CN105386088B - Electrolytic copper foil and its manufacturing method - Google Patents
Electrolytic copper foil and its manufacturing method Download PDFInfo
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- CN105386088B CN105386088B CN201510671938.0A CN201510671938A CN105386088B CN 105386088 B CN105386088 B CN 105386088B CN 201510671938 A CN201510671938 A CN 201510671938A CN 105386088 B CN105386088 B CN 105386088B
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- copper foil
- electrolytic copper
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- tensile strength
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 260
- 239000011889 copper foil Substances 0.000 title claims abstract description 219
- 238000004519 manufacturing process Methods 0.000 title description 49
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011630 iodine Substances 0.000 claims abstract description 73
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 73
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims description 57
- 238000005452 bending Methods 0.000 claims description 30
- 238000004381 surface treatment Methods 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 239000006182 cathode active material Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052801 chlorine Inorganic materials 0.000 abstract description 29
- 230000006641 stabilisation Effects 0.000 abstract description 6
- 238000011105 stabilization Methods 0.000 abstract description 6
- 239000000523 sample Substances 0.000 description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 55
- 229910052744 lithium Inorganic materials 0.000 description 55
- 230000000052 comparative effect Effects 0.000 description 43
- 239000011888 foil Substances 0.000 description 18
- 238000011835 investigation Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000010339 dilation Effects 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 230000003746 surface roughness Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical group [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 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 5
- 239000004615 ingredient Substances 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- CZKYLWACZPRYOR-UHFFFAOYSA-N [S].OS(O)(=O)=O Chemical compound [S].OS(O)(=O)=O CZKYLWACZPRYOR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- FTCLAXOKVVLHEG-UHFFFAOYSA-N sodium;3-sulfanylpropane-1-sulfonic acid Chemical compound [Na].OS(=O)(=O)CCCS FTCLAXOKVVLHEG-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- 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
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The object of the present invention is to provide the electrolytic copper foils for the characteristic that various stabilizations can be shown chlorine amount changes.And then, a kind of electrolytic copper foil is used in order to realize the purpose, is the electrolytic copper foil as obtained from being electrolysed copper electrolyte, it is characterised in that, iodine amount in electrolytic copper foil is more than 0.003 mass %, and the iodine amount is further preferably in the mass % ranges of 0.003 mass %~0.03.And then range of the chlorine amount of the electrolytic copper foil preferably below 0.0018 mass %.
Description
The application is divisional application, female case application No. is 201180032383.5 (international application no PCT/
JP2011/065147, international filing date are on July 1st, 2011), it is on December 28th, 2012 into the National Phase in China date,
Application is artificial：Mitsu Mining ＆ Smelting Co., Ltd, it is entitled：Electrolytic copper foil and its manufacturing method.
Technical field
The present invention relates to the manufacturing methods of electrolytic copper foil and the electrolytic copper foil.More particularly to suitable for lithium ion two
The physical characteristic of tensile strength, the elongation of primary cell current-collector etc., and could be used that covering in printed wiring board manufacture
Electrolytic copper foil in copper laminated board manufacture.
Background technology
In recent years, due to the raising that the raising of environmental protection consciousness and resource recycling require, lithium ion secondary electricity
Pond is popularized as reusable useful power supply, such as it is used in and carries to outdoor laptop, hand
It is mechanical, electrical to regard, in video camera products.With the miniaturization of these electric equipment products and electronic equipment, to as power supply supply source
Lithium rechargeable battery also proposed small-sized, high life, light weight, and play the requirement of high-energy density.
The exploitation history of lithium rechargeable battery is looked back, in the negative electrode current collector of cathode of lithium rechargeable battery is formed
Attempt the rolled copper foil for having used surface smoothness excellent.In the cathode current collection of the cathode of present composition lithium rechargeable battery
In device, any one in rolled copper foil or electrolytic copper foil is used.
In the manufacturing process of the cathode of the lithium rechargeable battery, as patent document 1 or it is disclosed Patent Document 2 that
There is the process of load high temperature in sample.In this process, as form cathode negative electrode current collector copper foil in be also supported height
Temperature.If as a result, the copper foil softens, there will be when easily being repeated charge and discharge by lithium rechargeable battery, cathode
The problem of influence for the distortional stress that the dilation of active material is brought.
For the problem, when using the rolled copper foil obtained by more cheap tough pitch copper, cause since heating easily occurs
Recrystallization and soften, so as to easily by repeat above-mentioned charge and discharge when dilation stress influenced, and lithium ion
The life-time dilatation of secondary cell is more difficult.In addition, rolled copper foil derives from its manufacturing method, therefore expensive, so as to be difficult to
It is provided with the price more less expensive than electrolytic copper foil.This point becomes to win world's sexual valence for operator
The obstacle of lattice competition.In addition, since rolled copper foil is difficult to be widened as copper foil, therefore, it is difficult to improve the effect of the production in battery manufacture
Rate, it is limited so as to the reduction of product cost, become unavoidable shortcoming.
In this regard, think all the time, electrolytic copper foil recrystallizes caused by heating due to being difficult to happen and is difficult to soften, so as to
The resistance of dilation stress during to the above-mentioned charge and discharge of repetition is strong.In addition, since electrolytic copper foil is more cheap than rolled copper foil, energy
Rentability of the lithium rechargeable battery in market in price level is improved, so as to the substitute as rolled copper foil, cathode copper
The use of foil is actively considered always.As a result, now, two sides all has the cathode copper for the thin surface for being equal to rolled copper foil
Foil is widely used in the negative electrode current collector purposes of lithium rechargeable battery.
All there are the relevant technologies of the electrolytic copper foil for the thin surface for being equal to rolled copper foil as the two sides, such as patent text
It offers as disclosed in 3, patent document 4 etc., is invented to reduce the surface roughness in the precipitation face of electrolytic copper foil,
The electrolyte composition, electrolyte temperature, current density of the copper electrolyte manufactured for electrolytic copper foil are controlled in the invention
Deng.
In patent document 3, to manufacture useful, etching performance and impedance control performance in printed circuit board manufacture
It for the purpose of outstanding electro-deposition copper foil, employs and " is flowed through between the anode and cathode, and then in the sun comprising (A) electrolytic solution
Apply between pole and the cathode so that the process of a effective amount of voltage of copper is precipitated on the cathode；Herein, which contains
Copper ion, sulfate ion and at least one organic additive or its derivative, the chlorine ion concentration of the solution is about 1ppm；
Current density is about 0.1~about 5A/cm2Range；And the process that (B) removes copper foil from the cathode." manufacturing method.That is,
Employ such electrolytic condition：Use the copper electrolyte for controlling cl concn.
