CN102959135A - Electrodeposited copper foil and process for production thereof - Google Patents

Electrodeposited copper foil and process for production thereof Download PDF

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Publication number
CN102959135A
CN102959135A CN2011800323835A CN201180032383A CN102959135A CN 102959135 A CN102959135 A CN 102959135A CN 2011800323835 A CN2011800323835 A CN 2011800323835A CN 201180032383 A CN201180032383 A CN 201180032383A CN 102959135 A CN102959135 A CN 102959135A
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copper foil
electrolytic copper
iodine
quality
lithium
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CN102959135B (en
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朝长咲子
稻场慎太郎
吉冈淳志
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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

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  • 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

Disclosed is an electrodeposited copper foil which can exhibit various properties stably even when the chlorine content therein is varied. Specifically disclosed is an electrodeposited copper foil produced by electrolyzing a copper electrolytic solution, which is characterized in that the iodine content in the electrodeposited copper foil is 0.003 mass% or more, more preferably 0.003 mass% to 0.03 mass%. Preferably, the chlorine content in the electrodeposited copper foil is 0.0018 mass% or less.

Description

Electrolytic copper foil with and manufacture method
Technical field
The present invention relates to the manufacture method of electrolytic copper foil and this electrolytic copper foil.Relate in particular to have and be applicable to lithium-ion secondary cell with the physical property of the tensile strength of running contact, elongation etc., and the electrolytic copper foil of the copper clad laminate that also can be used in printed wiring board manufacturing usefulness in making.
Background technology
In recent years; because the raising that the raising of environmental protection consciousness and resource recycling require; lithium-ion secondary cell is popularized as reusable useful power supply, and for example it is used in and is carried in outdoor notebook computer, mobile phone, TV, the video camera products.Along with the miniaturization of these electric equipment products and electronics, the lithium-ion secondary cell as the power supply supply source has also been proposed small-sized, high life, light weight, and the requirement of performance high-energy-density.
Look back the developing history of lithium-ion secondary cell, in the anode collector of the negative pole that consists of lithium-ion secondary cell, attempt having used the rolled copper foil of surface smoothness excellence.In the anode collector of the negative pole of present formation lithium-ion secondary cell, use be any one in rolled copper foil or the electrolytic copper foil.
In the manufacturing processed of the negative pole of this lithium-ion secondary cell, as patent documentation 1 or patent documentation 2 are disclosed, there is the operation of load high temperature.In this operation, as in the Copper Foil of the anode collector that consists of negative pole also by load high temperature.Its result, softening if this Copper Foil occurs, then have the problem of the impact of the deformation stress that dilation when easily being subject to lithium-ion secondary cell and repeating to discharge and recharge, negative active core-shell material brings.
For this problem, when adopting the rolled copper foil that is obtained by cheap tough pitch copper, soften owing to easily occuring to heat the recrystallization that causes, thus the impact of the dilation stress when easily being subject to repeating above-mentioned discharging and recharging, and the life-time dilatation of lithium-ion secondary cell is comparatively difficult.In addition, rolled copper foil derives from its manufacture method, and is therefore expensive, thereby is difficult to use the price cheaper than electrolytic copper foil to provide.This point becomes in order to win the obstacle of worldwide price competition for the manager.In addition, because rolled copper foil is difficult to broadening as Copper Foil, therefore be difficult to improve the production efficiency in the battery manufacture, thereby the reduction of product cost is limited, becomes unavoidable shortcoming.
To this, to think all the time, electrolytic copper foil is owing to being difficult to heat the recrystallization that causes and being difficult to soften, thus the resistibility of the dilation stress when repeating above-mentioned discharging and recharging is strong.In addition, because electrolytic copper foil is more cheap than the calendering Copper Foil, can improve lithium-ion secondary cell in the market in the rentability of price aspect, thereby as the substitute of rolled copper foil, the use of electrolytic copper foil is considered actively always.Its result, now, the two sides all has the electrolytic copper foil on the slim surface that is equal to rolled copper foil, is widely used in the anode collector purposes of lithium-ion secondary cell.
The correlation technique that all has the electrolytic copper foil on the slim surface that is equal to rolled copper foil as this two sides, as patent documentation 3, patent documentation 4 etc. are disclosed, invent for the surfaceness of the face of separating out that reduces electrolytic copper foil, in described invention, controlled the electrolytic solution composition that is used for the copper electrolyte that electrolytic copper foil makes, electrolyte temperature, current density etc.
