CN102959135B - Electrolytic copper foil and its manufacture method - Google Patents
Electrolytic copper foil and its manufacture method Download PDFInfo
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- CN102959135B CN102959135B CN201180032383.5A CN201180032383A CN102959135B CN 102959135 B CN102959135 B CN 102959135B CN 201180032383 A CN201180032383 A CN 201180032383A CN 102959135 B CN102959135 B CN 102959135B
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- copper foil
- electrolytic copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 239000011889 copper foil Substances 0.000 title claims abstract description 231
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 32
- 239000011630 iodine Substances 0.000 claims abstract description 74
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 74
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- 239000000460 chlorine Substances 0.000 claims abstract description 32
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 64
- 229910001416 lithium ion Inorganic materials 0.000 claims description 64
- 239000003792 electrolyte Substances 0.000 claims description 34
- 238000005452 bending Methods 0.000 claims description 33
- 238000004381 surface treatment Methods 0.000 claims description 21
- 239000011258 core-shell material Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 10
- 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 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 5
- 150000002496 iodine Chemical class 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 61
- 238000010438 heat treatment Methods 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 238000011835 investigation Methods 0.000 description 14
- 230000010339 dilation Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000011888 foil Substances 0.000 description 9
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 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
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 238000012545 processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 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
- 241000024287 Areas Species 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
- 239000001828 Gelatine 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
- 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
- 238000000137 annealing Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 150000001879 copper Chemical class 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
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 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
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009413 insulation 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
- 238000002156 mixing 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
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 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
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011179 visual inspection Methods 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 invention is to, even if provide the change of chlorine amount also can show the electrolytic copper foil of various stable characteristic.And then, adopt a kind of electrolytic copper foil to realize this object, it is the electrolytic copper foil obtained by electrolytic copper electrolytic solution, it is characterized in that, iodine amount in electrolytic copper foil is more than 0.003 quality %, and this iodine amount is preferred in 0.003 quality % ~ 0.03 quality % scope further.And then the chlorine amount of this electrolytic copper foil is preferably in the scope of below 0.0018 quality %.
Description
Technical field
The present invention relates to the manufacture method of electrolytic copper foil and this electrolytic copper foil.Particularly relate to the physical property with the tensile strength, elongation etc. that are applicable to lithium-ion secondary cell running contact, and also can be used in the electrolytic copper foil in the copper clad laminate manufacture of printed wiring board manufacture.
Background technology
In recent years; due to the raising that raising and the resource recycling of environmental protection consciousness require; lithium-ion secondary cell is popularized as reusable useful power supply, and such as it is used in and is carried in outdoor notebook computer, mobile phone, TV, video camera products.Along with the miniaturization of these electric equipment products and electronics, small-sized, high life, light weight be it is also proposed to the lithium-ion secondary cell as power supply supply source, and play the requirement of high-energy-density.
Look back the developing history of lithium-ion secondary cell, in the anode collector of negative pole forming lithium-ion secondary cell, attempt the rolled copper foil employing surface smoothness excellence.In the anode collector of the negative pole of present formation lithium-ion secondary cell, use any one in rolled copper foil or electrolytic copper foil.
In the manufacturing processed of the negative pole of this lithium-ion secondary cell, disclosed in patent documentation 1 or patent documentation 2, there is the operation of load high temperature.In this operation, as form negative pole anode collector Copper Foil in the also high temperature by load.Its result, if this Copper Foil occurs softening, then has the problem of the impact of the deformation stress that dilation when being easily subject to lithium-ion secondary cell repetition discharge and recharge, negative active core-shell material brings.
For this problem, when adopting the rolled copper foil obtained by more cheap tough pitch copper, owing to easily heating the recrystallization that causes and softening, thus be easily subject to the impact of dilation stress when repeating above-mentioned discharge and recharge, and the life-time dilatation of lithium-ion secondary cell is comparatively difficult.In addition, rolled copper foil derives from its manufacture method, therefore expensive, thus is difficult to provide by the price cheaper than electrolytic copper foil.This point, for manager, becomes the obstacle in order to win worldwide price competition.In addition, because rolled copper foil is difficult to broadening as Copper Foil, be therefore difficult to improve the production efficiency in battery manufacture, thus the reduction of product cost is limited, becomes unavoidable shortcoming.
To this, think, electrolytic copper foil is owing to being difficult to occur heat the recrystallization that causes and be difficult to soften, thus strong to the resistibility of dilation stress when repeating above-mentioned discharge and recharge all the time.In addition, because electrolytic copper foil is more cheap than rolled copper foil, the rentability of the lithium-ion secondary cell in market in price aspect can be improved, thus as the substitute of rolled copper foil, the use of electrolytic copper foil is actively considered always.Its result, now, two sides all has the electrolytic copper foil of the thin surface being equal to rolled copper foil, is widely used in the anode collector purposes of lithium-ion secondary cell.
All there is as this two sides the correlation technique of the electrolytic copper foil of the thin surface being equal to rolled copper foil, as patent documentation 3, patent documentation 4 etc. Suo Gongkai, inventing to reduce the surfaceness in the precipitation face of electrolytic copper foil, in described invention, controlling the electrolytic solution composition, electrolyte temperature, current density etc. of the copper electrolyte manufactured for electrolytic copper foil.
In patent documentation 3, by be manufactured on tellite manufacture in useful, etching performance and impedance Control excellent performance electro-deposition copper foil for the purpose of, have employed " comprise (A) electrolytic solution to flow through between the anode and cathode, and then between this anode and this negative electrode, apply the operation making the voltage of the significant quantity this negative electrode being separated out copper; Herein, this electrolytic solution contains cupric ion, sulfate ion and at least one organic additive or its derivative, and the chlorine ion concentration of this solution is for about to reach 1ppm; Current density is about 0.1 ~ about 5A/cm
2scope; And (B) removes the operation of Copper Foil from this negative electrode." manufacture method.That is, have employed such electrolytic condition: use the copper electrolyte controlling cl concn.
And, in patent documentation 4, have employed such electrolytic condition, it is characterized in that, employ the thiocarbamide or derivatives thereof containing 0.05 ~ 2.0 weight ppm, the high molecular polysaccharide of 0.08 ~ 12 weight ppm, and the glue of molecular weight less than 10000,0.03 ~ 4.0 weight ppm is as the electrolytic solution of additive.Its result, has produced the electrolytic copper foil of surfaceness close to rolled copper foil level of surface roughness in the precipitation face of this electrolytic copper foil.