And in patent document 4, such electrolytic condition is employed, which is characterized in that used and contained 0.05~2.0
Thiocarbamide of weight ppm or derivatives thereof, the high molecular polysaccharide and molecular weight of 0.08~12 weight ppm below 10000,
Electrolyte of the glue of 0.03~4.0 weight ppm as additive.As a result, it is manufactured that the table in the precipitation face of the electrolytic copper foil
Surface roughness is close to the electrolytic copper foil of rolled copper foil level of surface roughness.
And then pointed out in patent document 5, crystalline structure miniaturization and reduce surface roughness patent document 3,
Electrolytic copper foil presence recorded in each bulletin such as patent document 4 can not fully meet market to cycle charge discharge electric life, overcharge
The situation of demand in terms of characteristic.According to the patent document 5 it is found that as influencing cycle charge discharge electric life and overcharging electrical characteristics
The flatness on surface that copper foil characteristic can not be represented with 10 mean roughness Rz, room temperature tensile strength, elongation, non-heavy knot
Elongation in crystalline substance, hot environment is important, and as in secondary cell characteristic obtain best effects copper foil into
Work(example discloses such a electrolytic copper foil in the embodiment 1 of patent document 5.I.e. " containing cupric sulfate pentahydrate 280g/L,
Sulfuric acid 100g/L, chlorion 35ppm sulfuric acid copper sulfate electrolyte in addition average molecular weight 3000 low molecular weight it is bright
Glue 7ppm, hydroxyethyl cellulose 3ppm, 3-sulfydryl-1-propane sulfonic acid sodium 1ppm, and 55 DEG C of electrolyte temperature, 0.3m/ points of flow velocity
Clock, current density 50A/dm2Condition " etc. come the electrolytic copper foil that manufactures, " it is characterized in that, the surface in face is precipitated in electrolytic copper foil
Roughness represents that the crystalline structure under room temperature is less than 2.5 μm of fine crystal with 10 mean roughness Rz, meanwhile, mountain base
Distance is 5 μm or more between the smallest peaks of plinth, and room temperature tensile strength is 40kg/mm2Hereinafter, and in 130 DEG C, the heat treatment of 15 hours
Being reduced within 15% for room temperature tensile strength afterwards, does not occur thermal softening.”
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-236684 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2008-282550 bulletins
Patent document 3：Japanese Unexamined Patent Publication 7-188969 bulletins
Patent document 4：Japanese Unexamined Patent Publication 8-53789 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2004-79523 bulletins
Invention content
Problems to be solved by the invention
But in the electrolytic copper foil for the negative electrode current collector of lithium rechargeable battery, as above patent document 5 is signified
As going out, not only always requirement improvement influences the characteristic of cycle charge discharge electric life and the copper foil of overcharge characteristic, but also
There are problems that the situation that the deviation of the physical characteristics such as elongation, the tensile strength of electrolytic copper foil becomes.
Spy is traced it to its cause, it is believed that the chlorine that electrolytic copper foil copper electrolyte used when manufacturing includes is reason.The chlorine, has
When intentionally added and be controlled, be mixed into sometimes also by vinyl chloride piping etc. and as impurity can not be kept away.And then it is based on
Electrochemistry viewpoint, the chlorine in electrolyte, even if only micro variation and the ingredient easily affected to product quality.
Therefore, those skilled in the art think, although for the electrolytic copper foil electrochemically manufactured, have carried out reducing cathode copper
The improvement of manufacturing method for the purpose of the deviation of foil quality itself, but the variation of cl concn is the main reason for can not keeping away.
On the other hand, to being used for lithium rechargeable battery higher stay in grade is proposed with the electrolytic copper foil in current-collector
Requirement, that is, on the basis of existing electrolytic copper foil is received, it is desirable that have be difficult to soften heating it is heat-resisting anti-softening
Property, bending resistance characteristic, actually immobilized negative electrode active material " current-collector (cathode) for carrying negative electrode active material "
The stabilization of the quality of the high level of current-collector bending property under state etc..
Solution to the problem
Therefore, the present inventor concentrate on studies as a result, as the composition for serving as lithium rechargeable battery current-collector
The suitable electrolytic copper foil of material and the copper clad laminate of printed wiring board manufacture, it is contemplated that electrolytic copper foil as described below.
In addition, by using manufacturing method as described below so that the efficient production of electrolytic copper foil of the invention is possibly realized.
The electrolytic copper foil of the present invention：The electrolytic copper foil of the present invention is the electrolytic copper foil obtained by being electrolysed copper electrolyte,
It is characterized in that, the iodine amount in electrolytic copper foil is more than 0.003 mass %.
The surface treatment copper foil of the present invention：The surface treatment copper foil of the present invention, which is characterized in that the above-mentioned electricity containing iodine
The surface of solution copper foil implements surface treatment.
The manufacturing method of the electrolytic copper foil of the present invention：The manufacturing method of the electrolytic copper foil of the present invention is above-mentioned containing iodine
Electrolytic copper foil manufacturing method, which is characterized in that use sulfuric acid sulphur of the iodine concentration for 1.5mg/L~15.0mg/L ranges
Sour copper electrolyte is as copper electrolyte.And the further preferred cl concn of the copper electrolyte is below 1.0mg/L.
And in the manufacturing method of the electrolytic copper foil in the present invention, preferably using the temperature of copper electrolyte as 40 DEG C~60 DEG C, electricity
Current density 50A/dm2~85A/dm2Electrolytic condition be electrolysed.
The lithium ion secondary battery cathode obtained with the surface treatment copper foil of the present invention：The lithium ion secondary electricity of the present invention
The cathode in pond, which is characterized in that use the surface treatment copper foil of the invention described above as negative electrode current collector.
The effect of invention
The electrolytic copper foil of the present invention, is the electrolytic copper foil containing 0.003 mass % more than iodine as described above.By
This, contains iodine in the plank copper by making electrolytic copper foil, even if so as to which the chlorine amount in electrolytic copper foil changes, can also represent
Stable physical characteristic.
Therefore, by by the present invention electrolytic copper foil for lithium rechargeable battery cathode in, so as to inexpensively to
Market provides excellent to the resistance of the dilation phenomenon with charge and discharge generation and the long-life lithium rechargeable battery.
Description of the drawings
Fig. 1 is for " electrolytic copper foil physical property " and " the iodine amount that electrolytic copper foil contains and chlorine amount " to be examined to close
The figure of system.
Specific embodiment
Next coming in order are obtained to the manufacturing method of electrolytic copper foil of the invention, surface treatment copper foil, with the surface treatment copper foil
To the cathode of lithium rechargeable battery elaborate.
The form of the electrolytic copper foil of the present invention：The electrolytic copper foil of the present invention is the electrolysis as obtained from being electrolysed copper electrolyte
Copper foil.The electrolytic copper foil is characterized in that, range of the iodine amount in electrolytic copper foil more than 0.003 mass %.So
Electrolytic copper foil containing iodine can improve heat-resisting softening resistance, bending resistance simultaneously suitable for serving as lithium rechargeable battery current-collector
The state of " current-collector (cathode) for carrying negative electrode active material " of bent characteristic and actually immobilized negative electrode active material
Under current-collector bending property.
