CN108026653A - Electrolytic copper foil, lithium ion secondary battery cathode electrode, lithium rechargeable battery and printed circuit board (PCB) - Google Patents
Electrolytic copper foil, lithium ion secondary battery cathode electrode, lithium rechargeable battery and printed circuit board (PCB) Download PDFInfo
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- CN108026653A CN108026653A CN201780003044.1A CN201780003044A CN108026653A CN 108026653 A CN108026653 A CN 108026653A CN 201780003044 A CN201780003044 A CN 201780003044A CN 108026653 A CN108026653 A CN 108026653A
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- copper foil
- electrolytic copper
- elongation
- electrolytic
- elongations
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 239000011889 copper foil Substances 0.000 title claims abstract description 195
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000007788 roughening Methods 0.000 claims description 15
- 238000011282 treatment Methods 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 230000037303 wrinkles Effects 0.000 description 36
- 238000012360 testing method Methods 0.000 description 27
- 239000000654 additive Substances 0.000 description 25
- 230000000996 additive effect Effects 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000007747 plating Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 238000004080 punching Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- -1 0.5m/s.In addition Chemical compound 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 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 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- 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
- H05K1/03—Use of materials for the substrate
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of high intensity, high-fire resistance and small electrolytic copper foil, lithium ion secondary battery cathode electrode, lithium rechargeable battery and the printed circuit board (PCB) of elongation anisotropy.The surface treatment copper foil of the present invention is the electrolytic copper foil of the carbon containing 0.001~0.020 mass %, it is characterized in that, 10 mean roughness (Rz) of the electrolytic copper foil are less than 1.8 μm, with regard to the electrolytic copper foil is heated at 150 DEG C 1 it is small when after under room temperature measure when tensile properties for, the tensile strength of the copper foil is more than 400MPa, the elongation of the width (TD) of copper foil is more than 2%, and represent the parameter of the difference of the elongation of the length direction (MD) of copper foil and the elongation of the width (TD), i.e., elongation anisotropy { [(MD elongation TD elongations)/MD elongations] × 100 } is less than 50%.
Description
Technical field
The present invention relates to a kind of electrolytic copper foil, have the lithium ion secondary battery cathode electrode of the electrolytic copper foil, lithium from
Sub- secondary cell and printed circuit board (PCB).
Background technology
In recent years, in order to realize small-sized/lightweight of lithium (Li) ion secondary battery, use and making collector
The research of copper foil thin foil, is accompanied by this, and acting on the stress of copper foil and strain tends to increase.In addition, in order to realize lithium ion
The high capacity of secondary cell, is try to also be mixed active material with silicon systems in addition to conventional carbon system, makes it
Increase theoretical capacity, or to fill active material layer higher than conventional density, increase capacity of unit volume etc., under formal exploitation
Generation lithium rechargeable battery, is accompanied by this, and the stress for acting on the copper foil as collector further improves, and limits situation
Become strong, its result causes, after discharge and recharge the wrinkle of electrolytic copper foil, fracture show more than ever before, battery behavior may be because
This is reduced.
As the conventional method for the thin foil for being used for realization copper foil, such as implement：The high intensity of electrolytic copper foil, carry
Also characteristic (high resistance to thermalization) (such as the patent document of the deterioration in characteristics such as softening is difficult to happen in the heat treatment of high battery manufacture process
1~4 etc.).
, generally can be by adding additive in the electrolytic solution, in electricity for high intensity, high resistance to thermalization with regard to electrolytic copper foil
Make in the crystal grain of additive component intake parent phase or in crystal boundary, high intensity or profit are realized using the miniaturization of crystal grain in analysis
Realized with flux pinning effect.
But in the case of it can realize high intensity and high resistance to thermalization, in lithium rechargeable battery of future generation
In be also difficult to entirely prevent wrinkle, fracture, it is necessary to consider the viewpoint different from existing design further to implement characteristic improvement.
Prior art literature
Patent document
Patent document 1：No. 5771392 publications of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2008-285727 publications
Patent document 3：Japanese Unexamined Patent Publication 2014-224321 publications
Patent document 4：No. 5598700 publications of Japanese Patent No.
Patent document 5：No. 3850155 publications of Japanese Patent No.
The content of the invention
Problems to be solved by the invention
It is an object of the invention to provide a kind of high intensity, high-fire resistance and the small electrolytic copper foil of elongation anisotropy,
Lithium ion secondary battery cathode electrode, lithium rechargeable battery and printed circuit board (PCB).
Technical solution
The inventors of the present invention are studied based on exploitation of the above-mentioned design guideline to new electrolytic copper foil, it was found that following thing
It is real：With high intensity, high-fire resistance electrolytic copper foil in, showing elongation anisotropy, (elongation values are according to implementation
The direction of tension test and different phenomenons), additionally, it is observed that the following fact：It is described in detail below, elongation anisotropy
Reduction can effectively reduce the wrinkle after discharge and recharge, the generation of fracture, the wrinkle after punching press, the generation of fracture.
It should be noted that electrolytic copper foil can generally be such that copper separates out to titanium cathode drum surface, by the way that it is continuously torn
And wind, manufacture the product (electrolytic copper foil) of long size.At this time, by bulging direction of rotation, the length direction of i.e. long sized products
Labeled as MD, the width in the direction orthogonal with MD directions, i.e. copper foil is labeled as TD.