And then, point out in patent documentation 5, crystal structure miniaturization and the electrolytic copper foil described in each publication such as the patent documentation 3, patent documentation 4 etc. that reduce surfaceness exist fully cannot meet the situation of market to the demand of cycle charge discharge electric life, overcharge characteristic aspect.According to this patent documentation 5, elongation in the smoothness on the surface that cannot represent with 10 mean roughness Rz as the Copper Foil characteristic affecting cycle charge discharge electric life and overcharge characteristic, normal temperature tensile strength, elongation, non-re-crystallizing, hot environment is important, and as obtaining the successful examples of Copper Foil of best effects in secondary cell characteristic, in the embodiment 1 of patent documentation 5, disclose so a kind of electrolytic copper foil.That is: " in the sulfuric acid copper sulfate electrolyte containing cupric sulfate pentahydrate 280g/L, sulfuric acid 100g/L, chlorion 35ppm, add the low molecular weight gelatine 7ppm of molecular-weight average 3000, Natvosol 3ppm, 3-sulfydryl-1-propane sulfonic acid sodium 1ppm, and electrolyte temperature 55 DEG C, flow velocity 0.3m/ minute, current density 50A/dm
2condition " etc. the electrolytic copper foil that manufactures; " it is characterized in that, the surfaceness that face separated out by electrolytic copper foil represents with 10 mean roughness Rz, crystal structure under normal temperature is less than the fine crystalline of 2.5 μm, simultaneously, the smallest peaks spacing on basis, mountain is more than 5 μm, and normal temperature tensile strength is 40kg/mm
2below, and normal temperature tensile strength after the thermal treatment of 130 DEG C, 15 hours be reduced within 15%, there is not thermal softening.”
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-236684 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-282550 publication
Patent documentation 3: Japanese Unexamined Patent Publication 7-188969 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-53789 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2004-79523 publication
Summary of the invention
The problem that invention will solve
But, in the electrolytic copper foil of the anode collector for lithium-ion secondary cell, pointed by above-mentioned patent documentation 5, not only always require that improvement affects the characteristic of the Copper Foil of cycle charge discharge electric life and overcharge characteristic, but also the deviation that there is the physical property such as elongation, tensile strength of electrolytic copper foil becomes the situation of problem.
Spy is traced it to its cause, and the chlorine that copper electrolyte used when can think that electrolytic copper foil manufactures comprises is reason.This chlorine, is sometimes added wittingly and is controlled, being sometimes also mixed into as keeping away impurity by vinylchlorid pipe arrangement etc.And then based on electrochemistry viewpoint, even if the chlorine in electrolytic solution, the variation only having trace, is also the composition easily product quality being brought to impact.Therefore, although those skilled in the art considered that the electrolytic copper foil for electrochemically manufacturing, carried out the improvement of the manufacture method for the purpose of the deviation reducing the quality of electrolytic copper foil own, the variation of cl concn is the major cause that can not keep away.
On the other hand, to the requirement proposing higher stay in grade for the electrolytic copper foil in lithium-ion secondary cell running contact, namely, on the basis accepting existing electrolytic copper foil, though require to have the heat-resistant property of softening that heating is also difficult to soften, bending resistance characteristic, immobilized actually negative active core-shell material " running contact (negative pole) with negative active core-shell material " state under quality stable of high level of running contact bending property etc.
The method of dealing with problems
Therefore, the present inventor carries out the result of concentrating on studies, and as the suitable electrolytic copper foil of the copper clad laminate of the constituent material and printed wiring board manufacture that serve as lithium-ion secondary cell running contact, contemplates electrolytic copper foil as described below.In addition, by adopting the manufacture method of the following stated, the High-efficient Production of electrolytic copper foil of the present invention is made to become possibility.
Electrolytic copper foil of the present invention: electrolytic copper foil of the present invention is the electrolytic copper foil obtained by electrolytic copper electrolytic solution, and it is characterized in that, the iodine amount in electrolytic copper foil is more than 0.003 quality %.
Surface treatment copper foil of the present invention: surface treatment copper foil of the present invention, is characterized in that, implements surface treatment to the surface of the above-mentioned electrolytic copper foil containing iodine.
The manufacture method of electrolytic copper foil of the present invention: the manufacture method of electrolytic copper foil of the present invention, it is the manufacture method of the above-mentioned electrolytic copper foil containing iodine, it is characterized in that, adopt iodine concentration to be that the sulfuric acid copper sulfate electrolyte of 1.5mg/L ~ 15.0mg/L scope is as copper electrolyte.And this copper electrolyte further preferred cl concn is below 1.0mg/L.
And, in the manufacture method of electrolytic copper foil of the present invention, be preferably 40 DEG C ~ 60 DEG C, current density 50A/dm with the temperature of copper electrolyte
2~ 85A/dm
2electrolytic condition carry out electrolysis.
Lithium ion secondary battery cathode with surface treatment copper foil of the present invention obtains: the negative pole of lithium-ion secondary cell of the present invention, is characterized in that, uses the surface treatment copper foil of the invention described above as anode collector.
The effect of invention
Electrolytic copper foil of the present invention as described above, is the electrolytic copper foil containing the above iodine of 0.003 quality %.Thus, by the sheet material copper that makes electrolytic copper foil containing iodine, even if thus chlorine amount variation in electrolytic copper foil, also can indicate stable physical property.
Therefore, by being used in the negative pole of lithium-ion secondary cell by electrolytic copper foil of the present invention, thus can provide excellent to the resistibility of the dilation phenomenon occurred with discharge and recharge at an easy rate to market and long-life lithium-ion secondary cell.
Accompanying drawing explanation
Fig. 1 is the figure for checking " electrolytic copper foil physical properties " and " the iodine amount that electrolytic copper foil contains and chlorine amount " relation.
Embodiment
Next coming in order elaborate to the manufacture method of electrolytic copper foil of the present invention, surface treatment copper foil, the negative pole of lithium-ion secondary cell that obtains with this surface treatment copper foil.
The form of electrolytic copper foil of the present invention: electrolytic copper foil of the present invention is the electrolytic copper foil obtained by electrolytic copper electrolytic solution.The feature of this electrolytic copper foil is, the iodine amount in electrolytic copper foil is in the scope of more than 0.003 quality %.So be suitable for serving as lithium-ion secondary cell running contact containing the electrolytic copper foil of iodine, and the running contact bending property under the state that simultaneously can improve " running contact (negative pole) with negative active core-shell material " of the heat-resistant property of softening, bending resistance characteristic and immobilized actually negative active core-shell material.