Herein, the iodine amount in electrolytic copper foil is preferably more than 0.003 mass %.When the iodine amount is less than 0.003
During quality %, any characteristic is all unstable, and the stabilization of product quality becomes difficult.On the other hand, if iodine in electrolytic copper foil
Amount is more than 0.003 mass %, even if the chlorine amount then in electrolytic copper foil changes, it is special also to show stable physics
Property, so as to preferably.But strictly speaking, if the iodine amount is more than 0.03 mass %, above-mentioned all characteristics can not obtain
To further improving, the embrittlement of electrolytic copper foil can be led to instead, flexural property is deteriorated, and the drop of the exterior quality under visually observing
It is low also to have the serious tendency of change, so as to which iodine amount is preferably below 0.03 mass %.
In addition, in the electrolytic copper foil of the application, preferably on the basis of above-mentioned iodine is controlled, also control in electrolytic copper foil
Chlorine amount.That is, in the electrolytic copper foil of the present invention, the chlorine amount measured by chemical analysis is preferably in 0.0000 mass %
The range of~0.0018 mass %.That is, when the chlorine amount that electrolytic copper foil contains is below 0.0018 mass %, due to being precipitated
The surface roughness in face is lower, and is easy to get the precipitation face of slimming, so as to preferably as lithium rechargeable battery current-collector
Constituent material.And then be described in detail at the comparison of embodiment and comparative example, in brief that is, receiving height to improve
Heat-resisting softening resistance during temperature heating, preferably the chlorine amount is in the mass % of 0.0006 mass %~0.0018.
And then in the electrolytic copper foil of the present invention, the chlorine amount and iodine amount measured by chemical analysis is preferred
Meet with the relationship of following formula 1 (be suitable for the negative electrode current collector purposes of lithium rechargeable battery, electrolytic copper foil chlorine amount and
The relationship of iodine amount).By relationship as satisfaction, even if so as to receive heating at a temperature of 350 DEG C or so, can also show
High heat-resisting softening resistance is shown.It is described in detail in the embodiment that will be described below about this point.First chlorine is contained below
The amount of having and the analysis method of iodine amount are illustrated.
[formula 1]
[iodine amount (quality %)] >=-30 × [chlorine amount (quality %)]+0.03
Chlorine amount is measured in accordance with the following methods.After copper foil is heated in nitric acid and dissolves it, a certain amount of nitre is added in
Sour silver solution.Then, a certain amount of KBr solution is added in, is co-precipitated chloride ion together with silver bromide.It is quiet in the dark
After putting 15 minutes, filter out sediment and cleaned.Later, sediment is transferred in beaker, will be precipitated with thiourea solution
Object is dissolved, and places a Dinner in the dark.The solution and constant volume are diluted, (Dionex companies manufacture with ion chromatograph
ICS-2000, conductivity detector, eluent KOH, column AS-20) chloride ion concentration is measured, calculate chlorine amount.
Iodine amount is measured as follows.Copper foil is heated in chloroazotic acid makes its acidification dissolving, is carried out after cooling
Constant volume measures I by ICP-AES (SPS3000 of Seiko Precision KK's manufacture)：The intensity of 178nm (Ar cleanings) calculates
Iodine amount.
In addition, the result being measured with eudiometry to the electrolytic copper foil of the present invention：The electrolytic copper foil tool of the present invention
Have such composition characteristics, that is, carbon, oxygen, sulphur, nitrogen each ingredient total major impurity amount 0.01 mass % with
Under.At this stage, in the electrolytic copper foil for the negative electrode current collector of lithium rechargeable battery, these major impurity amounts have assorted
The effect of sample is still uncertain.But major impurity ingredient mentioned here be easily in the element of cyrystal boundary segregation, it is and if main
Impurity amount is wanted as 0.01 mass % hereinafter, the then toughness enhancing of electrolytic copper foil, elongation and tensile strength are shown well
Balance.
And then the present inventor has carried out the electrolytic copper foil of the present invention with glow discharge mass spectroscopy the measure of copper purity.Its
As a result, the value for the high-purity for being more than 99.99 mass % with the copper purity that glow discharge mass spectroscopy obtains.Really, if it is considered that
To the iodine amount and chlorine amount that are measured with above-mentioned chemical analysis and the carbon, oxygen, sulphur, the nitrogen that are measured with eudiometry
Each ingredient total major impurity amount, then, can not shape with the copper purity obtained from the glow discharge mass spectroscopy
Into mutually identical value, but can consider this is because analysis method is different and the error that generates.
Secondly, physical features possessed by the electrolytic copper foil of the present invention are illustrated.And illustrating the physical features
When, it is assumed that the sheet metal thickness of electrolytic copper foil is 18 μm ± 1.8 μm of situation to illustrate.
The surface roughness in the precipitation face of the electrolytic copper foil of the present invention is illustrated.It is found that the electrolytic copper foil of the present invention
Precipitation face surface roughness Rzjis value in 0.70 μm~2.0 μm of range, be slim precipitation face.Herein, if
The value of Rzjis is more than 2.0 μm, then when manufacturing lithium ion secondary battery cathode, equably immobilized negative electrode active material becomes
It is difficult.If in addition, repeating charge and discharge, in the protrusion of current collector surface, lithium is easily grown to the crystalline tendency of branches and tendrils and becomes strong,
So as to not preferred.On the other hand, when the value of Rzjis is less than 0.7 μm, then surface state is excessively smooth, serves as lithium ion secondary
The negative electrode current collector of battery is come in use, the adhesiveness between negative electrode active material and negative electrode current collector is lower, so as to not preferred.
And then in order to make the stability of characteristics as lithium rechargeable battery, preferably the difference of the Rzjis values on electrolytic copper foil two sides is at 0.6 μm
Within.And Rzjis (10 mean roughness) mentioned here is surveyed based on JIS B0601, and with probe-type surface roughness
Determine the value of instrument (0.2 μm of the radius of curvature of tips of probes) measure.
The physical features measured under normal conditions to the electrolytic copper foil of the present invention are illustrated.The present invention electrolytic copper foil it is normal
The value of state elongation (E0) preferably 2.0%~9.0% range.When normality elongation be more than 2.0% when, suitable for lithium from
The negative electrode current collector of sub- secondary cell.On the other hand, when normality elongation is less than 9.0%, for lithium rechargeable battery
Negative electrode current collector in when, with charge and discharge when dilation deformation drag in appropriate range.And in the application
In, the measure of the measure of the elongation and aftermentioned tensile strength is drawn by the electrolytic copper foil sample to 10mm wide
The value stretched experiment and measured.
