CN111525138B - 具有优异接着性的铜箔 - Google Patents
具有优异接着性的铜箔 Download PDFInfo
- Publication number
- CN111525138B CN111525138B CN202010040543.1A CN202010040543A CN111525138B CN 111525138 B CN111525138 B CN 111525138B CN 202010040543 A CN202010040543 A CN 202010040543A CN 111525138 B CN111525138 B CN 111525138B
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- China
- Prior art keywords
- copper foil
- electrolytic copper
- thickness
- void volume
- roll
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011889 copper foil Substances 0.000 title claims abstract description 107
- 239000011800 void material Substances 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 230000008021 deposition Effects 0.000 claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 4
- 239000010410 layer Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 21
- 239000011149 active material Substances 0.000 description 18
- 238000000151 deposition Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical group [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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- C25D5/48—After-treatment of electroplated surfaces
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- H—ELECTRICITY
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- H01M4/04—Processes of manufacture in general
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- H01M4/0469—Electroforming a self-supporting electrode; Electroforming of powdered electrode material
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- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0237—High frequency adaptations
- H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
- H05K1/181—Printed circuits structurally associated with non-printed electric components associated with surface mounted components
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- B32B2255/06—Coating on the layer surface on metal layer
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- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
本公开涉及具有适用于锂离子二次电池的集电体特性的电解铜箔。该电解铜箔包括辊筒面及沉积面。该沉积面或该辊筒面的至少一者具有约0.17至约1.17μm3/μm2的空隙体积(Vv)值。
Description
技术领域
本公开涉及具有高耐久性及可加工性的电解铜箔。本公开也涉及包括该电解铜箔作为组件的锂离子二次电池。
背景技术
锂离子二次电池具有高能量及高功率密度的组合,使其作为便携式电子装置、电动工具、电动车(EVs)、能量储存系统(ESS)、移动电话、平板电脑、航空航天应用、军事应用、及铁路的技术选择。电动车(EVs)包括混合动力电动车(HEVs)、插电式混合动力电动车(PHEVs)、及纯电池电动车(BEVs)。若电动车(EVs)取代大部分以化石燃料(例如,汽油、柴油等)作为动力的运输工具,则锂离子二次电池将显著减低温室气体排放。锂离子二次电池的高能量效率亦可允许其用于各种电网应用中,包括改善从风力、太阳能、地热及其他可再生能源收集的能量的品质,因此有助于其更广泛地用于建立永续能源的经济。
因此,锂离子二次电池引起商业资本以及政府和学术实验室的基础研究的强烈兴趣。尽管近年来此领域的研究及发展已经大量存在,且锂离子二次电池当前已在应用中,但对于关于更高容量、更高电流生成以及可进行更多次充电/放电循环从而延长其使用寿命的电池仍存在改善的需求。此外,需要改善电池的重量以改善其在例如车辆、可携式电子装置及航空航天应用等多种环境中的应用。
锂离子二次电池通常包括涂布有活性材料的金属箔的集电体。铜箔经常用作集电体,盖因铜是良好的电流导体。由于对较低重量的电池的需求变得越来越迫切,需要更薄的集电体以降低锂离子二次电池的尺寸及重量。此外,为了增加锂离子二次电池的电容量,将诸如硅(Si)、锗(Ge)及锡(Sn)的材料与高电容量活性材料混合或填充于电池中,会加剧该活性材料的膨胀及收缩以及其所接触的铜箔上的应力。再者,于一些近期的进展中,为了增加电池的电容量,将用作电极的铜箔折叠或弯曲并卷绕。如果铜箔在电池使用期间不能承受该活性材料的膨胀及收缩,或不能承受电池制造过程中的折叠及卷绕,则该电池的循环特性受到负面影响。
因此,仍需要改进用于锂离子二次电池的铜箔。对于具有提升的可加工性及耐久性的更薄铜箔亦存在需求,并且当该铜箔与活性材料组合以提供锂离子二次电池时,不会因该铜箔与该活性材料之间的分离或者铜箔的断裂而在高度充放电循环下失效。为了满足降低锂离子二次电池的重量并增加其电容量的目标,需要更薄的铜箔,且不会于电池的制造过程中或在电池的使用过程中失效。
发明内容
总的来说,本文中所述的发明涉及一种铜箔,例如可用作锂离子二次电池中的集电体的电解铜箔。举例而言,电解铜箔业经制备为具有如空隙体积(void volume,Vv)的受控特性。
在第一方面,本发明包含一种电解铜箔,包含辊筒面以及相对该辊筒面的沉积面,其中,该辊筒面及沉积面的至少一者具有0.17至1.17μm3/μm2的空隙体积(Vv)值。任选地,该辊筒面及沉积面各自具有0.17至1.17μm3/μm2的空隙体积(Vv)值。任选地,该辊筒面及沉积面的至少一者还具有0.16至1.07μm3/μm2的核心部空隙体积(corevoid volume,Vvc)值。任选地,该辊筒面及沉积面各自还具有0.16至1.07μm3/μm2的核心部空隙体积(Vvc)值。任选地,该辊筒面及沉积面的至少一者还具有0.01至0.10μm3/μm2的波谷部空隙体积(dalevoidvolume,Vvv)值。任选地,该辊筒面及该沉积面各自还具有0.01至0.10μm3/μm2的波谷部空隙体积(Vvv)值。任选地,铜箔的表面包含选自锌-铬涂层、铬涂层及有机涂层所组成组的至少一种涂层。任选地,铜箔的表面包含铬镀层。