Herein, the iodine amount in electrolytic copper foil is preferably more than 0.003 quality %.When this iodine amount is less than 0.003 quality %, any characteristic is all unstable, and the stable of product quality becomes difficulty.On the other hand, if the iodine amount in electrolytic copper foil is more than 0.003 quality %, even if the chlorine amount variation then in electrolytic copper foil, also stable physical property can be shown, thus preferably.But, strictly speaking, if this iodine amount is more than 0.03 quality %, then above-mentioned all characteristics all cannot be further enhanced, the embrittlement of electrolytic copper foil can be caused on the contrary, curved characteristic is deteriorated, and the reduction of exterior quality under visual inspection also has and becomes serious tendency, thus iodine amount is preferably below 0.03 quality %.
In addition, in the electrolytic copper foil of the application, preferably on the basis controlling above-mentioned iodine, also control the chlorine amount in electrolytic copper foil.That is, in electrolytic copper foil of the present invention, the chlorine amount measured by chemical analysis is preferably in the scope of 0.0000 quality % ~ 0.0018 quality %.That is, when the chlorine amount that electrolytic copper foil contains is at below 0.0018 quality %, owing to separating out the surfaceness step-down in face, the precipitation face of slimming is easily obtained, thus preferably as the constituent material of lithium-ion secondary cell running contact.And then have detailed describing in contrast place of embodiment and comparative example, in brief namely, in order to improve heat-resistant property of softening when accepting heat, preferably this chlorine amount is at 0.0006 quality % ~ 0.0018 quality %.
And then, in electrolytic copper foil of the present invention, the chlorine amount measured by chemical analysis and iodine amount are preferably met with the relation of following formula 1 (be applicable to the anode collector purposes of lithium-ion secondary cell, the chlorine amount of electrolytic copper foil and the relation of iodine amount).By meeting such relation, even if thus at the temperature of about 350 DEG C, accept heating, also can demonstrate the high heat-resistant property of softening.Be described in detail about in the embodiment that this point will be described below.Below first the analytical procedure of chlorine amount and iodine amount is set forth.
[formula 1]
[iodine amount (quality %)] >=-30 × [chlorine amount (quality %)]+0.03
Measure chlorine amount in accordance with the following methods.In nitric acid, heat Copper Foil and after making it dissolve, add a certain amount of silver nitrate solution.Then, add a certain amount of KBr solution, make chloride ion carry out co-precipitation together with Silver monobromide.In the dark leave standstill after 15 minutes, filter out throw out and clean.Afterwards, throw out is transferred in beaker, with thiourea solution, throw out is dissolved, and in the dark place a Dinner.Dilute this solution and constant volume, measure chloride ion concentration with ion chromatograph (elutriant is KOH, and post is AS-20 for the ICS-2000 that Dionex company manufactures, conductivity detector), calculate chlorine amount.
Iodine amount is measured according to following method.Being heated in chloroazotic acid by Copper Foil makes its acidifying dissolve, and carries out constant volume after cooling, by ICP-AES(Seiko Precision KK manufacture SPS3000) measure I:178nm(Ar cleaning) intensity, calculate iodine amount.
In addition, the result measured electrolytic copper foil of the present invention by catharometry: electrolytic copper foil of the present invention has such composition characteristics, that is, the major impurity amount of the total of each composition of carbon, oxygen, sulphur, nitrogen is at below 0.01 quality %.Present stage, in the electrolytic copper foil of the anode collector for lithium-ion secondary cell, which type of effect these major impurity amounts have still uncertain.But major impurity composition mentioned here is easily at the element of grain boundary segregation, and if major impurity amount is below 0.01 quality %, then the toughness of electrolytic copper foil strengthens, and elongation and tensile strength show good balance.
And then the present inventor has carried out the mensuration of copper purity to electrolytic copper foil of the present invention with glow discharge mass spectroscopy.Its result, the copper purity obtained with glow discharge mass spectroscopy is the highly purified value of more than 99.99 quality %.Really, if consider the iodine amount and chlorine amount that measure with above-mentioned chemical analysis, with the major impurity amount of the total of each composition of the carbon measured by catharometry, oxygen, sulphur, nitrogen, then with the copper purity obtained with this glow discharge mass spectroscopy, the value of mutually coincideing can not be formed, but the error that analytical procedure can be thised is presumably because different and produce.
Secondly, the physical features that electrolytic copper foil of the present invention has is set forth.And, when this physical features is described, assume that the sheet metal thickness of electrolytic copper foil is that the situation of 18 μm ± 1.8 μm is described.
The surfaceness in the precipitation face of electrolytic copper foil of the present invention is described.Known, the value of the Rzjis of the surfaceness in the precipitation face of electrolytic copper foil of the present invention, the scope of 0.70 μm ~ 2.0 μm, is slim precipitation face.Herein, if the value of Rzjis is more than 2.0 μm, then when manufacturing lithium ion secondary battery cathode, immobilized negative active core-shell material becomes difficulty equably.In addition, if repeat discharge and recharge, then in the protuberance of current collector surface, lithium is easily grown to the crystalline tendency grow of branches and tendrils, thus not preferred.On the other hand, when the value of Rzjis is less than 0.7 μm, then condition of surface is too level and smooth, when the anode collector of serving as lithium-ion secondary cell is to use, and the adhesivity step-down between negative active core-shell material and anode collector, thus not preferred.And then in order to make the stability of characteristics as lithium-ion secondary cell, the difference of the Rzjis value on preferred electrolytic copper foil two sides is within 0.6 μm.And, Rzjis(mentioned here 10 mean roughness) be based on JISB0601, and by the value that probe-type roughness tester (radius-of-curvature of tips of probes 0.2 μm) measures.
The physical features that electrolytic copper foil of the present invention measures under normal conditions is set forth.Normality elongation (the E of electrolytic copper foil of the present invention
0) value preferably 2.0% ~ 9.0% scope.When normality elongation is more than 2.0%, be applicable to the anode collector of lithium-ion secondary cell.On the other hand, when normality elongation is less than 9.0%, in the anode collector of lithium-ion secondary cell time, with the resistance to deformation of dilation during discharge and recharge in suitable scope.And in this application, the mensuration of this elongation and the mensuration of tensile strength described later carry out tension test by the electrolytic copper foil sample wide to 10mm and the value measured.
And then, the normality tensile strength (F of electrolytic copper foil of the present invention
0) value show as at 48kgf/mm
2~ 72kgf/mm
2scope.As normality tensile strength (F
0) value be 48kgf/mm
2time above, in the anode collector of lithium-ion secondary cell time, the resistance to deformation corresponding with dilation during discharge and recharge have and become good tendency.On the other hand, as normality tensile strength (F
0) value be 72kgf/mm
2time following, it is stably in the scope of above-mentioned suitable normality elongation.