And then the value of the normality tensile strength (F0) of electrolytic copper foil of the invention is shown as in 48kgf/mm2~72kgf/
mm2Range.When the value of normality tensile strength (F0) is 48kgf/mm2More than when, for the cathode current collection of lithium rechargeable battery
Deformation drag when in device, corresponding with dilation during charge and discharge, which has, becomes good tendency.On the other hand, when normality stretches
The value of intensity (F0) is 72kgf/mm2When following, it is steadily in the range of above-mentioned suitable normality elongation.
In the following, the physical features measured after certain heat treatment is carried out to the electrolytic copper foil of the present invention are illustrated
(there is the situation referred to as " after heat " below.).Heat treatment described herein is referred in atmospheric environment to the electrolysis of normality
Copper foil implements the heat treatment of 180 DEG C × 60 minutes.
Range of the value of elongation (Ea) 4%~10% after the heat of the electrolytic copper foil of the present invention.In printed wiring board
The circuit formed in manufacturing process with copper foil and being manufactured with copper foil in the manufacturing process of the cathode of lithium rechargeable battery
Negative electrode current collector, be exposed in various high-temperature load environment.Therefore, physical property becomes left and right after the heat of the electrolytic copper foil
The very important element of product quality.It is in lithium rechargeable battery if the value of elongation (Ea) is more than 4% after heat
Negative electrode current collector purposes in suitable elongation.On the other hand, when after heat elongation be less than 10% when, for lithium from
The deformation drag of dilation during when in the negative electrode current collector of sub- secondary cell, adjoint charge and discharge is in suitable range.
And then the hot post-tensioning intensity (Fa) of electrolytic copper foil of the invention after the heat treatment of 180 DEG C × 60 minutes
Value is shown as in 38kgf/mm2~72kgf/mm2Range.When the value of hot post-tensioning intensity (Fa) is 38kgf/mm2More than when,
Be difficult to the influence of the hot resume during being subject to processing, and during in the negative electrode current collector of lithium rechargeable battery, with filling
The corresponding deformation drag of dilation during electric discharge, which also has, becomes good tendency.On the other hand, if hot post-tensioning intensity (Fa)
Value be 72kgf/mm2Hereinafter, the range of above-mentioned suitable normality elongation is then easily maintained, therefore preferably.
In addition, the present invention electrolytic copper foil in, as physical features, the value of above-mentioned normality tensile strength (F0) and on
The value for stating the hot post-tensioning intensity (Fa) after the heat treatment of 180 DEG C × 60 minutes is preferably satisfied with the relationship of following formula 2.
[formula 2]
[normality tensile strength (F0)]-[hot post-tensioning intensity (Fa)]≤10kgf/mm2
The meaning of the formula 2 is that the difference of " normality tensile strength (F0) " and " hot post-tensioning intensity (Fa) " is small, even if by one
Fixed heating is also difficult to soften.In the manufacture process of the cathode of lithium rechargeable battery, copper foil is by various hot resume
Influence.If as a result, the copper foil soften, as required by the cathode intensity of lithium rechargeable battery bending property,
All deviations of the corresponding deformation drag of dilation during during in negative electrode current collector and charge and discharge will become larger, can not
Ensure the quality stability as lithium rechargeable battery, therefore not preferably.So as to, it is desirable that there is the heating phase with such degree
Corresponding anti-softening ability.
And then the physical features of electrolytic copper foil of the invention preferably show high bending property, i.e., at 180 DEG C × 60 minutes
Heat treatment after heat after in resist bending experiment, number of bends until fracture be 3000 times or more.It is if resistance to after heat
Number of bends in bend test is 3000 times or more, then in the negative electrode current collector of lithium rechargeable battery when, with filling
The corresponding deformation drag of dilation during electric discharge is tremendous raising so that the extension of life of product is possibly realized.This place
Resist bending is tested after the heat said, even if in the case of the electrolytic copper foil of printed wiring board-use and the important spy that is required
Property.And about the number of bends, although not being clearly set forth out upper limit value, rule of thumb for be 6500 times or so.
And resist bending experiment is after heat described herein, the assay method based on JIS C 5016, with TESTER Industry Co., Ltd system
The flexural buckling made tests a machine (bending radius：1mm, rate of bending：100cpm, stroke：20mm), to wide 10mm × long 10cm
Short strip shape electrolytic copper foil, after the heat treatment of 180 DEG C × 60 minutes, measure its to fracture until number of bends examination
It tests.
The form of the surface treatment copper foil of the present invention：The surface treatment copper foil of the present invention, which is characterized in that contain to above-mentioned
Implement various surface treatments in the surface for having the electrolytic copper foil of iodine.The surface treatment refers to real in above-mentioned electrolytic copper foil surface
Apply one or more kinds of processing in roughening treatment, antirust treatment, silane coupling agent processing.The surface treatment is,
The requirement characteristic of different purposes is considered, for the purpose of paying adhesive strength, chemical resistance, heat resistance etc., to cathode copper
The processing that foil surface is implemented.In addition, about silane coupling agent processing, the negative electrode current collector of lithium rechargeable battery if it is for
In electrolytic copper foil when, then preferably the two sides of electrolytic copper foil implement, when if it is for the electrolytic copper foil in printed wiring board,
Then preferably implement in a face of electrolytic copper foil.
The manufacture form of the electrolytic copper foil of the present invention：The manufacturing method of the electrolytic copper foil of the present invention is above-mentioned containing iodine
The manufacturing method of electrolytic copper foil, which is characterized in that the composition of sulfuric acid copper electrolyte used herein.And sulphur described herein
Copper concentration in acids copper electrolyte uses the range of 50g/L~120g/L, further preferably using the model of 50g/L~80g/L
It encloses.In addition, free sulphuric acid concentration consider on the basis of the range of 60g/L~250g/L, further preferably consider with 80g/L~
On the basis of the range of 150g/L.
Iodine concentration in the sulfuric acid copper electrolyte is preferably in the range of 1.5mg/L~15.0mg/L.Further preferably exist
The range of 2.5mg/L~7.0mg/L.When the iodine concentration in sulfuric acid copper electrolyte is less than 1.5mg/L, it is precipitated by electrolysis
Electrolytic copper foil in iodine number it is insufficient, so as to which the electrolytic copper foil obtained can not obtain the surface roughness of above-mentioned optimum range, prolong
The physical characteristics such as exhibition rate, tensile strength, various physical properties also have the tendency that changing aggravation, therefore not over time
It is preferred that.On the other hand, if the iodine concentration is more than 15.0mg/L, the iodine amount in electrolytic copper foil increases, and will occur aforementioned
Problem.In addition, by making the iodine concentration in 7.0mg/L hereinafter, the flatness in face and good is precipitated so as to take into account electrolytic copper foil
Mechanical strength., it is preferable to use the iodide such as NaI, KI in the addition of iodine at this moment.