For existing general electrolytic copper foil and existing high intensity, high-fire resistance electrolytic copper foil, it is respectively prepared
The test film that MD directions and TD directions are cut out, utilizes stretching test machine determination stress and strain, the load-deformation curve of gained
The typical example of (SS curves) is as shown in Figure 1.As shown in Figure 1, in existing high intensity, high resistance to hot paper tinsel, the strain (elongation in MD directions
Rate) it is that the elongation in 5.8%, TD directions is 2.0%, big elongation anisotropy is shown, about 65.5% ((5.8-
2.0)/5.8 × 100%).But high intensity, the elongation of high-fire resistance electrolytic copper foil it are not conceived in patent document 1~4
Anisotropy, according to the composition, can not effectively inhibit the wrinkle in lithium rechargeable battery of future generation and the production of fracture
It is raw.It should be noted that in existing general electrolytic copper foil, some elongation anisotropy are also produced, about 11.1%,
But think its be probably due to being present in the concave-convex surface that generates after polishing trace (buff streaks) transfer of electrolysis drum and
Caused, elongation anisotropy is small, it is difficult to as wrinkle, the Producing reason of fracture.
In view of can formally develop lithium rechargeable battery of future generation from now on, it may be necessary to develop high intensity, high-fire resistance
Paper tinsel, the anisotropic reduction of elongation shown therewith can be described as important topic.That is, in the collection of high-capacity lithium-ion secondary cell
In electric body purposes, the copper foil for developing a kind of high intensity, height is heat-resisting and elongation anisotropy is small it is expected.
In addition, in the printed circuit boards, it is contemplated that isotropic stress can be assigned when being bonded with resin, it is believed that preferably stretch
Long rate anisotropy is small, it is expected to develop a kind of small copper foil of elongation anisotropy.
Therefore, the inventors of the present invention are found that the method for solving the above subject after being furtherd investigate, and complete the present invention.
That is, purport of the invention forms as follows：
(1) a kind of electrolytic copper foil, it is characterised in that the carbon containing 0.001~0.020 mass %, the ten of the electrolytic copper foil
Point mean roughness (Rz) is less than 1.8 μm, the electrolytic copper foil is heated at 150 DEG C 1 it is small when when being measured under room temperature
Tensile properties, i.e. the tensile strength of the copper foil is more than 400MPa, and the elongation of the width (TD) of copper foil is 2%
More than, and represent the parameter of the difference of the elongation of the length direction (MD) of copper foil and the elongation of the width (TD),
That is, elongation anisotropy { [(MD elongation-TD elongations)/MD elongations] × 100 } is less than 50%.
(2) electrolytic copper foil as described in above-mentioned (1), wherein, { [(MD elongations-TD extends the elongation anisotropy
Rate)/MD elongations] × 100 it is less than 30%.
(3) electrolytic copper foil as described in above-mentioned (1) or (2), wherein, the tensile properties obtain under following states, should
State is：The state of the electrolytic copper foil (former paper tinsel) of roughening treatment layer is not formed in two faces.
(4) a kind of lithium ion secondary battery cathode electrode, wherein, there is the electricity any one of above-mentioned (1)~(3)
Copper foil is solved as collector.
(5) a kind of lithium rechargeable battery, wherein, possess the electrolytic copper foil any one of with above-mentioned (1)~(3)
Lithium ion secondary battery cathode electrode as collector.
(6) printed circuit that one kind forms the electrolytic copper foil any one of above-mentioned (1)~(3) with insulation film lamination
Plate.
Invention effect
According to the present invention, electrolytic copper foil contains the carbon of 0.001~0.020 mass %, and 10 points of the electrolytic copper foil are average thick
Rugosity (Rz) is less than 1.8 μm, the electrolytic copper foil heat at 150 DEG C 1 it is small when stretching spy when measure under room temperature
Property, i.e. the tensile strength of the copper foil is more than 400MPa, and the elongation of the width (TD) of copper foil is more than 2%, and
Represent the parameter of the difference of the elongation of the length direction (MD) of copper foil and the elongation of the width (TD), i.e. elongation
Anisotropy { [(MD elongation-TD elongations)/MD elongations] × 100 } is less than 50%, therefore is capable of providing high intensity, height
Heat resistance and the small electrolytic copper foil of elongation anisotropy.
If in addition, for example, using the present invention electrolytic copper foil be used for possess with the electrolytic copper foil as collector lithium from
The lithium rechargeable battery of sub- secondary battery cathode electrode, then fracture, wrinkle when can prevent discharge and recharge, can improve battery
Capacity, cycle characteristics and security, therefore suitable for lithium rechargeable battery purposes of future generation.And then if by the present invention's
Electrolytic copper foil is used for the dielectric film printed circuit board (PCB) that together lamination is formed, then fracture, the production of wrinkle when can prevent punching press
It is raw, it can additionally improve dimensional stability.
Brief description of the drawings
Fig. 1 is that existing general electrolytic copper foil and existing high intensity, high-fire resistance electrolytic copper foil are respectively prepared
The test film cut out on MD directions and TD directions, it is representational obtained from stretching test machine determination stress and strain to answer
Force-strain curve (SS curves).
Fig. 2 is the concept map for illustrating the major part of the manufacture device of the electrolytic copper foil of the manufacture present invention.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.