Below, the physical features measured after carrying out certain heat treated electrolytic copper foil of the present invention is set forth (has the situation referred to as " after heat " below.）。Said heat treated refers to the heat treated implemented the electrolytic copper foil of normality in atmospheric environment 180 DEG C × 60 minutes herein.
Elongation (E after the heat of electrolytic copper foil of the present invention
a) value 4% ~ 10% scope.The circuit formed with Copper Foil in the manufacturing processed of printed wiring board and the anode collector manufactured with Copper Foil in the manufacturing processed of the negative pole of lithium-ion secondary cell, be exposed in various high-temperature load environment.Therefore, after the heat of this electrolytic copper foil, physical properties becomes the very important key element of left and right product quality.If elongation (E after heat
a) value be more than 4%, be then the suitable elongation in the anode collector purposes of lithium-ion secondary cell.On the other hand, when elongation after heat is less than 10%, time in for the anode collector of lithium-ion secondary cell, with the resistance to deformation of dilation during discharge and recharge in suitable scope.
And then, the hot back draft intensity (F of electrolytic copper foil of the present invention after the heat treated of 180 DEG C × 60 minutes
a) value show as at 38kgf/mm
2~ 72kgf/mm
2scope.As hot back draft intensity (F
a) value be 38kgf/mm
2time above, be difficult to the impact of the hot resume be subject to processing in process, and in the anode collector of lithium-ion secondary cell time, the resistance to deformation corresponding with dilation during discharge and recharge also have and become good tendency.On the other hand, if hot back draft intensity (F
a) value be 72kgf/mm
2below, then the scope of above-mentioned suitable normality elongation is easily maintained, therefore preferably.
In addition, in electrolytic copper foil of the present invention, as physical features, above-mentioned normality tensile strength (F
0) value and the heat treated of above-mentioned 180 DEG C × 60 minutes after hot back draft intensity (F
a) value preferably meet with the relation of following formula 2.
[formula 2]
[normality tensile strength (F
0)]-[hot back draft intensity (F
a)]≤10kgf/mm
2
The implication of this formula 2 is, " normality tensile strength (F
0) " and " hot back draft intensity (F
a) " difference little, be also difficult to soften even if be subject to certain heating.In the manufacture course of processing of the negative pole of lithium-ion secondary cell, Copper Foil is subject to the impact of various hot resume.Its result, if this Copper Foil softens, then as lithium-ion secondary cell negative pole intensity required by bending property, in anode collector time all deviations of the resistance to deformation corresponding with dilation during discharge and recharge will become large, the quality stability as lithium-ion secondary cell cannot be guaranteed, therefore not preferred.Thus, require that there is the anti-softening ability corresponding with the heating of such degree.
And then the physical features of electrolytic copper foil of the present invention preferably shows high bending property, after the heat namely after the heat treated of 180 DEG C × 60 minutes in resist bending test, to fracture number of bends is more than 3000 times.If the number of bends after heat in resist bending test is more than 3000 times, then in the anode collector of lithium-ion secondary cell time, the resistance to deformation corresponding with dilation during discharge and recharge be tremendous raising, makes the prolongation of product life become possibility.Resist bending test after said heat herein, even if when the electrolytic copper foil of printed wiring board-use, is also the important characteristic be required.And, about this number of bends, although do not record out higher limit clearly, be rule of thumb about 6500 times.And, after said heat, resist bending test is herein, based on JISC5016 measuring method, to test a machine (bending radius: 1mm with the flexural buckling that TESTER Industry Co., Ltd manufactures, rate of bending: 100cpm, stroke: 20mm), to the electrolytic copper foil of the short strip shape of wide 10mm × long 10cm, after the heat treated of 180 DEG C × 60 minutes, measure its test of number of bends to fracture.
The form of surface treatment copper foil of the present invention: surface treatment copper foil of the present invention, is characterized in that, implements various surface treatment to the surface of the above-mentioned electrolytic copper foil containing iodine.This surface treatment refers to the one or more kinds of process in above-mentioned electrolytic copper foil surface enforcement roughened, antirust treatment, silane coupling agent process.This surface treatment is, considers the requirement characteristic of different purposes, to pay for the purpose of bond strength, chemical proofing, thermotolerance etc., to the process that electrolytic copper foil surface is implemented.In addition, about silane coupling agent process, if for electrolytic copper foil in the anode collector of lithium-ion secondary cell time, then the preferred two sides at electrolytic copper foil is implemented, if for electrolytic copper foil in printed wiring board time, then a preferred face at electrolytic copper foil is implemented.
The manufacture form of electrolytic copper foil of the present invention: the manufacture method of electrolytic copper foil of the present invention is the manufacture method of the above-mentioned electrolytic copper foil containing iodine, it is characterized in that, the composition of sulfuric acid based copper electrolyte used herein.And the copper concentration herein in said sulfuric acid based copper electrolyte adopts the scope of 50g/L ~ 120g/L, preferably adopts the scope of 50g/L ~ 80g/L further.In addition, free sulphuric acid concentration is considered, with the scope of 60g/L ~ 250g/L for benchmark, preferably to consider with the scope of 80g/L ~ 150g/L for benchmark further.
Iodine concentration in this sulfuric acid based copper electrolyte is preferably in the scope of 1.5mg/L ~ 15.0mg/L.The preferred scope at 2.5mg/L ~ 7.0mg/L further.When the iodine concentration in sulfuric acid based copper electrolyte is less than 1.5mg/L, the iodine number entered in the electrolytic copper foil of being separated out by electrolysis is not enough, thus the electrolytic copper foil obtained cannot obtain the physical property such as surfaceness, elongation, tensile strength of above-mentioned optimum range, As time goes on various physical properties also has and changes the tendency of aggravation, therefore not preferred.On the other hand, if this iodine concentration is more than 15.0mg/L, then the iodine amount in electrolytic copper foil increases, and foregoing problems will occur.In addition, by making this iodine concentration at below 7.0mg/L, thus the smoothness in electrolytic copper foil precipitation face and good physical strength can be taken into account.In the interpolation of iodine at this moment, preferably use the iodide such as NaI, KI.
In addition, the concentration of preferred below the 1.0mg/L of cl concn of the copper electrolyte of the present invention's use.If this cl concn is more than 1.0mg/L, then the electrolytic copper foil obtained is easily brittle, therefore not preferred.And then, in order to stablize the scope of the cl concn that electrolytic copper foil of the present invention contains further, preferably in the scope of 0.4mg/L ~ 0.8mg/L.By adopting the cl concn of this scope, thus balance is well containing above-mentioned each composition, and separates out face slimming, makes the stable of the electrolytic copper foil of high strength create possibility.When carrying out the adjustment of the cl concn in this sulfuric acid based copper electrolyte, preferably adjust with hydrochloric acid or cupric chloride (II).This is because they can not bring detrimentally affect to the solution proterties of sulfuric acid based copper electrolyte.