In patent documentation 3, the outstanding electro-deposition copper foil of, etching performance useful in the tellite manufacturing to be manufactured on and impedance Control performance is as purpose, adopted " comprise (A) electrolytic solution and between anode and negative electrode, flow through, and then between this anode and this negative electrode, apply so that this negative electrode is separated out the operation of voltage of the significant quantity of copper; Herein, this electrolytic solution contains cupric ion, sulfate ion and at least a organic additive or its derivative, and the chlorine ion concentration of this solution is for approximately reaching 1ppm; Current density is about 0.1～approximately 5A/cm 2Scope; And the operation of (B) removing Copper Foil from this negative electrode." manufacture method.That is, adopted such electrolytic condition: use the copper electrolyte of having controlled cl concn.
And, in patent documentation 4, adopted such electrolytic condition, it is characterized in that, used the thiocarbamide or derivatives thereof that contains 0.05～2.0 ppm by weight, 0.08 the high molecular polysaccharide of～12 ppm by weight, and the glue of molecular weight below 10000,0.03～4.0 ppm by weight is as the electrolytic solution of additive.Its result has produced the surfaceness of the face of separating out of this electrolytic copper foil near the electrolytic copper foil of rolled copper foil level of surface roughness.
And then, in patent documentation 5, point out crystal structure miniaturization and reduced electrolytic copper foil that each communique such as patent documentation 3, patent documentation 4 of surfaceness puts down in writing and exist fully satisfying the market to the situation of the demand of cycle charge discharge electric life, the characteristic of overcharging aspect.According to this patent documentation 5 as can be known, as affect the cycle charge discharge electric life and the smoothness on the surface that the Copper Foil characteristic of the characteristic of overcharging can't represent with 10 mean roughness Rz, normal temperature tensile strength, elongation, non-recrystallization, hot environment in elongation be important, and the successful example as obtain the Copper Foil of best effects in the secondary cell characteristic discloses a kind of like this electrolytic copper foil among the embodiment 1 of patent documentation 5.That is: " in the sulfuric acid copper sulfate electrolyte that contains cupric sulfate pentahydrate 280g/L, sulfuric acid 100g/L, chlorion 35ppm, add low molecular weight gelatine 7ppm, Natvosol 3ppm, the 3-sulfydryl-1-propane sulfonic acid sodium 1ppm of molecular-weight average 3000, and 55 ℃ of electrolyte temperatures, flow velocity 0.3m/ minute, current density 50A/dm 2Condition " etc. the electrolytic copper foil made; " it is characterized in that, the surfaceness that electrolytic copper foil is separated out face represents with 10 mean roughness Rz, crystal structure under the normal temperature is the fine crystalline less than 2.5 μ m, simultaneously, distance is more than the 5 μ m between the smallest peaks on basis, mountain, and the normal temperature tensile strength is 40kg/mm 2Below, and being reduced in 15% of the normal temperature tensile strength after 130 ℃, 15 hours thermal treatment, thermal softening does not occur.”
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-236684 communique
Patent documentation 2: TOHKEMY 2008-282550 communique
Patent documentation 3: Japanese kokai publication hei 7-188969 communique
Patent documentation 4: Japanese kokai publication hei 8-53789 communique
Patent documentation 5: TOHKEMY 2004-79523 communique
Summary of the invention
The problem that invention will solve
But, electrolytic copper foil in the anode collector that is used for lithium-ion secondary cell, as above-mentioned patent documentation 5 is pointed, not only always require improvement to affect the characteristic of the Copper Foil of cycle charge discharge electric life and overcharge characteristic, but also exist the deviation of the physical propertys such as elongation, tensile strength of electrolytic copper foil to become the situation of problem.
Probe into its reason, can think that the chlorine that used copper electrolyte comprised when electrolytic copper foil was made is reason.This chlorine is sometimes added wittingly and is controlled, and sometimes also sneaks into as keeping away impurity by vinylchlorid pipe arrangement etc.And then based on the electrochemistry viewpoint, the chlorine in the electrolytic solution even only have the change of trace, also is easily product quality to be brought the composition of impact.Therefore, although those skilled in the art considered that the electrolytic copper foil of making for electrochemical method, carried out the improvement take the deviation that reduces the quality of electrolytic copper foil own as the manufacture method of purpose, the change of cl concn is the major cause that can not keep away.