The present invention electrolytic copper foil be characterized in that, the carbon containing 0.001~0.020 mass %, the ten of the electrolytic copper foil
Point mean roughness (Rz) is less than 1.8 μm, the electrolytic copper foil is heated at 150 DEG C 1 it is small when after (20 DEG C ± 15 of room temperature
DEG C) under measure when tensile properties, i.e. the tensile strength of the copper foil is more than 400MPa, the width (TD) of copper foil
Elongation is more than 2%, and represents the elongation of the length direction (MD) of copper foil and the elongation of the width (TD)
Difference parameter, i.e. elongation anisotropy { [(MD elongation-TD elongations)/MD elongations] × 100 } be less than 50%.
<Carbon content in copper foil>
In the present invention, the carbon in electrolytic copper foil (C) content is needed for 0.001~0.020 mass %.The reason is that
If carbon content is less than 0.001 mass %, sufficient intensity and heat resistance can not be obtained, if in addition, carbon content exceeds 0.020 matter
% is measured, then ductility can reduce, and in operation or when discharge and recharge is easily broken.Therefore, carbon content is set to 0.001~
0.020 mass %.It should be noted that for the measure of the carbon content in copper foil, such as carbon/sulphur content analysis apparatus can be used
EMIA-810W (hole field makes made), is surveyed using (tubular electric furnace mode)-infrared absorption of burning in oxygen flow
It is fixed.
<10 mean roughness (Rz) of copper foil surface>
In addition, in the present invention, 10 mean roughness (Rz) of electrolytic copper foil are needed for less than 1.8 μm.Its reason exists
In, if 10 mean roughness (Rz) more than 1.8 μm, the elongation produced by the concave-convex surface of electrolytic copper foil respectively to
The opposite sex can increase and show, and obvious wrinkle are easily produced in the copper foil after charge and discharge test.Therefore, by electrolytic copper foil
10 mean roughness (Rz) are set to less than 1.8 μm.It should be noted that 10 mean roughness (Rz) with regard to electrolytic copper foil
For measure, based on JIS B0601：1994 implement measure.In addition, aspect of measure is set to not form the unprocessed of roughening treatment layer
Electrolytic copper foil (former paper tinsel) the S faces surface of side (cathode (Ti) drum), measure direction is set to and polishing trace direction (=MD side
To) vertical direction (=TD directions).
<The tensile properties of copper foil when heating 1 is small at 150 DEG C when being measured under room temperature>
And then electrolytic copper foil of the invention heated at 150 DEG C 1 it is small when after under room temperature measure when tensile properties meet
Following each characteristic.That is, it needs to meet：The tensile strength of copper foil is more than 400MPa, and width (TD's) of copper foil stretches
Long rate is more than 2%, and represent the elongation of the length direction (MD) of copper foil and the width (TD) elongation it
The parameter of difference, i.e. elongation anisotropy { [(MD elongation-TD elongations)/MD elongations] × 100 } is less than 50%.
Requirement of the existing general electrolytic copper foil also sometimes to high intensity, high resistance to thermalization is few, it is general using without using
The electrolytic copper foil (such as patent document 5) of the high-purity of additive, although or in order to realize smoothing and add additive,
Electrolysis process additive can less take in the electrolytic copper foil (such as The Furakawa Electric Co., Ltd. NC-WS) in copper foil.
But with the high capacity of battery, miniaturization, lightweight, for the demand with high intensity, the electrolytic copper foil of high-fire resistance
It has been expanded that, therefore actively using the cases of additive types in paper tinsel can be taken in during electrolysis also in increase (such as patent
Document 1~4 etc.).
The inventors of the present invention have been manufactured to possess the high intensity, the high-fire resistance that are suitable for battery use or printed circuit board (PCB) purposes
Premised on and used the electrolytic copper foil of various additives, anode is contained Si systems active material lithium ion secondary of future generation electricity
Pond implements charge and discharge test, be realised that：If only improving the in the past required characteristic such as intensity, extensibility, heat resistance, can not fill
Divide the wrinkle of the copper foil after ground suppression discharge and recharge.Therefore, have made intensive studies to further suppress wrinkle, as a result send out
It is existing：By making to realize high intensity, the electrolytic copper foil of high resistance to thermalization show elongation anisotropy, and reduce elongation it is each to
The opposite sex, can effectively inhibit wrinkle.Hereinafter, elongation anisotropy is illustrated.
Elongation anisotropy refers to, in tension test, the elongation values property different according to draw direction.This hair
Person of good sense etc. has investigated the anisotropy of elongation to multiple electrolytic copper foils with high intensity, high-fire resistance, be realised that：To copper foil
Length direction (MD directions) stretching when elongation values it is maximum, elongation when being stretched to the width (TD directions) of copper foil
Value is minimum.Therefore, in the present invention, as the value for representing the anisotropic size of elongation, { [(MD elongations-TD stretches for utilization
Long rate)/MD elongations] × 100 calculating formula calculate elongation and the width side of the length direction (MD) for representing copper foil
To the parameter of the difference of the elongation of (TD), i.e. elongation anisotropy, and evaluated.Hereinafter, to elongation anisotropy
Illustrated with the relation of wrinkle.