And then, in the manufacture method of electrolytic copper foil of the present invention, be preferably 40 DEG C ~ 60 DEG C, current density 50A/dm in the temperature of copper electrolyte
2~ 85A/dm
2scope under carry out electrolysis.When solution temperature is less than 40 DEG C, lack electric stability of solution, the deviation of the physical strengths such as the tensile strength of the electrolytic copper foil obtained and elongation has the tendency that change is large.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 not enough, thus makes process management become numerous and diverse, therefore not preferred.
In addition, if said electrolysis herein time current density less than 50A/dm
2, then cannot obtain the production efficiency required by industrialness, production efficiency reduces, thus not preferred.On the other hand, if electrolysis time current density more than 85A/dm
2, then easily there is deviation in the physical property aspect such as surfaceness, tensile strength that face separated out by the electrolytic copper foil manufactured, thus not preferred.
The lithium ion secondary battery cathode obtained with surface treatment copper foil of the present invention: the lithium ion secondary battery cathode obtained with surface treatment copper foil of the present invention, is characterized in that, have employed above-mentioned surface treatment copper foil as anode collector.Usually, the negative pole of lithium-ion secondary cell is, carries out the immobilized of negative active core-shell material on the surface of the surface treatment copper foil as anode collector, thus obtains the negative pole of the anode collector state with negative active core-shell material.In this manufacturing process, by the surface treatment copper foil using electrolytic copper foil of the present invention, thus the running contact bending property under the good heat-resistant property of softening, bending resistance characteristic and immobilized actually " running contact (negative pole) with negative active core-shell material " state of negative active core-shell material can be improved simultaneously.
Other Application Areass of electrolytic copper foil of the present invention: electrolytic copper foil of the present invention and surface treatment copper foil also can be diverted to printed wiring board manufacture copper clad laminate (has the situation referred to as " copper clad laminate " in context.) manufacture in.Such as, above-mentioned surface-treated electro-deposited copper foil and insulation layer constituent material are carried out stacked, thus also can obtain printed wiring board manufacture copper clad laminate.And spy herein means bright for the purpose of prudent, in the concept of said copper clad laminate herein, comprise both rigidity copper clad laminate and flexible copper clad laminate.Electrolytic copper foil of the present invention owing to being slim, thus is applicable to the formation of the fine-line of level required by the flexible printed circuit board containing TAB, COF etc.
Below, in order to easy understand electrolytic copper foil of the present invention etc., thus show embodiment.
Embodiment
In this embodiment, have employed the basic solution of the copper concentration 80g/L in copper-bath, free sulphuric acid concentration 140g/L as sulfuric acid based copper electrolyte, and be adjusted to each additive concentration shown in table 1.Iodine now adds use potassiumiodide (KI) and carries out, and employs hydrochloric acid in the adjustment of cl concn.And then, with the sulfuric acid based copper electrolyte of the different additive mixing ratio composition of having shown in table 1, produce eight kinds of sample 1 ~ sample 8 electrolytic copper foil containing iodine.And, this embodiment be for, by carrying out contrasting with comparative example thus making as the clear embodiment of the difference of the general physical properties of Copper Foil.
In the manufacture of electrolytic copper foil, adopt the titanium plate electrode ground by the sand paper effects on surface of 2000# as negative electrode, and anode adopts DSA, and at solution temperature 50 DEG C, current density 75A/dm
2condition under carry out electrolysis, thus produce thickness 18 μm, electrolytic copper foil containing iodine.The surfaceness (Rzjis) of the glossy surface (separating out the face of the opposition side in face) of these electrolytic copper foils is 1.4 μm.The assessment result of each characteristic of the electrolytic copper foil herein obtained is summarized in table 2, thus can contrasts with following comparative example.
Here various condition determinations etc. are described.Tensile strength after the normality of embodiment sample and heat, the mensuration of elongation are carried out based on IPC-TM-650.In addition, the mensuration of surfaceness is carried out based on JISB0601-2001.Following comparative example is also identical.
Comparative example
The duplicate 1 of this comparative example and duplicate 2 have employed the copper electrolyte of below iodine concentration 0.5mg/L, and this comparative example is for carrying out with above-described embodiment the comparative example that contrasts.And then duplicate 3 and duplicate 4 have employed the copper electrolyte (copper electrolyte not containing iodine) of iodine concentration 0.0mg/L.Other has obtained duplicate 1 ~ duplicate 4 with the manufacturing condition identical with embodiment.Above-mentioned electrolytic solution composition is formed with the electrolytic solution of embodiment and is shown in the lump in table 1 below.
By the result that the contrast of embodiment and comparative example can be clear and definite
Contrast as the basic physical properties of Copper Foil: with reference to table 1, table 2 and accompanying drawing, carry out the contrast of embodiment and comparative example.
[table 1]
According to this table 1, the sample 1 ~ sample 8 of embodiment, have employed sulfuric acid copper sulfate electrolyte in the proper range being included in " below cl concn 1.0mg/L, iodine concentration 1.5mg/L ~ 15.0mg/L " as copper electrolyte of the present invention.On the other hand, known, duplicate 1 ~ duplicate 4 does not all adopt the sulfuric acid copper sulfate electrolyte in the scope being included in " iodine concentration 1.5mg/L ~ 15.0mg/L ", does not use the copper electrolyte containing this suitable chlorine and iodine.
[table 2]
Note) after heat: the situation after the heat treated of 180 ° of C × 60 minute.
The surfaceness in precipitation face: mark with Rzjis
From this table 2, in the manufacture method of the electrolytic copper foil containing iodine of the application, by the sulfuric acid copper sulfate electrolyte using copper electrolyte to meet the condition of " below cl concn 1.0mg/L, iodine concentration 1.5mg/L ~ 15.0mg/L ", thus the electrolytic copper foil of iodine amount 0.005 quality % ~ 0.063 quality % can be obtained.Known, the precipitation face of this electrolytic copper foil is level and smooth, and the difference of tensile strength after normality and heat meets ［ normality tensile strength (F
0)-［ hot back draft intensity (F
a) value be 10kgf/mm
2following condition.