根据本发明的第一方面包括下列一些额外特性。任选地,电解铜箔还包括大于5次/μm的疲劳寿命/厚度。任选地,该疲劳寿命/厚度为8至40次/μm。任选地,该电解铜箔具有2μm至25μm的厚度。
在第二方面,本发明包含用于锂离子二次电池的集电体,包含电解铜箔,举例而言,如本发明第一方面所述的电解铜箔。任选地,该集电体还包含与该电解铜箔的沉积面接触的负极活性材料。任选地,该集电体还包含与该电解铜箔的辊筒面接触的负极活性材料。
在第三方面,本发明包含锂离子二次电池,包含集电体,举例而言,如本发明的第二方面所述的集电体。
本文所述的电解铜箔用于例如锂离子二次电池时,展现优异特性。除了可制造具有高电容量的轻型二次电池外,使用此等电解铜箔制备的电池亦具有优异的充放电循环特性。举例而言,于锂离子二次电池的大量充放电循环期间,该铜箔与活性材料不会分离或破碎。未受限于特定机制,其意味此等改善的至少一部分是由于该铜箔与活性材料之间的优异接着力,以及该铜箔中断裂点或失效点的数量减少。
上述发明内容并非试图代表本发明的所有实施例或所有方面。反的,前述发明内容仅提供本文阐述的新颖方面及特征的示例。当结合所附图式及权利要求书时,由下述用以实施本发明的代表性具体实施例和模式的详细说明,上述特征及优点与本公开的其他特征及优点将是显而易见的。
附图说明
由以下例示性实施例的说明结合参考附图将更佳地理解本发明。
图1显示3D表面图以及负载率(material ratio)图。
图2显示负载率图的细节。
本公开可接受进行各种修改及替代形式。藉由图式中的示例显示一些代表性具体实施例,并将于本文中对其详细描述。但应理解,本公开并不受所公开的特定形式所限。反之,本公开涵盖所有落入本发明的权利要求书所定义的精神及范围内的修饰、等效物及替代物。
应明确理解,所有图表及图式的呈递仅为示意之用。于图式的各个图中,相同的数字用以表示相似元件,以便理解所公开的具体实施例。
符号说明
110 峰
112 孔
114、210、212、214、216 区域。
具体实施方式
本文所制造的物品涉及电解铜箔,具有可量化的特征且其用作集电体时提供良好的效能。举例而言,此等电解铜箔可与活性材料组合以提供锂离子二次电池的负极。于一些具体实施例中,该电解铜箔的特征在于调整铜箔的空隙体积至特定量。
如本文中所用,铜箔的“辊筒面”是与电沉积过程中使用的辊筒接触的铜箔表面,而“沉积面”是该辊筒面的相对侧,或在形成铜箔的电沉积过程中与电解液接触的电解铜箔表面。此等术语关于生产电解铜箔的制造方法,包括将转动的辊筒组件部分地浸没于含有铜离子以及任选地的其他添加剂(如稀土金属及表面活性剂)的电解液中。因此,于电流的作用下,铜离子被吸引至该辊筒并被还原,导致铜金属镀覆于该辊筒的表面上,并于该辊筒的表面上形成电解铜箔。藉由旋转该辊筒,并于所形成的铜箔随着该辊筒一起转出该电解液时移除该铜箔,从而于连续工艺形成并从辊筒上移除电解铜箔。举例而言,该电解铜箔可随着其形成而被拉离辊筒,并于连续工艺中横越或通过辊。
该电解铜箔具有影响其特性及用于电池时的最终效能的表面纹理或特征,其中一个上述特征是如图1所示的空隙体积参数。图1显示例如电解铜箔的辊筒面或沉积面的3D表面以及用于获得空隙体积参数的负载率图的推导。图1的左侧为代表性表面的表面几何形状的三维图示。图1的右侧显示藉由ISO标准方法ISO 25178-2:2012以得到负载率曲线的推导,从位于最高的峰110的顶部的0%负载率(materialratio,mr)跨越至mr为100%的最低的谷或孔112的底部。空隙体积(Vv)藉由将设定在对应于介于0%(峰110的顶部)与100%(孔112的底部)之间的特定负载率(mr)的高度下的表面上方及水平切割平面下方所围住的空隙的体积积分而计算。举例而言,mr为70%的Vv显示为图1的右侧曲线图中的阴影区域114。如本文中所用,除非另有说明,否则所列出的Vv是负载率为10%的Vv。