If because of the discharge and recharge of battery or with the punching press of resin etc., electrolytic copper foil loads isotropic stress, then is extending
In the case that rate anisotropy is big, it can be formed in advance at the low direction of elongation values (such as width (TD) of copper foil) uneven
Even deformed region (attenuates region) equivalent to so-called part in single tension test, therefore can be mixed according to direction and deposit homogeneous deformation
Region and inhomogeneous deformation region, produce the partial deviations of strain, its result causes, and copper foil easily produces wrinkle.On the other hand,
In the case where elongation anisotropy is small, the mixed homogeneous deformation region and inhomogeneous deformation region deposited as above is not easy, because
This inhibits the deviation of strain, as a result thinks to be difficult to produce wrinkle.
Therefore, for the electrolytic copper foil of the present invention, by stretching when heating 1 is small at 150 DEG C when being measured under room temperature
Characteristic, i.e. tensile strength is maintained to more than 400MPa, or is suppressed tensile strength and decreased below 400MPa, formed high intensity and
High-fire resistance, while make the elongation of the width (TD) of copper foil be more than 2%, and make the elongation anisotropy of copper foil
For less than 50%, preferably less than 30%.The reason is that if the tensile strength after heating is less than 400MPa, thin foil is realized
The intensity deficiency of the copper foil of change, easily produces fracture.In addition, its reason also resides in, if the width of the copper foil after heating
(TD) elongation is less than 2%, then easily produces fracture.And then if the reason is that heating after copper foil elongation respectively to
The opposite sex can then mix more than 50% and deposit homogeneous deformation region and inhomogeneous deformation region, produce the partial deviations of strain, its result is led
Cause, copper foil easily produces wrinkle.
Therefore, electrolytic copper foil of the invention by 150 DEG C heating 1 it is small when after under room temperature measure when tensile properties, i.e.
Tensile strength maintains to more than 400MPa or suppresses its reduction, forms high intensity and high-fire resistance, while make the width side of copper foil
To (TD) elongation be more than 2%, and make copper foil elongation anisotropy be less than 50%.
In addition, the tensile strength (initial strength) when being measured before above-mentioned heating under room temperature is preferably 400~900MPa
Scope.If the reason is that the tensile strength is less than 400MPa, initial strength deficiency, heating is after normal at 150 DEG C
Tensile strength under temperature during measure is unable to reach more than 400MPa, tends to easily produce fracture, if in addition, the tensile strength surpasses
900MPa is crossed, then elongation deficiency, the elongation of heating width (TD) of copper foil when being measured under room temperature at 150 DEG C
More than 2% is unable to reach, tends to easily produce fracture.
In addition, in particular for forming the electrolytic copper foil of printed circuit board (PCB), in order to ensure it is with forming printed circuit board (PCB)
The adhesion of resin, as the post processing of manufactured electrolytic copper foil (former paper tinsel), implements roughening treatment using roughening plating mostly.
Roughening plating generally refers to the electrolysis by implementing high current density with the short period in sulfuric acid-copper sulphate plating solution, in electricity
Solve the granular copper particle that copper foil surface forms about 0.1~1 μm of level.In contrast, for the electrolytic copper foil of the present invention, two
The tensile properties that face is not formed in the state of the untreated electrolytic copper foil (former paper tinsel) of roughening treatment layer when measuring have bright
Aobvious feature.Although also depending on the thickness of roughening plating layer, since roughening plating layer is generally present in the surface of electrolytic copper foil,
Therefore the bumps of electrolytic copper foil surface can become thick.In addition, the electrolytic condition of general roughening plating is with manufacturing untreated electricity
The electrolytic condition of solution copper foil (former paper tinsel) is very different.Therefore, using roughening plating formed copper particle crystalline structure and
Crystalline structure and construction of the construction different from untreated electrolytic copper foil (former paper tinsel).
The detailed mechanism is not yet clear for it, but according to multiple reasons, it is (former with not possessing the electrolytic copper foil of roughening plating layer
Paper tinsel) compare, for possessing the electrolytic copper foil of roughening plating layer, in appearance, elongation anisotropy seems big sometimes, has
When seem small.Therefore, for the electrolytic copper foil of the present invention, in correctly measure (evaluation) above-mentioned tensile properties, preferably not
Possesses the roughening treatment layer formed by roughening plating.
It should be noted that tension test is measured based on IPC standards (IPC-TM-650).Each sample is measured 10 times
Afterwards, using its tensile strength and the mean values of elongation as intensity and the numerical value of elongation.In addition, the number with regard to tensile strength
For value, due to the test film that is cut out along the length direction of copper foil and along the test film that cuts out of width of copper foil, do not have
Obvious anisotropy is confirmed, therefore in the present invention, the test film cut out using the length direction along copper foil measures stretching
Intensity, 50mm/min is set to by tension test speed.
[manufacture method of electrolytic copper foil]
The inventors of the present invention have made intensive studies for the anisotropic reduction method of elongation, it turns out that：Pass through drop
The flow velocity of electrolyte in low copper electrolysis, it is generally desirable to which the foliation under state without mixing, can be greatly decreased elongation anisotropy.
Various parsings are implemented for the mechanism, but do not confirm what is occurred because whetheing there is elongation anisotropy on metal structure
Difference is specified, therefore mechanism there is no final conclusion.But in the electrolytic copper foil for almost not taking in additive as example existing paper tinsel
In, do not confirm elongation anisotropy, it is believed that this be have high intensity, high-fire resistance electrolytic copper foil endemism
(with reference to Fig. 1).With regard to additive component absorption and thereafter by additive component take in copper foil in for, it is also well known that
It can be influenced be subject to the flow velocity of electrolyte, therefore be speculated：Electrolyte during due to manufacture electrolytic copper foil flows to copper with fast speed
Paper tinsel length direction, therefore there are some differences in the effect of additive, it was found that the elongation anisotropy of copper foil.