In addition, the concentration of preferred below the 1.0mg/L of the cl concn of copper electrolyte that the present invention uses.If the cl concn surpasses
1.0mg/L is crossed, then the electrolytic copper foil obtained is easily brittle, therefore not preferably.And then for the electrolysis for further stablizing the present invention
The range for the cl concn that copper foil contains, preferably in the range of 0.4mg/L~0.8mg/L.By using the cl concn of the range, from
And balance well containing above-mentioned each ingredient, and face slimming is precipitated so that the stabilization of the electrolytic copper foil of high intensity is manufactured as
It may.When the adjustment for carrying out the cl concn in the sulfuric acid copper electrolyte, preferably it is adjusted with hydrochloric acid or copper chloride (II).
This is because they will not bring harmful effect to the solution character of sulfuric acid copper electrolyte.
And then the present invention electrolytic copper foil manufacturing method in, preferably the temperature of copper electrolyte for 40 DEG C~60 DEG C,
Current density 50A/dm2~85A/dm2Range under be electrolysed.When solution temperature is less than 40 DEG C, lack the stabilization of electrolysis
Property, the deviation of the physical strengths such as the tensile strength of obtained electrolytic copper foil and elongation has bigger tendency.On the other hand, if
Solution temperature is more than 60 DEG C, then the moisture evaporation aggravation in solution, the stability of solution composition is insufficient, so as to become process management
It obtains numerous and diverse therefore not preferred.
In addition, if current density during electrolysis described herein is less than 50A/dm2, then required by can not obtaining industrialness
Production efficiency, production efficiency reduce, so as to not preferably.On the other hand, if current density when being electrolysed is more than 85A/dm2,
In terms of the physical characteristics such as surface roughness, the tensile strength in face are precipitated deviation easily occurs for the electrolytic copper foil then manufactured, so as to not
It is preferred that.
The lithium ion secondary battery cathode obtained with the surface treatment copper foil of the present invention：With the surface treatment of the present invention
Copper foil and the lithium ion secondary battery cathode obtained, which is characterized in that employ above-mentioned surface treatment copper foil as cathode
Current-collector.In general, the cathode of lithium rechargeable battery is, carried out on the surface of the surface treatment copper foil as negative electrode current collector
Negative electrode active material it is immobilized, so as to obtain with negative electrode active material negative electrode current collector state cathode.In the manufacture work
It is soft so as to improve good heat-resistant simultaneously by using the surface treatment copper foil of the electrolytic copper foil with the present invention in sequence
The property changed, bending resistance characteristic and actually immobilized negative electrode active material " current-collector with negative electrode active material is (negative
Pole) " current-collector bending property under state.
The other application field of the electrolytic copper foil of the present invention：The electrolytic copper foil and surface treatment copper foil of the present invention can also turn
(there is the situation of referred to as " copper clad laminate " in context for printed wiring board manufacture copper clad laminate.) manufacture in.
For example, above-mentioned surface-treated electro-deposited copper foil and insulating layer constituent material are laminated, so as to can also obtain printed wiring board
Manufacture copper clad laminate.And it is special for the sake of prudent it is hereby stated that, comprising firm in the concept of copper clad laminate described herein
Property both copper clad laminate and flexible copper clad laminate.The electrolytic copper foil of the present invention is due to being slim, so as to suitable for containing
The formation of the fine-line of level required by having the flexible printed circuit board of TAB, COF etc..
Hereinafter, for easy understanding electrolytic copper foil of the invention etc., so as to show embodiment.
Embodiment
In this embodiment, copper concentration 80g/L, the free sulphur in copper-bath are employed as sulfuric acid copper electrolyte
The basic solution of acid concentration 140g/L, and adjust to each additive concentration shown in table 1.Iodine addition at this time uses potassium iodide
(KI) it carries out, and hydrochloric acid has been used in the adjustment of cl concn.And then with shown in table 1 there is different additives to coordinate
The sulfuric acid copper electrolyte of ratio composition produces eight kinds of electrolytic copper foils containing iodine of 1~sample of sample 8.And the embodiment
It is to be used for, by being compared with comparative example so that the clear implementation of the difference for being used as the general physical property of copper foil
Example.
In the manufacture of electrolytic copper foil, the titanium plate ground by the sand paper of 2000# to surface is used as cathode
Electrode, and anode uses DSA, and in 50 DEG C of solution temperature, current density 75A/dm2Under conditions of be electrolysed, so as to manufacture
Go out 18 μm of thickness, electrolytic copper foil containing iodine.The surface of the glassy surface (face that the opposition side in face is precipitated) of these electrolytic copper foils
Roughness (Rzjis) is 1.4 μm.The assessment result of each characteristic of the electrolytic copper foil obtained herein is summarized in table 2, so as to
It is compared with following comparative example.
Here various determination conditions etc. are illustrated.Tensile strength, extension after the normality and heat of embodiment sample
The measure of rate is carried out based on IPC-TM-650.In addition, the measure of surface roughness is carried out based on JIS B 0601-2001.
Following comparative example is also identical.
Comparative example
The comparative sample 1 and comparative sample 2 of the comparative example employ the copper electrolyte below iodine concentration 0.5mg/L, and should
Comparative example is the comparative example for being compared with above-described embodiment.And then to employ iodine dense for comparative sample 3 and comparative sample 4
Spend the copper electrolyte (copper electrolyte for not containing iodine) of 0.0mg/L.It is other with the manufacturing condition identical with embodiment, ratio has been made
Compared with 1~comparative sample of sample 4.Above-mentioned electrolyte composition and the electrolyte composition of embodiment are shown in together in table 1 below.It is logical
The comparison for crossing embodiment and comparative example can explicitly comparison of the result as the basic physical property of copper foil：With reference to table 1,2 and of table
Attached drawing carries out the comparison of embodiment and comparative example.
[table 1]
According to the table 1,1~sample of sample 8 of embodiment is employed included in " below cl concn 1.0mg/L, iodine concentration
Copper electrolyte of the sulfuric acid copper sulfate electrolyte as the present invention in the proper range of 1.5mg/L~15.0mg/L ".With this
Relatively, it is known that, 1~comparative sample of comparative sample 4 is not using the range included in " iodine concentration 1.5mg/L~15.0mg/L "
The copper electrolyte containing the appropriate chlorine and iodine is not used in interior sulfuric acid copper sulfate electrolyte.
[table 2]
Note) heat after：Situation after the heat treatment of 180 DEG C × 60 minutes.
The surface roughness in precipitation face：It is marked with Rzjis
From the table 2 it is found that in the manufacturing method of the electrolytic copper foil containing iodine of the application, by using cupric electrolysis hydroful
The sulfuric acid copper sulfate electrolyte of the condition of foot " below cl concn 1.0mg/L, iodine concentration 1.5mg/L~15.0mg/L ", from
And the electrolytic copper foil of the mass % of 0.005 mass % of iodine amount~0.063 can be obtained.It is found that the precipitation face of the electrolytic copper foil is put down
It is sliding, and the difference of the tensile strength after normality and heat meets the value of [normality tensile strength (F0)]-[hot post-tensioning intensity (Fa)]
For 10kgf/mm2Following condition.
