector, its manufacturing method, and method of manufacturing nonaqueous solvent secondary battery negative electrode |
| JP2009-294318 | 2009-12-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9705155B2 (en) | 2012-03-15 | 2017-07-11 | Kabushiki Kaisha Toshiba | Electrode for solid electrolyte secondary battery, solid electrolyte secondary battery, and battery pack |
| JPWO2020240746A1 (en) * | 2019-05-29 | 2020-12-03 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013140590A1 (en) * | 2012-03-23 | 2013-09-26 | 株式会社 東芝 | Negative electrode for non-aqueous electrolytic secondary cell, non-aqueous electrolytic secondary cell, and cell pack |
| JPWO2014156362A1 (en) * | 2013-03-28 | 2017-02-16 | 古河電気工業株式会社 | Surface treatment electrolytic copper foil |
| KR102029139B1 (en) * | 2015-11-09 | 2019-10-07 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| JP6925109B2 (en) * | 2016-09-02 | 2021-08-25 | 株式会社エンビジョンＡｅｓｃジャパン | Electrode junction for lithium ion secondary battery |
| JP7100560B2 (en) | 2018-10-29 | 2022-07-13 | Ｊｘ金属株式会社 | Lithium-ion battery Rolled copper foil for collector and lithium-ion battery |
| US20240379967A1 (en) * | 2021-04-27 | 2024-11-14 | Nissan Chemical Corporation | Composition for forming thin film for energy storage device electrode |
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| JPH1021928A (en) * | 1996-06-28 | 1998-01-23 | Furukawa Circuit Foil Kk | Electrode material for secondary battery |
| JPH11273683A (en) * | 1998-03-19 | 1999-10-08 | Furukawa Electric Co Ltd:The | Copper foil for negative electrode current collector of nonaqueous solvent secondary battery and its manufacture |
| JP2008226800A (en) * | 2007-03-16 | 2008-09-25 | Fukuda Metal Foil & Powder Co Ltd | Copper foil for lithium secondary battery negative electrode collector and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9705155B2 (en) | 2012-03-15 | 2017-07-11 | Kabushiki Kaisha Toshiba | Electrode for solid electrolyte secondary battery, solid electrolyte secondary battery, and battery pack |
| JPWO2020240746A1 (en) * | 2019-05-29 | 2020-12-03 | ||
| EP3979357A4 (en) * | 2019-05-29 | 2023-03-01 | Daicel Corporation | Slurry |
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| JP2011134651A (en) | 2011-07-07 |
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