Investigation 1 to the characteristic of the anode collector as lithium-ion secondary cell: in this investigation 1, by the data of aforementioned table 2 in X-Y coordinate plane, represent " the iodine amount in paper tinsel " by the Y-direction of the longitudinal axis, the X-direction of transverse axis represents " cl concn in paper tinsel ", and that draw is exactly Fig. 1.And then, at this Fig. 1
shown in iodine amount 0.003 quality % straight line more than region in, contain the data of all embodiments.On the other hand, known, the iodine amount of the duplicate of comparative example is less than 0.003 quality %.
Herein, if look back the contents of table 2, in an embodiment known, only have the iodine amount of the electrolytic copper foil of sample 7 to exceed 0.03 quality %.As this result, the number of bends that after finding the heat of sample 7, resist bending is tested is 1105 times, is the value lower than the number of bends of other samples.This also demonstrates effectively, if the iodine amount in electrolytic copper foil is more than 0.03 quality %, then the tissue of electrolytic copper foil has brittle tendency.
And then, there is the situation of iodine amount in the region (region represented by above-mentioned formula 1) on the upside of the straight line of Fig. 1 and chlorine amount, due to as the characteristic required by the electrolytic copper foil in the anode collector purposes of lithium-ion secondary cell, namely the heat-resistant property of softening of heating is strengthened especially, and the heat-resistant property of softening is stablized, and therefore has preference.Namely can think, for in the electrolytic copper foil in the anode collector purposes of lithium-ion secondary cell, not only consider the iodine amount in electrolytic copper foil, and consider the chlorine amount in electrolytic copper foil, thus meet the relation shown in formula 1, be especially preferred.
Consider foregoing can judge, the application containing iodine electrolytic copper foil in, iodine amount is 0.003 quality % ~ 0.03 quality %, chlorine amount is 0.0006 quality % ~ 0.0018 quality %, and be in the scope meeting condition shown in formula 1, be just provided with the most preferred characteristic of the anode collector as lithium-ion secondary cell.
Investigation 2 to the characteristic of the anode collector as lithium-ion secondary cell: this investigation 2 for illustration of the distinctive heat-resisting property of softening in the electrolytic copper foil containing iodine of the present invention, and is set forth " relation of normality tensile strength and the heating back draft intensity after carrying out at 350 DEG C heating ".That is, it considers the hot environment be applied in the manufacturing processed of the negative pole of lithium-ion secondary cell, and be used for the change of the physical property after having carried out the heating at 350 DEG C, carry out with comparative example the investigation that contrasts.In this investigation 2, for convenience of explanation, be described with the sample extracted out from the sample 1 ~ sample 8 of the above embodiments and comparative example duplicate 1 ~ duplicate 4 used.
Table 3 represents " normality tensile strength (F
0) " and " carried out the heating back draft intensity (F after the heating at 350 DEG C
b) " relation.This be with heating Copper Foil having been carried out to 350 DEG C × 60 minutes after, the short strip shape sample of long 10cm × wide 10mm carries out tension test and the result obtained.
[table 3]
Note) after heat (Fb): the situation after the heat treated of 350 ° of C × 60 minute.
Also known according to table 3, even if the electrolytic copper foil containing iodine, the sample 3 not containing chlorine is after the heat treated of 350 DEG C × 60 minutes, and tensile strength also can sharply decline.In addition, duplicate 1, duplicate 2 and duplicate 4, although the tensile strength after heat shows as less than 30kgf/mm
2value, but sample 1 ~ sample 3 maintains 30kgf/mm
2above value.On the other hand, sample 2 is arranged in the region meeting the relation shown in previously described formula 1, and is arranged in the shadow region of Fig. 1, even if after receiving the heat treated of 350 DEG C × 60 minutes, still possess 40kgf/mm
2above high tensile strength, and the number of bends of the resist bending test shown in table 2 also shows as outstanding value.
On the other hand, according to the scope (formula shown in above-mentioned formula 1) that the straight line A in Fig. 1 divides, the physical properties of the electrolytic copper foil of the application after known 350 DEG C × 60 minutes heat treated obtains differentiation, and described Fig. 1 is the figure illustrating " the iodine amount in the electrolytic copper foil physical properties after heat treated and the relation of chlorine amount " shown in investigation 1.
Namely, there is the situation of iodine amount in the region (meeting the region of condition shown in formula 1) on the upside of the straight line of this Fig. 1 and chlorine amount, due to as the characteristic required by the electrolytic copper foil in the anode collector purposes of lithium-ion secondary cell, namely the heat-resistant property of softening for heating strengthens especially, and the heat-resistant property of softening is stablized, therefore preferably.Thus it is clearly known, for in the electrolytic copper foil in the anode collector purposes of lithium-ion secondary cell, not only consider the iodine amount in electrolytic copper foil, and consider the chlorine amount in electrolytic copper foil, thus meet the relation shown in formula 1, be especially preferred.
As from the foregoing, must balance in electrolytic copper foil well containing iodine and chlorine.Be classified as the sample 1 of such electrolytic copper foil and the electrolytic copper foil of sample 2, the anti-softening ability for heating is strong, is namely used in the negative pole manufacture of lithium-ion secondary cell, also can shows sufficient non-deformability to dilation phenomenon during discharge and recharge.
Investigation 3 to the characteristic of the anode collector as lithium-ion secondary cell: this investigation 3 also contains the distinctive heat-resisting property of softening in the electrolytic copper foil of iodine for illustration of of the present invention, and sets forth " heat-resisting bending tensile test result ".This heat-resisting bending tensile test (jus singular) obtains the result of tension test after Copper Foil being implemented to the heat treated of 350 DEG C × 60 minutes.Table 4 has carried out record to this result.The test method of said heat-resisting bending tensile test (jus singular) is as follows herein.
Heat-resisting bending tensile test step
1., in atmospheric environment, by the certain Heating temperature Heating temperature 350 DEG C of the jus singular (, other 180 DEG C), the Copper Foil sample of the short strip shape of the 1cm × 10cm of tension test is carried out to the heat treated of 60 minutes, and carry out placement cooling.
2. after, this sample bending, under the state applying 15kg load, load 180 ° of stress in bendinges of 1 minute and form bend, and then return 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 (eliminating the resistance to hot tensile strength of heat-resisting bending tensile test step (2))
Heat-resisting bend tension intensity
Here to adopting the reason of above-mentioned heat-resisting bending tensile test (jus singular) to be described.When lithium-ion secondary cell forms active material layer in the negative pole running contact employing Copper Foil, load high temperature.And then, in square lithium-ion secondary cell, have this negative pole of making to be subject to high-temperature load and defining active material layer with positive pole or the stacked state of pad under bending and slimming becomes square operation.Therefore, heat-resisting bending tensile test (jus singular) is, imports relative to the patience of the Copper Foil of load when having been executed such bending machining to assess.