图2显示负载率图与关于各种空隙体积参数所定义的一些关系的更多细节。核心部空隙体积(Vvc)是两个负载率之间的空隙体积差,例如区域210所示的mr1及mr2的间的空隙体积差。举例而言,如本文所用,除非另有指明,否则Vvc的计算选择mr1为10%且mr2为80%。波谷部空隙体积(Vvv),也称为谷空隙体积(valley void volume),为特定mr值的空隙体积,如区域212所示的mr为80%的空隙体积。如本文中所用,除非另有指明,否则Vvv以负载率80%计算。在mr1的空隙体积(Vv)是mr1与mr2之间的核心部空隙体积(Vvc)(区域210)与在mr2的波谷部空隙体积(Vvv)(区域212)的总和。其他区域包括波峰部实体体积(peak material volume,Vmp)(区域214),以及核心部实体体积(core material ratio,Vmc)(区域216)。
于一些具体实施例中,电解铜箔具有介于低值与高值之间的受控范围内的空隙体积,例如,介于约0.17(μm3/μm2)的低值与约1.17(μm3/μm2)的高值之间。当Vv过低时,例如低于约0.17(μm3/μm2),由于锚固效应(anchor effect)薄弱,铜箔对活性材料的接着力差。换言之,由于材料无法顺利锚固至表面,因此其接着性差。相反地,如果Vv过高,例如高于约1.17(μm3/μm2),则该活性材料不能均匀地涂覆在铜箔的表面上。换言之,大的Vv对应于铜箔表面上的大空隙,而活性材料不能有效地填充所有空隙,使铜箔与活性材料层之间留下一些未覆盖及被覆盖的空隙。是以,在过低及过高的两个区域内,活性材料对电解铜箔的接着力皆不良,且使用不具有该受控范围内的Vv的铜箔制备的电池可能会显现出较差的电池特性。
电解铜箔的沉积面或辊筒面的至少一者的Vv值描述为在0.17至1.17(μm3/μm2)范围内,且该值独立选自沉积面与辊筒面之间。应明确理解的是,此等范围是连续范围且可表示为:0.17、0.18、0.19、0.20、0.21、0.22、0.23、0.24、0.25、0.26、0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、0.39、0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.61、0.62、0.63、0.64、0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、及1.17(μm3/μm2),且每一个值都代表范围数值的端点。于一些具体实施例中,电解铜箔的沉积面或辊筒面的至少一者的核心部空隙体积(Vvc)值位于0.16至1.07(μm3/μm2)范围内,且如针对Vv所述,此等范围是连续范围且可由介于0.16与1.07(μm3/μm2)之间的任何范围或值表示。于一些具体实施例中,电解铜箔的沉积面或辊筒面的至少一者具有波谷部空隙体积(Vvv)值,其在0.01至0.10(μm3/μm2)范围内,且如针对Vv及Vvc所述,此等范围是连续范围且可由介于0.01与0.10(μm3/μm2)之间的任何范围或值表示。
如本文中所用,“疲劳寿命”是与电解铜箔的弯曲特征有关的量化测量,本文中以疲劳寿命相对于厚度(疲劳寿命/厚度)的值表示铜箔的疲劳寿命,且疲劳寿命测试详述如下。铜箔的弯曲特性可能影响如导电碳材料的活性材料对铜箔的接着性,并因此可能影响电池的效能。于一些具体实施例中,铜箔具有高疲劳寿命,例如疲劳寿命/厚度大于5次/μm(例如,大于8、10、20或30次/μm)。低疲劳寿命可能产生在充放电循环测试中更容易受影响而失效(例如断裂)的电解铜箔。
于一些具体实施例中,电解铜箔可用来形成电池。举例而言,叠片型锂离子电池或钮扣型锂离子电池。因此,于一些具体实施例中,使用该铜箔制成的电极可形成正极,且涂布于其上的活性材料是正极活性材料。于一些其他具体实施例中,使用该铜箔制成的电极可形成负极,且涂布于其上的活性材料是负极活性材料。