On the other hand, the requirement of higher stay in grade has been proposed with the electrolytic copper foil of running contact being used for lithium-ion secondary cell, namely, accepting on the basis of existing electrolytic copper foil, even require to have quality stable of the high level of running contact bending property under the state of " with the running contact (negative pole) of negative active core-shell material " of the heat-resistant property of softening that heating also is difficult to soften, bending resistance characteristic, immobilized actually negative active core-shell material etc.
The method of dealing with problems
Therefore, the result that the inventor concentrates on studies as serving as the suitable electrolytic copper foil of lithium-ion secondary cell with the copper clad laminate of the constituent material of running contact and printed wiring board manufacturing usefulness, has expected electrolytic copper foil as described below.In addition, by adopting the manufacture method of the following stated, so that the High-efficient Production of electrolytic copper foil of the present invention becomes possibility.
Electrolytic copper foil of the present invention: electrolytic copper foil of the present invention is the electrolytic copper foil that obtains by electrolytic copper electrolytic solution, it is characterized in that, the iodine amount in the electrolytic copper foil is more than the 0.003 quality %.
Surface treatment copper foil of the present invention: surface treatment copper foil of the present invention, it is characterized in that, surface treatment has been implemented on the above-mentioned surface of containing the electrolytic copper foil of 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 above-mentioned manufacture method that contains the electrolytic copper foil of iodine, it is characterized in that, adopting iodine concentration is that the sulfuric acid copper sulfate electrolyte of 1.5mg/L～15.0mg/L scope is as copper electrolyte.And the further preferred cl concn of this copper electrolyte is below the 1.0mg/L.
And, in the manufacture method of electrolytic copper foil of the present invention, preferably take the temperature of copper electrolyte as 40 ℃～60 ℃, current density 50A/dm 2～85A/dm 2Electrolytic condition carry out electrolysis.
The lithium ion secondary battery cathode that obtains with surface treatment copper foil of the present invention: the negative pole that lithium-ion secondary cell of the present invention is used, it is characterized in that, the surface treatment copper foil of the invention described above is used as anode collector.
The effect of invention
Electrolytic copper foil of the present invention as described above, is the electrolytic copper foil that contains the above iodine of 0.003 quality %.Thus, contain iodine by the sheet material copper that makes electrolytic copper foil, thereby even the change of the chlorine amount in the electrolytic copper foil also can be expressed stable physical property.
Therefore, by electrolytic copper foil of the present invention being used for the negative pole of lithium-ion secondary cell, thereby can provide at an easy rate and long-life lithium-ion secondary cell excellent to the resistibility of following the dilation phenomenon that discharges and recharges generation to market.
Description of drawings
Fig. 1 is the figure for check " electrolytic copper foil physical properties " and " the iodine amount that electrolytic copper foil contains and chlorine amount " relation.
Embodiment
The negative pole that the lithium-ion secondary cell that next coming in order obtain to the manufacture method of electrolytic copper foil of the present invention, surface treatment copper foil, with this surface treatment copper foil is used elaborates.
The form of electrolytic copper foil of the present invention: electrolytic copper foil of the present invention is the electrolytic copper foil that obtains by electrolytic copper electrolytic solution.This electrolytic copper foil is characterised in that, the scope of the iodine amount in the electrolytic copper foil more than 0.003 quality %.Contain so that the electrolytic copper foil of iodine is suitable to serve as the lithium-ion secondary cell running contact, and can improve simultaneously the running contact bending property under the state of " with the running contact (negative pole) of 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 the electrolytic copper foil is preferably more than the 0.003 quality %.When this iodine amount less than 0.003 quality %, any characteristic is all unstable, the stable difficult of product quality.On the other hand, if the iodine amount in the electrolytic copper foil is more than the 0.003 quality %, even the change of the chlorine amount then in the electrolytic copper foil also can show stable physical property, thus preferred.But, strictly speaking, if this iodine amount surpasses 0.03 quality %, then above-mentioned all characteristics all can't be further enhanced, can cause on the contrary the embrittlement of electrolytic copper foil, the curved characteristic variation, and the reduction of the exterior quality under the visual inspection also has the tendency that becomes serious, thus the iodine amount is preferably below the 0.03 quality %.