[table 4]
From this table 4, embodiment (sample 1, sample 2, sample 5, sample 6), compared with duplicate 1, the bend tension intensity after heating in 180 DEG C × 60 minutes is also relatively high.It can thus be appreciated that, even if the electrolytic copper foil containing iodine of the present invention has the characteristic being subject to heat and being also difficult to soften, even and if bending, its tensile strength also reduces few, is difficult to rupture.
Herein, if by the sample 5 of table 4, sample 6, and duplicate 1 contrasts, and perhaps can feel can not see that large difference exists in the tensile strength after the heating of 350 DEG C × 60 minutes.Moreover if observe the bend tension intensity after the heating of their 180 DEG C × 60 minutes, then, compared with duplicate 1, the value of the bend tension intensity of sample 5 and sample 6 obviously uprises.Therefore known, sample 5 and sample 6, compared to duplicate 1, even if the heating being subject to large temperature range also can show good tensile strength, even if bending, the reduction of its tensile strength is also few, is difficult to fracture.
In addition, if observe the change of the sample 1 suitable with embodiment, sample 2, sample 5, the bend tension intensity of sample 6 after the heating of 180 DEG C × 60 minutes and after the heating of 350 DEG C × 60 minutes, just known to draw a conclusion.In sample 1 and sample 2, compared with the bend tension intensity after the heating of 180 DEG C × 60 minutes, the bend tension intensity after the heating of 350 DEG C × 60 minutes uprises.Their iodine amount is respectively 0.018 quality %, 0.019 quality %, by the iodine containing such degree, thus significantly improves the heat-resistant property of softening of material for heating.On the other hand, in sample 5 and sample 6, compared with the bend tension intensity after the heating of 180 DEG C × 60 minutes, the bend tension intensity after the heating of 350 DEG C × 60 minutes becomes especially low.Their iodine amount is 0.005 quality %, when the iodine amount of this degree, cannot realize significantly improving of the heat-resistant property of softening.But can say, even if sample 5 and sample 6 are compared to comparative example, really also can improve the heat-resistant property of softening of material.
Investigation 4 to the characteristic of the anode collector as lithium-ion secondary cell: in this investigation 4, the electrolytic copper foil that the electrolytic solution comprised beyond with the composition of table 1 record forms and obtains, and do more detailed research with the paper tinsel physical properties after 350 DEG C of heat tests.Describe in this table 5 composition of electrolytic solution, often kind of copper electrolyte composition correspondence the heat test of 350 DEG C × 60 minutes after paper tinsel physical properties.And the manufacturing condition beyond electrolytic solution composition is identical with embodiment.Herein, according to the result of table 1 and table 2, the S series (general name of " sample S-1 ~ sample S-8 " of table 5.) be the Copper Foil suitable with electrolytic copper foil of the present invention.Known on the other hand, the C series (general name of " sample C-1 ~ sample C-4 " of table 5.) not the Copper Foil suitable with electrolytic copper foil of the present invention.And hereby indicate as a reference, sample S-2 is the sample 1 described in embodiment, sample S-5 is the sample 2 described in embodiment, sample C-1 is the duplicate 1 described in comparative example, and sample C-2 is the duplicate 2 described in comparative example, and sample C-4 is the duplicate 4 described in comparative example.
[table 5]
Note) 1. hot back draft intensity: Fb (kgf/mm
2)
2. heat-resisting bend tension intensity (kgf/mm
2)
3. poor tensile strength: 1.-2. (kgf/mm
2)
From this table 5, " S series ", compared with " C series ", the tensile strength of carrying out after the heat treated of 350 DEG C × 60 minutes uprises.That is, the tendency of observing this tensile strength is known, and " the S series " that manufactures with the sulfuric acid copper sulfate electrolyte containing a certain amount of iodine, showing tensile strength to the harsh heating of 350 DEG C × 60 minutes is 27kgf/mm
2above sufficient anti-softening ability.And " S series " has also shown 28kgf/mm even if carry out bending
2above high tensile strength.In addition, observe preferred form in " S series ", the while of showing resistance to hot tensile strength and heat-resisting bend tension intensity, also show 30kgf/mm
2above high tensile strength be sample S-1 ~ sample S-6.And be sample S-1 ~ sample S-3 as further preferred form, they, while showing resistance to hot tensile strength and heat-resisting bend tension intensity, also show 40kgf/mm
2above high tensile strength.
Investigation 5 to the characteristic of the anode collector as lithium-ion secondary cell: in this investigation 5, with reference to table 6, is described the advantage when electrolytic copper foil containing iodine of the present invention being served as the anode collector of lithium-ion secondary cell.In this explanation, adopt the duplicate 1 of the sample 1 ~ sample 3 of embodiment, comparative example, duplicate 2 and duplicate 4, section's Ademilson Alloy Foil, calendering copper alloy foil, and they are contrasted.And, in this investigation 5, consider electric conductivity, and in the mensuration of electric conductivity, utilize the B1500A semiconducter device analyser of Agilent Technologies and the four-point probe method that have employed based on JISK7194.
[table 6]
* after heat: the situation after the heat treated of 350 ° of C × 60 minute.
* section Ademilson Alloy Foil: the C7025 that Nippon Mining and Metals Co., Ltd manufactures
* * rolls copper alloy foil: the HCL02Z that Hitachi Cable Ltd. manufactures
In order to extend the cycle life of lithium-ion secondary cell, the voltage loss that the resistance that must reduce anode collector as far as possible brings, supplies equably the negative active core-shell material in battery or collects electronics, and making it react.Physical properties after the heat treated of 350 DEG C × 60 minutes of the electrolytic copper foil used as anode collector, is considered to require that characteristic produces large impact to this.
That is, as shown in Table 6, the electrolytic copper foil containing iodine of the application, the tensile strength shown after the heat treated of 350 DEG C × 60 minutes is 30kgf/mm
2above high value, simultaneously no matter under normality or all stably show high electric conductivity after heating.On the other hand, the electrolytic copper foil not containing iodine, although electric conductivity is high, heating result in tensile strength and significantly reduces.Therefore can judge, the electrolytic copper foil not containing iodine cannot tolerate the dilation phenomenon that lithium-ion secondary cell anode collector when discharge and recharge is subject to.
In addition, in table 6, as comparing use, show section's Ademilson Alloy Foil and calendering copper alloy foil.Although the tensile strength after section's Ademilson Alloy Foil heating is very good, alloy composition makes electric conductivity low.Therefore, when using as anode collector, being difficult to that anticathode entirety occurs and supplying electronics equably and in negative active core-shell material, collect the reaction of lithium equably, thus not preferred.