于一些具体实施例中,该电解铜箔包括形成于其表面上的防锈层,且该防锈层可保护该电解铜箔免于如由于腐蚀造成的劣化。防锈层可藉由任何已知方法制备,包括令所形成的电解铜箔浸没于或通过含有形成防锈层的添加剂的溶液,或将金属或合金膜镀覆(例如,电镀)于所形成的电沉积片材上。举例而言,包括锌、铬、镍、钴、钼、钒及其组合的任一者或多者的电镀浴;或形成防锈层的有机化合物。该过程可为连续工艺且制备该电解铜箔的整体制程的一部分。
如本文中所用,充放电测试是指下述测试:施加横跨电池的正极及负极的电势以对该电池充电;随后将该正极和负极与负载连结,并令电流通过该负载以将该电池放电。这一充放电表示一次充放电循环。可进行该测试以模拟电池于重复使用方面的表现。“循环寿命”或“充放电循环寿命”定义为电池在其标称电容量低于其初始额定电容量的80%的前可执行的充放电循环次数。
于一些具体实施例中,该电解铜箔可作为集电体用于电池(例如,锂离子二次电池)以及用于装置中。如本文中所用,装置包含其运作需要电能的任何物品或器件。举例而言,独立的、隔离的和移动式器件及装置,其需要小且轻的电池。可包括但不限于载运工具(汽车、有轨电车、公交车、卡车、轮船、潜艇、飞机)、电脑(例如,微控制器、笔记本电脑、平板电脑)、电话(例如,智能手机、无线电话)、个人健康监控及维持设备(例如,血糖监测器、心律调整器)、工具(例如,电钻、电锯)、照明器(例如,手电筒、紧急照明、标志)、手持型测量装置(例如,酸碱度测定计、空气监测装置)以及居住单位(例如,太空舱中、拖车中、房屋中、飞机内、潜艇内)。
应理解,于本公开的范畴内,上述及下述提及的技术特征(诸如实施例)可自由且相互组合以形成新的或优选的技术方案,为简要起见省略。
[实施例]
电解铜箔的制备
使用可旋转的金属阴极辊筒及不溶性金属阳极制备电解铜箔。将该不溶性金属阳极放置于该金属阴极辊筒的大约下半部并环绕该金属阴极辊筒。使用连续电沉积以制造电解铜箔,藉由令硫酸铜电解液流动于该金属阴极辊筒与不溶性金属阳极之间,并在阴极与阳极之间施加电流而使铜电沉积在该金属阴极辊筒上,从而形成电解铜箔。
于一些实验中,如下表2中所示,于电沉积的形成过程中,以阳极袋(BEIP308W10L20,由中国台湾恩慈股份有限公司制造)覆盖阳极,以制备电解铜箔。阳极袋包住阳极但在其位于电解液外的顶部为敞开的,使得氧气气泡流出该电解液并远离该阳极。
于制备未处理的电解铜箔后,将铜箔从辊筒拉出,并以连续方式藉由导辊使该电解铜箔通过电镀浴,而用防锈材料处理电解铜箔的表面。
电解液的组成及镀覆条件提供如下。
[电解液]
硫酸(50重量%):75g/L
硫酸铜(CuSO4·5H2O):280g/L
氯离子浓度:15mg/L(来自盐酸,购自RCI Labscan公司)
硫酸铈(Ce(SO4)2):0至55mg/L(购自Sigma-Aldrich)
液体温度:40℃电流密度:33至65A/dm2
[防锈处理]
三氧化铬(CrO3):1500mg/L(购自Sigma-Aldrich)
液体温度:25℃
电流密度:0.5A/dm2
镀覆时间:1秒
叠片式锂离子二次电池
如下述制备叠片式锂离子二次电池,并进行高C倍率(c-rate)充放电测试。
使用N-甲基-2-吡咯烷酮(NMP)作为溶剂以制备正极浆料及负极浆料。以固液比195重量%(195g的NMP:100g的正极活性材料)配制正极浆料。以固液比60重量%(60g的NMP:100g的负极活性材料)调配负极浆料。正极活性材料及负极活性材料的配方显示于表1中。
将正极浆料涂布于铝箔上,并将负极浆料涂布于电解铜箔上。溶剂蒸发后,压合负极及正极并切割为所需的尺寸。将正极与负极交替堆叠,并将隔离膜(Celgard Company)夹置于其间,再置于由层叠膜塑造的容器中。该容器填充有电解液,并将其密封以形成电池。叠片式电池的尺寸为41mm×34mm×53mm。
表1:活性材料配方
就高C倍率充电及放电测试(例如,充电-放电测试)而言,充电模式是恒定电流-恒定电压(CCCV)模式,其中充电电压为4.2V,且充电电流为5C。放电模式是恒定电流(CC)模式,放电电压为2.8V,且放电电流为5C。电池的充放电测试在高温下(于55℃)执行。
电解铜箔实施例