Hereinafter, the example of the representational manufacture method of the electrolytic copper foil of the present invention is illustrated.
Fig. 2 is the outline for representing to be used to manufacture the major part of the representational manufacture device 1 of the electrolytic copper foil M of the present invention
Figure, its mainly from be filled with electrolyte 2 electrolytic cell 3, have cylinder formed surface cathode drum 4 and with the cathode drum 4 to
The anode 5 of positioning is formed.Electrolyte 2 is preferably using sulfuric acid-copper sulfate solution.Anode 5 is preferably using by by white metal member
The insoluble anode that element or the titanium of its oxide elements covering are formed.
Moreover, the manufacture method of electrolytic copper foil M is：By in insoluble anode 5 and the titanium system being arranged oppositely with the anode 5
It is full of between cathode drum 4 in the state of electrolyte 2, while with fixed speed rotating cathode drum 4, while between the two poles of the earth 4,5
DC current is connected, copper is separated out to cathode drum surface 4, separated out copper of tearing from the surface of cathode drum 4, forms cathode copper
Paper tinsel M, is wound the electrolytic copper foil formed by take-up roll 6, so as to manufacture.
Electrolyte 2, therefore the stream of electrolyte 2 are supplied from the bottom for being arranged on electrolytic cell 3 and the part that is referred to as distribution board 7
Fast direction is that the direction is with being formed in the moon from distribution board 7 towards the direction of the overflow part 8 for the top both sides for being arranged on electrolytic cell 3
The length direction of copper foil extremely on the surface of drum 4 is identical.The flow velocity of electrolyte 2 can suitably be changed by pump power etc., if but
Manufactured under electrolytic condition more than limiting current density, then can produce so-called burning plating, therefore in such as this implementation
Example like that by flow velocity be down to it is extremely low in the case of, it is necessary to electrobath composition, bath temperature, current density etc. suitably be adjusted, to reach small
In the electrolytic condition of limiting current density.Hereinafter, the appropriate electrolytic condition of the electrolytic copper foil for manufacturing the present invention is shown.
Copper concentration：120~155g/L
Sulfuric acid concentration：30~100g/L
Cl concn：60~140mg/L
Additive concentration：2~20mg/L
Bath temperature：65~80 DEG C
Current density：10~35A/dm2
Flow velocity：0.02~0.05m/s
It should be noted that high intensity, the electrolytic copper foil of high-fire resistance in order to obtain, it is necessary to addition addition in the electrolytic solution
Agent.As the method for selecting of additive, can suitably select to use the effect with being adsorbed to copper surface and making crystal grain realize micromation
Fruit and intake intragranular and the additive with heat-resisting effect.The problem of not special even if using multiple additives yet, but examine
Consider the viewpoint of the convenience of economy, manufacture stability and concentration management, preferably its species is as far as possible few.As with above-mentioned
The additive of effect, it is known that there is the additive of the functional groups of unshared electron pair such as S, N, O, in the present embodiment, also use
Containing more than one S, N, O and have the additive of miniaturization and heat-resisting effect concurrently.It should be noted that additive is dense
Additive in the more high then intake copper foil of degree is more, and intensity and heat resistance are higher, but then, ductility reduction, therefore grasp
When making or when discharge and recharge, easily produces fracture.Therefore, there is optimum concentration range.As additive, preferably using for example poly- second
Glycol (PEG), hydroxyethyl cellulose (HEC), thiocarbamide etc..
Compared with existing general manufacturing condition, the present invention carries out the following studies：By greatly improving copper concentration, bath
Temperature, reduces current density, under extremely low flow velocity, perfect condition are without mixing, can also meet less than limiting current density
Electrolytic condition.In addition, using small-sized micro- current meter CM-1SX types (east nation of Co., Ltd. electrical resistivity survey system), before electrolysis in the state of will
Current meter is installed to from the distribution board 7 of electrolytic cell to the position between overflow part 8, and the flow velocity of electrolyte in electrolytic cell is counted
Survey.The electrolytic copper foil of the present invention can be manufactured by the above method.
If in addition, using the electrolytic copper foil of the present invention for for example possessing the lithium ion with the electrolytic copper foil as collector
The lithium rechargeable battery of secondary battery cathode electrode, then fracture, wrinkle when can prevent discharge and recharge, can improve battery appearance
Amount, cycle characteristics and security.And then if the electrolytic copper foil of the present invention is used for and the dielectric film printing that together lamination is formed
Circuit board, then fracture, the generation of wrinkle when can prevent punching press, can improve dimensional stability.
It these are only an example of embodiments of the present invention, can be made various changes in the range of claims.
Embodiment
(embodiment 1~7 and comparative example 1~8)
For embodiment 1~7 and comparative example 1~8, using the manufacture device of the electrolytic copper foil shown in Fig. 2, by
It is full of between insoluble anode 5 and the titanium cathode drum 4 being arranged oppositely with the anode 5 in the state of electrolyte 2, while with fixation
Speed rotating cathode drum 4, while connecting DC current between the two poles of the earth 4,5, copper is separated out to cathode drum surface 4, from the moon
The surface of extremely drum 4 is torn the copper of precipitation, and the electrolytic copper foil M of 8 μm of thickness is made.Electrolyte bath composition, additive species and
Additive amount, bath temperature, the flow velocity of current density and electrolyte are as shown in table 1.It should be noted that in embodiment 1~5 and 7,
It is not without mixing, and flow velocity is set to 0.02m/s, the reason is that being produced when preventing continuous foliation because of the delay of bath dense
Degree changes.In addition, for cathode drum 4, surface is ground by polishing, until (polishing trace side with grinding direction
To) vertical direction measure when roughness Rz and the numerical value of the roughness Rz of the electrolytic copper foil (S faces) shown in table 2 be changed into equal
It is horizontal.