And, in calendering copper alloy, at first sight, can think that it achieves the balance between tensile strength and electric conductivity.But known, the electric conductivity of normality than as the sample of the embodiment of electrolytic copper foil or the sample of comparative example low.When using the tinsel with such physical properties as anode collector to use time, the heating carrying out generation during discharge and recharge can cause anode collector local for superheat state, the state of forming section annealing, only the tensile strength at this position and resistance reduce, distortion as anode collector aggravates, and be difficult to that anticathode entirety occurs and supply electronics equably, collect the reaction of lithium at negative active core-shell material equably, therefore not preferred.
Known as mentioned above, the electrolytic copper foil containing iodine of the present invention, even if with duplicate, section's Ademilson Alloy Foil of comparative example, roll compared with copper alloy foil, is also more suitable in the purposes as the anode collector of lithium-ion secondary cell.
Comprehensive descision: can say, suitable with above-described embodiment, containing iodine electrolytic copper foil, even if having the character bending and be also difficult to rupture.Therefore, if such electrolytic copper foil to be served as the collector materials of the coiled battery adopted in lithium-ion secondary cell, it is softening that the hot resume being then difficult to occur this battery institute's load in the fabrication process cause, and be difficult to the impact that heating when being subject to discharge and recharge brings, and then, also strong to the non-deformability of expansion/contraction phenomenon during discharge and recharge.Therefore can say, the electrolytic copper foil containing iodine of the present invention is the suitable Copper Foil as the collector materials adopted in lithium-ion secondary cell.
Industrial applicibility
Electrolytic copper foil of the present invention is the electrolytic copper foil come by the iodine do not contained in existing electrolytic copper foil containing more than 0.003 quality %.Even if the electrolytic copper foil chlorine amount change that should contain iodine also can demonstrate the electrolytic copper foil of various stable characteristic.
And the physical properties of this electrolytic copper foil, even if having the characteristic heating and be also difficult to soften, and has the good heat-resistant property of softening required by running contact and the bending resistance characteristic of lithium-ion secondary cell concurrently.Thus, if adopt this electrolytic copper foil as running contact, then can realize high-quality and the market supply of long-life lithium-ion secondary cell.
Claims (13)
1. electrolytic copper foil, it is the electrolytic copper foil obtained by electrolytic copper electrolytic solution, it is characterized in that,
Iodine amount in electrolytic copper foil is more than 0.003 quality % and below 0.03 quality %.
2. electrolytic copper foil as claimed in claim 1, it is characterized in that, chlorine amount is in the scope of below 0.0018 quality %.
3. electrolytic copper foil as claimed in claim 1, it is characterized in that, chlorine amount and iodine amount meet with the relation of following formula 1,
[formula 1]
[iodine amount (quality %)] >=-30 × [chlorine amount (quality %)]+0.03.
4. electrolytic copper foil as claimed in claim 1, is characterized in that having the value of Rzjis in the precipitation face of 0.70 μm ~ 2.0 μm of scopes.
5. electrolytic copper foil as claimed in claim 1, is characterized in that, normality tensile strength (F
0) value at 48kgf/mm
2~ 72kgf/mm
2scope.
6. electrolytic copper foil as claimed in claim 1, is characterized in that, the hot back draft intensity (F after the heat treated of 180 DEG C × 60 minutes
a) value be 38kgf/mm
2~ 72kgf/mm
2.
7. electrolytic copper foil as claimed in claim 1, is characterized in that, normality tensile strength (F
0) value, with the heat treated of 180 DEG C × 60 minutes after hot back draft intensity (F
a) value meet the relation of following formula 2,
[formula 2]
[normality tensile strength (F
0)]-[hot back draft intensity (F
a)]≤10kgf/mm
2.
8. electrolytic copper foil as claimed in claim 1, is characterized in that,
Normality tensile strength (F
0) value at 48kgf/mm
2~ 72kgf/mm
2scope, and, the hot back draft intensity (F after the heat treated of 350 DEG C × 60 minutes
b) value be 30kgf/mm
2above.
9. the electrolytic copper foil as described in claim 1 or 8, is characterized in that, when sheet metal thickness is 18 μm ± 1.8 μm, the number of bends in the test of after the heat treated of 180 DEG C × 60 minutes, resist bending is more than 3000 times.
10. surface treatment copper foil, is characterized in that, implements surface treatment to the surface of the electrolytic copper foil containing iodine described in claim 1 or 8.
The manufacture method of 11. electrolytic copper foils, it is the manufacture method of the electrolytic copper foil containing iodine according to claim 1, it is characterized in that,
Adopt iodine concentration at the sulfuric acid copper sulfate electrolyte of 1.5mg/L ~ 15.0mg/L scope as copper electrolyte.
The manufacture method of 12. electrolytic copper foils as claimed in claim 11, is characterized in that, employing cl concn is the sulfuric acid copper sulfate electrolyte of below 1.0mg/L.
13. lithium ion secondary battery cathodes, is characterized in that, immobilized in surface treatment copper foil according to claim 10 have negative active core-shell material.
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| 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 |
| KR101632852B1 (en) * | 2012-06-27 | 2016-06-22 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper foil for lithium ion secondary battery, negative electrode for 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 |
| KR101449342B1 (en) * | 2013-11-08 | 2014-10-13 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil |
| KR102272762B1 (en) * | 2013-11-27 | 2021-07-05 | 미쓰이금속광업주식회사 | Copper foil with carrier foil, copper clad laminate and printed wiring board |
| KR101737028B1 (en) * | 2014-07-10 | 2017-05-17 | 엘에스엠트론 주식회사 | Method for producing electrolytic copper foil |
| KR102122425B1 (en) | 2015-06-18 | 2020-06-12 | 케이씨에프테크놀로지스 주식회사 | Electrolytic copper foil for lithium secondary battery and Lithium secondary battery comprising the same |
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| WO2016208869A1 (en) * | 2015-06-23 | 2016-12-29 | 엘에스엠트론 주식회사 | Electrolytic copper foil for lithium secondary battery and lithium secondary battery including same |
| KR102130011B1 (en) | 2015-06-23 | 2020-07-03 | 케이씨에프테크놀로지스 주식회사 | Electrolytic copper foil for lithium secondary battery and Lithium secondary battery comprising the same |
| KR102473557B1 (en) * | 2015-09-24 | 2022-12-01 | 에스케이넥실리스 주식회사 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| KR102413674B1 (en) * | 2015-09-25 | 2022-06-27 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper foil and various products using 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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