表2显示设计为例示性说明电解铜箔的具体实施例的实验。于阳极袋一栏中,X表示不存在阳极袋,而O表示存在阳极袋。表3显示该电解铜箔的所得特性或特征。于Vv一栏中,Δ表示沉积面与辊筒面之间的Vv的差(绝对值)。湿式接着力是指如下文“湿式接着力测试”中所述而制备的负极的湿式接着力。各列列出7个实施例(E.1至E.7)及5个比较例(C.1至C.5)。
数据尤其显示,当电解铜箔的至少一侧的空隙体积(Vv)为介于约0.17至约1.17μm3/μm2的范围内时,该铜箔具有高疲劳寿命,具有很强的湿式接着力,且使用此等铜箔制备的电池的循环寿命高。当铜箔的空隙体积(Vv)不在此等范围内时,疲劳寿命、接着力及循环寿命特性较差。举例而言,疲劳寿命/厚度小于约8次/μm,湿式接着力测试失败且循环寿命小于约800。
表2
1 O表示使用阳极袋;X表示不使用阳极袋
表3
测试方法
体积参数
表3中的空隙体积(Vv)藉由根据ISO 25178-2(2012)的步骤,从实施例及比较例中获得。以激光显微镜的图像进行表面纹理分析。激光显微镜为Olympus制造的LEXTOLS5000-SAF,且图像在24±3℃的空气温度以及63±3%的相对湿度下制成。滤波器设定为未滤波。光源为405nm波长的光源。物镜为100x倍率(MPLAPON-100xLEXT)。光学变焦设定为1.0x。图像面积设定为129μm x 129μm。分辨率设定为1024像素x 1024像素。条件设定为自动倾斜移除。
以p为10%而q为80%的负载率来计算Vvc,使用80%的负载率计算Vvv,并使用10%的负载率计算Vv。空隙体积的单位为μm3/μm2。
单位面积重量及厚度
单位面积重量是每单位面积的重量。使用具有100mm×100mm的测试试样以测定面积。重量藉由微量天平(AG-204型,Mettler Toledo International Inc.)测定,且单位面积重量通过重量除以面积而计算并转换单位为公克/平方公尺(g/m2)。
电解铜箔的厚度使用IPC-TM-650的测试方法2.4.18测量。使用下述公式:
厚度=M/(Aρ):厚度以微米(μm)计,M是以克(g)计的样本重量,A是以平方米(m2)计的样本面积,且ρ是样本密度。所使用的电解铜箔的密度为8.909g/cm3。
湿式接着力测试
藉由将负极浆料以5m/min的速度涂覆于铜箔的表面上至200μm的厚度,并通过160℃烘箱使其干燥,以制备负极。随后,使用压制机以1m/min的压速及3000psi的压力压制该负极。该压制机的压辊的尺寸为φ250mm×宽250mm,压辊的硬度为62至65HRC,且压辊的材料是高碳铬轴承钢(SUJ2)。之后将该负极切割成10cm×10cm的片材作为试片,并将其浸没在60℃的电解液(LBC322-01H,由深圳新宙邦科技股份有限公司(Shenzhen CapchemTechnology Co.,Ltd.)制造)中4小时。如果负极浆料从该铜箔上剥离或于与该铜箔之间膨胀,则视为失败。相反,如果没有剥离或膨胀,则视为通过。
疲劳寿命
疲劳寿命使用标准方法IPC-TM-650 2.4.2.1测试。简而言之,该方法包括将薄带形式的测试试样(例如,电解铜箔)附接至悬挂有配重的支架,随后使用具有设定直径的心轴(mandrel)快速上下振动该测试试样的中心。测试使用3FDF型号的疲劳延展性测试仪(Jovil Universal Manufacturing Company)进行。测试试样是12.7mm×200mm的电解铜箔条。测试条件如下:心轴直径=0.8mm,振动速度=100次振动/分钟,用于提供张力的配重=84.6g。为了测试,用胶带将试样附接至样品架上,使得其不能从该样品架上滑动。此外,对于取样方向,切割每一试样,使得其长边(200mm)平行于机器方向。
如本文中所用,术语“包含”或“包括”是关于所要求保护的发明必要的组合物、方法及其各自组分,但该术语可包括未具化的元件,无论其是否为必要。
如本文中所用,术语“主要由...组成”是指给定具体实施例所需的那些元件。该术语允许不实质上影响本发明所主张的具体实施例的基本及新颖或功能特征的元件的存在。
术语“由...组成”是指本文所述的组合物、方法及其各自组分,其不包含任何于该具体实施例的描述中未述及的元件。