Investigation 1 to the characteristic of the negative electrode current collector as lithium rechargeable battery：In the investigation 1, by aforementioned table 2
Data represent " the iodine amount in foil " that the X-direction of horizontal axis is represented " in foil in X-Y coordinate plane with the Y-direction of the longitudinal axis
Cl concn ", that draw is exactly Fig. 1.And then more than the straight line of the 0.003 mass % of iodine amount shown in the Fig. 1
In region, the data of all embodiments are contained.On the other hand, it is known that, the iodine amount of the comparative sample of comparative example is not
0.003 mass % of foot.
Herein, if looking back the contents of table 2, it is known that in embodiment, the iodine of the only electrolytic copper foil of sample 7 contains
Amount has been more than 0.03 mass %.As this as a result, the number of bends that resist bending is tested after the heat of discovery sample 7 is 1105 times, it is
The value lower than the number of bends of other samples.This is also effectively demonstrated, if the iodine amount in electrolytic copper foil is more than 0.03
Quality %, then the tissue of electrolytic copper foil there is embrittlement.
And then contain with the iodine amount in the region (region represented by above-mentioned formula 1) on the upside of the straight line of Fig. 1 and chlorine
The situation for the amount of having, due to as the spy required by the electrolytic copper foil in the negative electrode current collector purposes for lithium rechargeable battery
Property, i.e., the heat-resisting softening resistance of heating is especially enhanced, and heat-resisting softening resistance is stablized, therefore have preference.It can recognize
In the electrolytic copper foil in the negative electrode current collector purposes for lithium rechargeable battery, not only to consider in electrolytic copper foil
Iodine amount, and consider the chlorine amount in electrolytic copper foil, it is especially preferred so as to meet the relationship shown in formula 1.
Consider the above can determine whether, in the electrolytic copper foil containing iodine of the application, iodine amount is 0.003 matter
Measure the mass % of %~0.03, chlorine amount is the mass % of 0.0006 mass %~0.0018, and is in the condition shown in formula 1 that meets
Range, just it is provided with the most preferred characteristic of the negative electrode current collector as lithium rechargeable battery.
Investigation 2 to the characteristic of the negative electrode current collector as lithium rechargeable battery：The investigation 2 is used to illustrate the present invention's
The distinctive heat-resisting property of softening in electrolytic copper foil containing iodine, and to " adding after the heating at 350 DEG C of normality tensile strength and progress
The relationship of hot post-tensioning intensity " is illustrated.That is, its be the cathode for considering lithium rechargeable battery manufacturing process in institute's quilt
The hot environment of application, and for being carried out pair the variation of the physical characteristic after the heating in the case where having carried out 350 DEG C, with comparative example
The investigation of ratio.In the investigation 2, for convenience of description, with from the 1~sample of sample 8 of the above embodiments and comparative example institute
The sample extracted out in 1~comparative sample of comparative sample 4 illustrates.
Table 3 represents " normality tensile strength (F0) " and " has carried out the heating post-tensioning intensity after the heating at 350 DEG C
(Fb) " relationship.This is the short strip shape with 10cm × wide 10mm after the heating that 350 DEG C × 60 minutes have been carried out to copper foil, long
Sample carries out result obtained from tension test.
[table 3]
Note) heat after (Fb)：The situation of the heat treatment of 350 DEG C × 60 minutes.
Will also realize that according to table 3, even if the electrolytic copper foil containing iodine, do not contain the sample 3 of chlorine 350 DEG C × 60 minutes plus
After heat treatment, tensile strength also can drastically decline.In addition, comparative sample 1, comparative sample 2 and comparative sample 4, although after heat
Tensile strength is shown as less than 30kgf/mm2Value, but 1~sample of sample 3 maintains 30kgf/mm2Above value.In contrast
Ground, sample 2 are located at and meet in the region of the relationship shown in previously described formula 1, and in the shadow region of Fig. 1, even if receiving
After the heat treatment of 350 DEG C × 60 minutes, still has 40kgf/mm2Above high tensile strength, and the resist bending shown in table 2
The number of bends of experiment also shows as outstanding value.
On the other hand, the range (formula shown in above-mentioned formula 1) that the straight line A in Fig. 1 is divided, it is known that 350 DEG C × 60
The physical property of the electrolytic copper foil of the application after minute heat treatment is distinguished, and described Fig. 1 is illustrated shown in investigation 1
" relationship of iodine amount in electrolytic copper foil physical property and chlorine amount after heat treatment " figure.
That is, with iodine amount and chlorine in the region (region for meeting condition shown in formula 1) on the upside of the straight line of the Fig. 1
The situation of amount, due to as required by the electrolytic copper foil in the negative electrode current collector purposes for lithium rechargeable battery
Characteristic especially enhances the heat-resisting softening resistance of heating, and heat-resisting softening resistance is stablized, therefore preferably.So as to clearly may be used
Know, in the electrolytic copper foil in the negative electrode current collector purposes for lithium rechargeable battery, not only consider in electrolytic copper foil
Iodine amount, and consider the chlorine amount in electrolytic copper foil, it is especially preferred so as to meet the relationship shown in formula 1.
Contain iodine and chlorine well from the foregoing, it will be observed that must be balanced in electrolytic copper foil.It is classified as such electrolytic copper foil
Sample 1 and sample 2 electrolytic copper foil, it is strong for the anti-softening ability of heating, that is, be used in the cathode of lithium rechargeable battery
Manufacture, dilation phenomenon when also can be to charge and discharge show sufficient non-deformability.
Investigation 3 to the characteristic of the negative electrode current collector as lithium rechargeable battery：The investigation 3 is also used for illustrating the present invention
The electrolytic copper foil containing iodine in the distinctive heat-resisting property of softening, and " heat-resisting bending tensile test result " is expounded.It should
Heat-resisting bending tensile test (jus singular) has obtained tension test after the heat treatment of 350 DEG C × 60 minutes is implemented to copper foil
As a result.Table 4 records the result.This place
The test method of heat-resisting bending tensile test (jus singular) said is as follows.
Heat-resisting bending tensile test step
1. in atmospheric environment, with certain heating temperature 350 DEG C of the heating temperature of jus singular (, other 180 DEG C) to drawing
The copper foil sample for stretching the short strip shape of 1cm × 10cm of experiment carries out the heat treatment of 60 minutes, and carries out placement cooling.
2. after, the sample is bent, in the state of 15kg loads are applied, load 180 ° of bending stresses of 1 minute and shape
Into bending section, and then restore to original billet shape.
3. in room temperature environment, with stretching test machine determination tensile strength and elongation.