(comparative example 9~13)
In comparative example 9~13, respectively according to the condition suitable with the embodiment 1 of patent document 1~5,8 μm of thickness is made
Electrolytic copper foil M.It should be noted that due to having no special record for flow velocity, by electrolyte in comparative example 9~13
Flow velocity be set to the general flow conditions scope of existing electrolytic copper foil, i.e. 0.5m/s.In addition, for cathode drum 4, pass through
Polishing is ground surface, until the roughness Rz when being measured on the direction vertical with grinding direction (polishing trace direction)
It is changed into peer-level with the numerical value of the roughness Rz of the electrolytic copper foil (S faces) shown in table 2.
(comparative example 14)
" NC-WS " of the The Furakawa Electric Co., Ltd. as electrolytic copper foil is used, which uses extensively
Make copper foil for lithium ion secondary battery, although additive is with the addition of in the electrolytic solution in order to realize smoothing, in electrolysis mistake
Additive can be less taken in copper foil in journey.
[table 1]
<Evaluation method>
1. the measure of the carbon content in copper foil
Using the sample of carbon/sulphur content analysis apparatus EMIA-810W (hole field makes made), burning 0.5g or so, using oxygen
Burning (tubular electric furnace mode)-infrared absorption in air-flow, measures the carbon content in copper foil.The carbon content of the measure such as institute of table 2
Show.It should be noted that abundant careful operation during measure, avoids copper foil surface from polluting, has carried out acetone degreasing etc. as needed
Pre-treatment.
2. the measure of 10 mean roughness Rz of copper foil surface
Based on JIS B0601：1994, measure 10 mean roughness Rz.Aspect of measure for copper foil S faces (cathode drum side
Copper foil surface), measure direction is the direction (=TD direction) vertical with polishing trace direction (=MD directions).
3. battery performance test
(1) making of negative electrode for lithium secondary battery electrode
Active carbon material (containing 20 mass % of Si system alloy active material) and acetylene black are crushed using ball mill and mixed
Close, it is 8 to make its mass ratio:1, negative material is made.Using the negative material as 80 mass %, the Kynoar as bonding agent
(PVDF) mixed for the ratio of 20 mass %, prepare cathode agent, the cathode agent is dispersed to 1-methyl-2-pyrrolidinone
(solvent), is made active material slurry.Then, in banding (length direction and the copper foil according to 8 μm of thickness made of above-mentioned condition
MD directions are parallel) after the two sided coatings active material slurry of electrolytic copper foil, make its drying, which is electrolysed
Copper foil heated at 150 DEG C 1 it is small when, be then compressed shaping using roll squeezer so that shaping after cathode agent thickness
It is 120 μm on two sides, has obtained negative electrode for lithium secondary battery electrode.
(2) making of positive electrode for lithium secondary battery electrode
0.5 mole of lithium carbonate is mixed for 1 mole with cobalt carbonate, in atmosphere with 900 DEG C burn till 5 it is small when, be made just
Pole active material (LiCoO2).With the positive active material (LiCoO2) for 91 mass %, the graphite as conductive agent it is 6 matter
The ratio that amount %, the PVDF as bonding agent are 3 mass % is mixed, and cathode is made and closes material, is dispersed to N- methyl -2-
In pyrrolidones (NMP), pulp-like is formed.Then, which is equably applied to 20 μm of thickness and the banding formed by aluminium
The two sides of positive electrode collector, shaping is compressed after drying using roll squeezer, so that the thickness of the anode mixture after shaping is in table
Face is 95 μm, has obtained positive electrode for lithium secondary battery electrode.
(3) making of lithium rechargeable battery
As one kind of rechargeable nonaqueous electrolytic battery, lithium rechargeable battery has been made.To as described above made of just
Pole electrode and negative electrode implement lamination with the membrane formed by micro- porous polypropylene film, and laminate electrode body is made.The lamination
Electrode body using anode as inner side, repeatedly winds spirality along its length, is fixed the final end of membrane using adhesive tape
To most peripheral, screw type electrode body is made.In the state of the upper and lower surface of manufactured screw type electrode body is provided with insulation board,
The iron battery can after implementing nickel plating is accommodated in, in order to implement the current collection of cathode and anode, is exported from positive electrode collector
The positive wire of aluminum, is connected to battery cover, exports nickel negative wire from negative electrode collector, is connected to battery can.
Nonaqueous electrolytic solution is injected in the battery can for being accommodated with the screw type electrode body, the nonaqueous electrolytic solution is with 1 mole/L
Ratio by LiPF6 be dissolved to propene carbonate and diethyl carbonate etc. capacity in the mixed solvent.Then, applied via with pitch
The insulation sealing packing ring on cloth surface rivets battery can and fixes battery cover, maintains the air-tightness in battery can.As described above, system
Into diameter 18mm, the cylindrical shape lithium secondary battery of height 65mm.