如本说明书及所附权利要求书中所用,除非上下文中明确指出,否则单数形式“一”及“该”包括复数形式。因此,举例而言,关于“该方法”的描述包括一种或多种方法,及/或本文所述类型的步骤及/或在阅读本公开等之后,对于所属领域技术人员而言是显而易见的。同样,除非上下文明确指出,否则词语“或”旨在包括“及”。
除了操作的实施例或另外说明以外,在所有情况下,本文中用以表示成分数量及反应条件的数字应理解为均以术语“约”修饰。术语“约”可意指所指代的值的±5%(例如,±4%、±3%、±2%、±1%)。
若提供一数值范围,则介于该范围的上限与下限之间的每一数值且包括该范围的上限及下限,视为公开于本文中。
除非本文另外定义,否则本申请案中使用的科技术语应具有与发明所属领域技术人员所一般理解的含义。再者,除非文中另有要求,否则单数的术语应包括复数,且复数的术语应包括单数。
应理解,本发明并不限于本文所述的特定方法、方案及试剂等,且此等可变。本文所用的术语的目的仅在于描述特定具体实施例,并非意图限制本发明的范围,本发明的范围仅为权利要求书所界定。
本文中公开的任何包括ASTM、JIS方法的专利、专利申请案及出版物藉由引用而明确并入本文以用于描述及公开目的,例如,此等出版物中描述的方法可与本发明结合使用。此等出版物仅因为其在本申请案的申请日的前公开而提供。这方面的任何内容皆不应理解为承认本发明人无权凭藉先前的发明或出于任何其它原因而先于此等公开。所有关于日期的叙述或对此等文件内容的陈述基于申请人可获得的讯息,而不构成对该等日期或此等文件内容的正确性的承认。
Claims (15)
1.一种电解铜箔,包含:
辊筒面以及相对所述辊筒面的沉积面,其中,所述辊筒面及沉积面各自具有0.17至1.17μm3/μm2的空隙体积(Vv)值,其中,所述空隙体积(Vv)值是根据ISO 25178-2(2012)并使用10%的负载率(mr)计算获得。
2.根据权利要求1所述的电解铜箔,其特征在于,所述辊筒面及沉积面的至少一者还具有0.16至1.07μm3/μm2的核心部空隙体积(Vvc)值,其中,所述核心部空隙体积(Vvc)值是根据ISO 25178-2(2012)并以p为10%而q为80%的负载率(mr)计算获得。
3.根据权利要求1所述的电解铜箔,其特征在于,所述辊筒面及所述沉积面各自还具有0.16至1.07μm3/μm2的核心部空隙体积(Vvc)值,其中,所述核心部空隙体积(Vvc)值是根据ISO 25178-2(2012)并以p为10%而q为80%的负载率(mr)计算获得。
4.根据权利要求1所述的电解铜箔,其特征在于,所述辊筒面及所述沉积面的至少一者还具有0.01至0.10μm3/μm2的波谷部空隙体积(Vvv)值,其中,所述波谷部空隙体积(Vvv)值是根据ISO 25178-2(2012)并使用80%的负载率(mr)计算获得。
5.根据权利要求1所述的电解铜箔,其特征在于,所述辊筒面及所述沉积面各自还具有0.01至0.10μm3/μm2的波谷部空隙体积(Vvv)值,其中,所述波谷部空隙体积(Vvv)值是根据ISO 25178-2(2012)并使用80%的负载率(mr)计算获得。
6.根据权利要求1所述的电解铜箔,还具有大于5次/μm的疲劳寿命/厚度,其中,所述疲劳寿命是根据IPC-TM-650 2.4.2.1获得。
7.根据权利要求6所述的电解铜箔,其特征在于,所述疲劳寿命/厚度为8至40次/μm。
8.根据权利要求1所述的电解铜箔,其具有2μm至25μm的厚度。
9.根据权利要求1所述的电解铜箔,其表面包含选自锌-铬涂层、铬涂层及有机涂层所组成组的至少一种涂层。
10.根据权利要求1所述的电解铜箔,其表面包含铬镀层。
11.一种用于锂离子二次电池的集电体,包含根据权利要求1所述的电解铜箔。
12.根据权利要求11所述的集电体,还包含与所述电解铜箔的沉积面接触的负极活性材料。
13.根据权利要求11所述的集电体,还包含与所述电解铜箔的辊筒面接触的负极活性材料。
14.一种锂离子二次电池,包含根据权利要求11所述的集电体。
15.一种装置,包含根据权利要求14所述的锂离子二次电池。
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