4. evaluation item
Resistance to hot tensile strength (the resistance to hot tensile strength that heat-resisting bending tensile test step (2) is omitted)
Heat-resisting bend tension intensity
Here to being illustrated using the reasons why above-mentioned heat-resisting bending tensile test (jus singular).Work as lithium rechargeable battery
When active material layer is formed in the cathode current-collector for having used copper foil, load high temperature.And then in rectangular lithium ion two
In primary cell, having makes by high-temperature load and forms the cathode of active material layer in the state with anode or gasket stacking
Get off and be bent and being thinned becomes rectangular process.Therefore, heat-resisting bending tensile test (jus singular) is, in order to assess relative to
The patience of the copper foil of load when having been applied such bending machining and import.
[table 4]
By the table 4 it is found that embodiment (sample 1, sample 2, sample 5, sample 6), compared with comparative sample 1,180 DEG C × 60
Bend tension intensity after minute heating is also relatively high.Even if it follows that the electrolytic copper foil containing iodine of the present invention has
By being heated at high temperature the characteristic for being also difficult to soften, and even if bending, tensile strength also reduces few, it is difficult to be broken.
Herein, if the sample 5, sample 6 and comparative sample 1 of table 4 compared, perhaps can feel can not be 350
DEG C × heating of 60 minutes after tensile strength in terms of see that big difference exists.Furthermore if observe their 180 DEG C × 60
Bend tension intensity after the heating of minute, then compared with comparative sample 1, the value of the bend tension intensity of sample 5 and sample 6 is bright
It is aobvious to increase.Thus, it can be known that sample 5 and sample 6, compared to comparative sample 1, even if by the heating of big temperature range can table
Reveal good tensile strength, even if bending, the reduction of tensile strength is also few, it is difficult to be broken.
If in addition, observation with the comparable sample 1 of embodiment, sample 2, sample 5, sample 6 180 DEG C × 60 minutes plus
The variation of bend tension intensity after heat and after the heating of 350 DEG C × 60 minutes can be known to draw a conclusion.In sample 1 and sample
In 2, compared with the bend tension intensity after the heating of 180 DEG C × 60 minutes, the bend tension after the heating of 350 DEG C × 60 minutes
Intensity increases.Their iodine amount is respectively 0.018 mass %, 0.019 mass %, by containing the iodine of such degree, from
And significantly improve heat-resisting softening resistance of the material for heating.On the other hand, in sample 5 and sample 6, with 180 DEG C × 60
Bend tension intensity after the heating of minute is compared, and the bend tension intensity after the heating of 350 DEG C × 60 minutes becomes especially low.
Their iodine amount is 0.005 mass %, in the case of the iodine amount of the degree, can not realize heat-resisting softening resistance
It significantly improves.Even if but it can be said that sample 5 and sample 6 compared to comparative example, the heat-resistant that can also improve material really is soft
The property changed.
Investigation 4 to the characteristic of the negative electrode current collector as lithium rechargeable battery：In the investigation 4, comprising being remembered with table 1
Electrolytic copper foil obtained from electrolyte composition other than the composition of load, and made more with the foil physical property after 350 DEG C of heat runs
Detailed research.Composition, the composition of each copper electrolyte that electrolyte has been recorded in the table 5 are 350 DEG C × 60 minutes corresponding
Heat run after foil physical property.And the manufacturing condition other than electrolyte composition is identical with embodiment.Herein, according to table 1
Result with table 2 is it is found that the serial (general names of " sample S-1~sample S-8 " of the S of table 5.) it is suitable with the electrolytic copper foil of the present invention
Copper foil.On the other hand it is found that the serial (general names of " sample C-1~sample C-4 " of the C of table 5.) be not and cathode copper of the invention
The comparable copper foil of foil.And indicate hereby as reference, sample S-2 is the sample 1 described in embodiment, and sample S-5 is embodiment
Described in sample 2, sample C-1 be comparative example described in comparative sample 1, sample C-2 be comparative example described in comparison examination
Sample 2, sample C-4 are the comparative sample 4 described in comparative example.
[table 5]
Note) 1. hot post-tensioning intensity：Fb(kgf/mm2)
2. heat-resisting bend tension intensity (kgf/mm2)
3. poor tensile strength：①-②(kgf/mm2)
By the table 5 it is found that " S series " carries out the stretching after the heat treatment of 350 DEG C × 60 minutes compared with " C series "
Intensity increases.That is, the tendency of the tensile strength is observed it is found that with the sulfuric acid copper sulfate electrolyte system containing a certain amount of iodine
" the S series " made, shows the harsh heating of 350 DEG C × 60 minutes tensile strength as 27kgf/mm2Above is abundant
Anti-softening ability.And " S series " has shown 28kgf/mm even if be bent2Above high tensile strength.Separately
Outside, preferred form in observation " S series ", shows resistance to hot tensile strength and heat-resisting bend tension intensity simultaneously, also shows
30kgf/mm2Above high tensile strength is sample S-1~sample S-6.And as further preferred form it is sample
S-1~sample S-3, they also show 40kgf/ while resistance to hot tensile strength and heat-resisting bend tension intensity is shown
mm2Above high tensile strength.
Investigation 5 to the characteristic of the negative electrode current collector as lithium rechargeable battery：It is right with reference to table 6 in the investigation 5
The advantage when electrolytic copper foil containing iodine of the present invention is served as the negative electrode current collector of lithium rechargeable battery illustrates.At this
In explanation, using 1~sample of sample 3 of embodiment, the comparative sample 1 of comparative example, comparative sample 2 and comparative sample 4, section's Ademilson
Alloy Foil, calendering copper alloy foil, and they are compared.And in the investigation 5, it is contemplated that conductivity, and in conductivity
In measure, using Agilent Technologies B1500A semiconductor devices analyzer and employ based on JIS K 7194 four
Point probe method.
[table 6]
* after heat：Situation after the heat treatment of 350 DEG C × 60 minutes
* sections Ademilson Alloy Foil：The C7025 of Nippon Mining and Metals Co., Ltd's manufacture
* * roll copper alloy foil：The HCL02Z of Hitachi Cable Ltd.'s manufacture
In order to extend the cycle life of lithium rechargeable battery, it is necessary to what the resistance band of reduction negative electrode current collector as far as possible came
Voltage loss equably supplies or collects electronics to the negative electrode active material in battery, and makes its reaction.As negative electrode current collector
And the physical property after the heat treatment of 350 DEG C of the electrolytic copper foil used × 60 minutes, it is believed to characteristic be required to produce this
Raw big influence.
That is, as shown in Table 6, the electrolytic copper foil containing iodine of the application, after showing the heat treatment of 350 DEG C × 60 minutes
Tensile strength be more than 30kgf/mm2 high value, while under normality or heat after steadily show it is high
Conductivity.On the other hand, the electrolytic copper foil of iodine is not contained, although conductivity is high, heating results in tensile strength and significantly drops
It is low.Therefore can determine that, do not contain the electrolytic copper foil of iodine can not be resistant to lithium rechargeable battery in charge and discharge negative electrode current collector by
The dilation phenomenon arrived.