In accordance with the following methods, cell evaluation is implemented to the lithium rechargeable battery at 25 DEG C of temperature.(charge and discharge test
Condition)
Charging：Implement constant-current charge using the electric current equivalent to 1C, after reaching 4.2V, be switched to constant-voltage charge, charging
Complete charge when current reduction is to equivalent to 0.05C.
Electric discharge：Implement constant-current discharge using the electric current equivalent to 1C, terminate to discharge when reaching 3.0V.
It should be noted that C is C rates, be instigate battery total capacity discharge 1 it is small when the magnitude of current.(the folding after discharge and recharge
Wrinkle and the evaluation of fracture)
For the evaluation of the fracture after discharge and recharge, repeat discharge and recharge 1000 according to above-mentioned condition and circulate, cyclic test knot
Battery is disassembled after beam, visually confirms that copper foil has non-wrinkle and fracture.For the wrinkle in table 2 and the evaluation of fracture, completely
Do not have to be shown as " ◎ " when wrinkle and fracture, be shown as "○" when slightly having wrinkle, occur being shown as " wrinkle " during obvious wrinkle,
It is shown as " being broken " when being broken, while occurs being shown as " wrinkle, fracture " when obvious wrinkle and fracture.
After according to chromate condition as shown below to implementing antirust treatment according to electrolytic copper foil made of above-mentioned condition
Surface treatment copper foil be used as tension test, roughness measure, the sample of gas analysis and cell evaluation.
<Chromate treatment conditions>
1~10g/L of potassium bichromate
25 DEG C of temperature (DEG C)
2~20 seconds impregnation time
Evaluation result is as shown in table 2.
[table 2]
It is according to table 2 as a result, in embodiment 1~7, the carbon content in copper foil is 0.0015~0.018 matter
% is measured, in the proper range of the present invention (0.001~0.020 mass %), in addition, Rz is 1.0~1.7 μm, the present invention's
In proper range (less than 1.8 μm), and at 150 DEG C heating 1 it is small when after under room temperature measure when tensile properties, i.e. stretching
Intensity is 420~653MPa, and in the proper range of the present invention (more than 400MPa), the value of width elongation (TD) is
2.1~6.1%, in the proper range of the present invention (more than 2%), and elongation anisotropy is 6.2~47.5%, at this
It is almost unconfirmed to obvious wrinkle, fracture after charge and discharge test in the range of invention (less than 50%), especially in reality
Apply in example 1~4, elongation anisotropy is less than 30%, and wrinkle do not occur completely.
On the other hand, in comparative example 1~4, elongation anisotropy is 57.1~63.9%, beyond the appropriate of the present invention
The upper limit value (50%) of scope, has confirmed obvious wrinkle in the copper foil after charge and discharge test.Also, in comparative example 3 and 4
In, the value of the width elongation (TD) of copper foil is 1.3~1.8%, less than the lower limit of the proper range of the present invention
(2%), fracture has been confirmed in the copper foil therefore after charge and discharge test.In comparative example 5, carbon content is 0.023 mass %, more
In the upper limit value (0.02 mass %) of the proper range of the present invention, therefore confirm and resolve in the copper foil after charge and discharge test
Split.The carbon content of comparative example 6 is 0.0008 mass %, less than the present invention proper range lower limit (0.001 mass %), because
Tensile strength after being heated at this 150 DEG C is 370MPa, less than the lower limit (400MPa) of the proper range of the present invention, in addition,
Due to heating, obvious softening occurs in it, and fracture has been confirmed in the copper foil after charge and discharge test.In comparative example 7, copper
Width (TD) elongation of paper tinsel is 1.3%, and less than the lower limit (2%) of the proper range of the present invention, therefore discharge and recharge tries
Fracture has been confirmed in copper foil after testing.In comparative example 8, Rz is 2.0 μm, more than the upper limit value of the proper range of the present invention
(1.8 μm), therefore shown the elongation anisotropy caused by concave-convex surface, confirmed in the copper foil after charge and discharge test
Obvious wrinkle.Also, the value of the width elongation (TD) of copper foil is 1.8%, less than proper range of the invention
Upper limit value, therefore fracture has also been confirmed in the copper foil after charge and discharge test.In comparative example 9~12, elongation is respectively to different
Property be 53.6~70.0%, more than the present invention proper range upper limit value, therefore in the copper foil after charge and discharge test really
Obvious wrinkle are recognized.Also, in comparative example 9 and 10, the value of the width elongation (TD) of copper foil for 0.9~
1.3%, less than the lower limit of the proper range of the present invention, therefore also confirm fracture at the same time.In comparative example 13 and 14,
Tensile strength after being heated at 150 DEG C is 251~273MPa, less than the lower limit of the proper range of the present invention, therefore is being filled
Fracture has been confirmed in copper foil after discharge test.
According to result above, for meeting following electrolytic copper foil, even in the lithium rechargeable battery of high capacity type
In, it can also suppress wrinkle, fracture in discharge and recharge, be extremely suitable to the service life for extending battery：Contain 0.001~0.020 mass %'s
Carbon, 10 mean roughness (Rz) of electrolytic copper foil are less than 1.8 μm, at 150 DEG C by electrolytic copper foil heat 1 it is small when after normal
Tensile properties under temperature during measure, i.e. the tensile strength of the copper foil is more than 400MPa, and width (TD's) of copper foil stretches
Long rate is more than 2%, and represent the elongation of the length direction (MD) of copper foil and the width (TD) elongation it
The parameter of difference, i.e. elongation anisotropy { [(MD elongation-TD elongations)/MD elongations] × 100 } for less than 50%, it is excellent
Elect less than 30% as.In addition, confirm：In printed base plate purposes, meeting the copper foil of above-mentioned characteristic can also effectively inhibit
The wrinkle of copper foil, fracture after punching press.