In addition, in table 6, used as comparing, show section's Ademilson Alloy Foil and calendering copper alloy foil.Section's Ademilson Alloy Foil
Although the tensile strength after heating is very good, alloy forms so that conductivity is low.Therefore, it is used when as negative electrode current collector
When, it is difficult to the whole reaction that lithium is equably equably collected for electron and in negative electrode active material to cathode occurs, so as to
Not preferably.
And in copper alloy is rolled, at first sight, it will be considered that it achieves the balance between tensile strength and conductivity.But
It is found that the conductivity of normality is lower than the sample of the embodiment as electrolytic copper foil or the sample of comparative example.When in this way
The metal foil of physical property come as negative electrode current collector in use, the fever of generation can lead to cathode current collection when carrying out charge and discharge
General ability portion is superheat state, forms the state of part annealing, and the only tensile strength at the position and resistance reduces, as cathode current collection
The deformation aggravation of device, and be difficult to happen and lithium is equably equably collected for electron, in negative electrode active material to cathode entirety
Reaction, therefore not preferably.
Known as described above, the electrolytic copper foil of the invention containing iodine, even if the comparative sample, section's Ademilson with comparative example close
Goldleaf, calendering copper alloy foil are compared, and are also more suitable in the purposes as the negative electrode current collector of lithium rechargeable battery.
Comprehensive descision：It can be said that with embodiment described above is comparable, electrolytic copper foil containing iodine, even if with hair
Raw bending is also difficult to the property being broken.Therefore, if such electrolytic copper foil is served as employed in lithium rechargeable battery
The collector materials of coiled battery are then difficult to happen battery softening caused by the hot resume of institute's load in the fabrication process,
And the influence that heating tape when being difficult to by charge and discharge comes, and then, the non-deformability of expansion/shrinkage phenomenon during to charge and discharge
Also it is strong.Accordingly, it can be said that the electrolytic copper foil containing iodine of the present invention is as the current-collector employed in lithium rechargeable battery
The suitable copper foil of material.
Industrial applicibility
The electrolytic copper foil of the present invention is to come the iodine not contained in existing electrolytic copper foil containing more than 0.003 mass %
Electrolytic copper foil.The electrolytic copper foil for containing iodine can show the electrolysis of the characteristic of various stabilizations chlorine amount changes
Copper foil.
And the physical property of the electrolytic copper foil, have and be difficult to the characteristic softened, and have lithium ion secondary concurrently heating
Good heat-resisting softening resistance and bending resistance characteristic required by the current-collector of battery.So as to if made using the electrolytic copper foil
For current-collector, then the market supply of the lithium rechargeable battery of high-quality and long-life can be realized.
Claims (7)
1. a kind of electrolytic copper foil is the electrolytic copper foil as obtained from being electrolysed copper electrolyte, which is characterized in that
Normality tensile strength (F0) value be 48kgf/mm2~72kgf/mm2, after the heat after the heat treatment of 350 DEG C × 60 minutes
Tensile strength (Fb) value be more than 40kgf/mm2, the heat-resisting bend tension intensity after the heat treatment of 350 DEG C × 60 minutes exists
30kgf/mm2More than.
2. electrolytic copper foil as described in claim 1, which is characterized in that when sheet metal thickness is 18 μm ± 1.8 μm, 180 DEG C ×
Number of bends after the heat treatment of 60 minutes, in resist bending experiment is 3000 times or more.
3. electrolytic copper foil as described in claim 1, which is characterized in that the value with Rzjis is in 0.70 μm~2.0 μ ms
Precipitation face.
4. electrolytic copper foil as described in claim 1, which is characterized in that the hot post-tensioning after the heat treatment of 180 DEG C × 60 minutes
Stretch intensity (Fa) value be 38kgf/mm2~72kgf/mm2。
5. electrolytic copper foil as described in claim 1, which is characterized in that normality tensile strength (F0) value, with 180 DEG C × 60 points
Hot post-tensioning intensity (F after the heat treatment of clocka) value meet the relationship of following formula 2,
[formula 2]
[normality tensile strength (F0)]-[hot post-tensioning intensity (Fa)]≤10kgf/mm2。
6. surface treatment copper foil, which is characterized in that contain the electrolytic copper foil of iodine to any one of them of Claims 1 to 5
Surface implements surface treatment.
7. lithium ion secondary battery cathode, which is characterized in that immobilized in the surface treatment copper foil described in claim 6 to have cathode
Active material.
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| CN103649378B (en) * | 2011-06-30 | 2016-12-14 | 古河电气工业株式会社 | Electrolytic copper foil, the manufacture method of this electrolytic copper foil and using this electrolytic copper foil as the lithium rechargeable battery of collector body |
| JP5722813B2 (en) * | 2012-03-02 | 2015-05-27 | Jx日鉱日石金属株式会社 | Electrode copper foil and negative electrode current collector for secondary battery |
| JP5718476B2 (en) * | 2012-06-27 | 2015-05-13 | 古河電気工業株式会社 | Electrolytic copper foil for lithium ion secondary battery, negative electrode of lithium ion secondary battery, and lithium ion secondary battery |
| JP5698196B2 (en) * | 2012-08-17 | 2015-04-08 | Jx日鉱日石金属株式会社 | Electrolytic copper foil, and secondary battery current collector and secondary battery using the same |
| TWI518210B (en) | 2013-01-31 | 2016-01-21 | 三井金屬鑛業股份有限公司 | Electrolytic copper foil and method for manufacturing the same and surface-treated copper foil using the electrolytic copper foil |
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| JP6190980B2 (en) * | 2015-09-25 | 2017-08-30 | 古河電気工業株式会社 | Electrolytic copper foil and various products using the electrolytic copper foil |
| KR102109379B1 (en) * | 2016-08-19 | 2020-05-12 | 케이씨에프테크놀로지스 주식회사 | Electrolytic copper foil and Current collector for lithium secondary battery and Secondary battery comprising the electrolytic copper foil |
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| KR102103765B1 (en) | 2018-05-16 | 2020-04-28 | 일진머티리얼즈 주식회사 | Electrolytic Copper Foil and secondary battery using thereof |
| JP7087758B2 (en) * | 2018-07-18 | 2022-06-21 | 住友金属鉱山株式会社 | Copper-clad laminate |
| CN110331421A (en) * | 2019-04-30 | 2019-10-15 | 江苏华威铜业有限公司 | A kind of electrolytic copper foil and its manufacturing process |
| US20230074384A1 (en) * | 2020-01-30 | 2023-03-09 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil |
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| CN102959135B (en) | 2016-03-09 |
| WO2012002526A1 (en) | 2012-01-05 |
| CN102959135A (en) | 2013-03-06 |
| JP5373970B2 (en) | 2013-12-18 |
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| KR20130006504A (en) | 2013-01-16 |
| KR101385760B1 (en) | 2014-04-17 |
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| JPWO2012002526A1 (en) | 2013-08-29 |
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