It should be noted that the spy that the intensity, elongation anisotropy after heating are possessed by untreated electrolytic copper foil
Property, even if implementing the surface treatments such as antirust treatment, silane coupled processing, above-mentioned characteristic will not be influenced.
Industrial applicability
In accordance with the invention it is possible to provide a kind of high intensity, high-fire resistance and the small electrolytic copper foil of elongation anisotropy.This
Outside, if using the electrolytic copper foil of the present invention for for example possessing the lithium rechargeable battery use with the electrolytic copper foil as collector
The lithium rechargeable battery of negative electrode, then fracture, wrinkle when can prevent discharge and recharge, it is special can to improve battery capacity, circulation
Property and security.And then if by the present invention electrolytic copper foil be used for dielectric film together lamination formed printed circuit board (PCB),
Fracture, the generation of wrinkle when can prevent punching press, can additionally improve dimensional stability.
Symbol description
The manufacture device of 1 electrolytic copper foil
2 electrolyte
3 electrolytic cells
4 cathode drums
5 anodes
6 take-up rolls
7 distribution boards
8 overflow parts
Claims (6)
- A kind of 1. electrolytic copper foil, it is characterised in that the carbon containing 0.001~0.020 mass %,10 mean roughness Rz of the electrolytic copper foil are less than 1.8 μm,With regard to the electrolytic copper foil is heated at 150 DEG C 1 it is small when after under room temperature measure when tensile properties for, the copper foil Tensile strength be more than 400MPa, the elongation of the width TD of copper foil is more than 2%, and represents the length side of copper foil The parameter of the difference of the elongation of elongation and the width TD to MD, i.e. elongation anisotropy [(MD elongations- TD elongations)/MD elongations] × 100 it is less than 50%.
- 2. electrolytic copper foil according to claim 1, wherein, { [(MD elongations-TD extends the elongation anisotropy Rate)/MD elongations] × 100 it is less than 30%.
- 3. electrolytic copper foil according to claim 1 or 2, wherein, the tensile properties obtain under following states, the state For：The state of the electrolytic copper foil of roughening treatment layer, i.e., the state of former paper tinsel are not formed in two faces.
- 4. a kind of lithium ion secondary battery cathode electrode, wherein, there is cathode copper according to any one of claims 1 to 3 Paper tinsel is as collector.
- 5. a kind of lithium rechargeable battery, wherein, possess：With electrolytic copper foil conduct according to any one of claims 1 to 3 The lithium ion secondary battery cathode electrode of collector.
- A kind of 6. printed circuit board (PCB) for forming electrolytic copper foil according to any one of claims 1 to 3 with insulation film lamination.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016117547 | 2016-06-14 | ||
| JP2016-117547 | 2016-06-14 | ||
| PCT/JP2017/014131 WO2017217085A1 (en) | 2016-06-14 | 2017-04-04 | Electrolytic copper foil, lithium ion secondary cell negative electrode, lithium ion secondary cell, and printed wiring board |
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| Publication Number | Publication Date |
|---|---|
| CN108026653A true CN108026653A (en) | 2018-05-11 |
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| CN201780003044.1A Pending CN108026653A (en) | 2016-06-14 | 2017-04-04 | Electrolytic copper foil, lithium ion secondary battery cathode electrode, lithium rechargeable battery and printed circuit board (PCB) |
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| Country | Link |
|---|---|
| KR (1) | KR102218889B1 (en) |
| CN (1) | CN108026653A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093635A (en) * | 2019-04-24 | 2019-08-06 | 福建清景铜箔有限公司 | High-intensitive electrolytic copper foil and its various products for using the copper foil |
| CN112751035A (en) * | 2019-10-30 | 2021-05-04 | 长春石油化学股份有限公司 | Electrolytic copper foil having heat resistance and lithium ion secondary battery comprising same |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI791776B (en) * | 2018-02-23 | 2023-02-11 | 日商古河電氣工業股份有限公司 | Electrolytic copper foil, negative electrode for lithium ion secondary battery, lithium ion secondary battery, copper clad laminate, and printed circuit board using the electrolytic copper foil |
| JP6748332B2 (en) * | 2018-03-16 | 2020-08-26 | 株式会社シンク・ラボラトリー | Current collecting member for cylinder body plating device and plating device |
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| TWI792449B (en) * | 2021-07-27 | 2023-02-11 | 長春石油化學股份有限公司 | Electrolytic copper foil, and electrode and copper-clad laminate comprising the same |
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| CN112751035B (en) * | 2019-10-30 | 2024-02-02 | 长春石油化学股份有限公司 | Electrolytic copper foil having heat resistance and lithium ion secondary battery comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017217085A1 (en) | 2017-12-21 |
| TW201807260A (en) | 2018-03-01 |
| KR102218889B1 (en) | 2021-02-22 |
| TWI767910B (en) | 2022-06-21 |
| KR20190003451A (en) | 2019-01-09 |
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