In addition, in the application's electrolytic copper foil, preferably on the basis of the above-mentioned iodine of control, also control the chlorine amount in the electrolytic copper foil.That is, in the electrolytic copper foil of the present invention, the chlorine amount of measuring by chemical analysis is preferably in the scope of 0.0000 quality %～0.0018 quality %.That is, the chlorine amount that contains when electrolytic copper foil owing to separating out the surfaceness step-down of face, easily obtains the face of separating out of slimming when 0.0018 quality % is following, thereby preferably as the constituent material of lithium-ion secondary cell with running contact.And then, in contrast place of embodiment and comparative example detailed narration is arranged, in brief namely, the heat-resistant property of softening when accepting heat in order to improve, 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 of measuring by chemical analysis and iodine amount preferably satisfy the relation (the chlorine amount anode collector purposes, electrolytic copper foil and the iodine that are applicable to lithium-ion secondary cell contain the relationship between quantities) with following formula 1.By satisfying such relation, thereby even under the temperature about 350 ℃, accept heating, also can demonstrate the high heat-resistant property of softening.To in embodiment described later, be elaborated about this point.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 in accordance with the following methods the chlorine amount.After in nitric acid, heating Copper Foil and making its dissolving, add a certain amount of silver nitrate solution.Then, add a certain amount of KBr solution, make chloride ion carry out co-precipitation with Silver monobromide.After in the dark leaving standstill 15 minutes, filter out throw out and clean.Afterwards, throw out is transferred in the beaker, with thiourea solution throw out is dissolved, and in the dark place a Dinner.Dilute this solution and constant volume, and the usefulness ion chromatograph (ICS-2000 that Dionex company makes, conductivity detector, elutriant are KOH, post is AS-20) and measure chloride ion concentration, calculate the chlorine amount.
Measure the iodine amount according to following method.Copper Foil heated in chloroazotic acid make its acidifying dissolving, carry out constant volume after the cooling, the SPS3000 that makes by ICP-AES(Seiko Precision KK) measure I:178nm(Ar and clean) intensity, calculate the iodine amount.
In addition, the result who with catharometry electrolytic copper foil of the present invention is measured: 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 below 0.01 quality %.Present stage, at the electrolytic copper foil of the anode collector that is used for lithium-ion secondary cell, which type of effect these major impurity amounts have still uncertain.But said major impurity composition is easily at the element of grain boundary segregation here, and if the major impurity amount be below the 0.01 quality %, then the toughness of electrolytic copper foil strengthens, elongation and tensile strength show good balance.
And then the inventor has carried out the mensuration of copper purity to electrolytic copper foil of the present invention with the glow discharge mass spectrometry instrument.Its result, the copper purity that obtains with the glow discharge mass spectrometry instrument is the above highly purified values of 99.99 quality %.Really, if consider iodine amount and the chlorine amount measured with above-mentioned chemical analysis, major impurity amount with the total of each composition of the carbon of measuring with catharometry, oxygen, sulphur, nitrogen, then with the copper purity that obtains with this glow discharge mass spectrometry instrument, can not form the value of mutually coincideing, but can think that this is owing to the different errors that produce of analytical procedure.
Secondly, the physical features that electrolytic copper foil of the present invention has is set forth.And when this physical features of explanation, the sheet metal thickness of having supposed electrolytic copper foil is that the situation of 18 μ m ± 1.8 μ m describes.
Surfaceness to the face of separating out of electrolytic copper foil of the present invention describes.As can be known, the value of the Rzjis of the surfaceness of the face of separating out of electrolytic copper foil of the present invention is the slim face of separating out in the scope of 0.70 μ m～2.0 μ m.Herein, if the value of Rzjis surpasses 2.0 μ m, then when making lithium ion secondary battery cathode, immobilized negative active core-shell material difficult equably.In addition, if repeat to discharge and recharge, then in the protuberance on running contact surface, lithium easily is grown to the crystalline tendency grow of branches and tendrils, thereby not preferred.On the other hand, when the value less than 0.7 μ m of Rzjis, then condition of surface is too level and smooth, when the anode collector of serving as lithium-ion secondary cell is used, and the adhesivity step-down between negative active core-shell material and the 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 in 0.6 μ m.And, 10 mean roughness of said Rzjis(here) and be based on JIS B0601, and the value of measuring with probe-type roughness tester (the radius-of-curvature 0.2 μ m of tips of probes).
The physical features that electrolytic copper foil of the present invention is measured is under normal conditions set forth.Normality elongation (the E of electrolytic copper foil of the present invention 0) value preferably in 2.0%～9.0% scope.When the normality elongation is 2.0% when above, be applicable to the anode collector of lithium-ion secondary cell.On the other hand, when the normality elongation is 9.0% when following, resistance to deformation when being used for the anode collector of lithium-ion secondary cell, that follow the dilation when discharging and recharging is in suitable scope.And in this application, the mensuration of this elongation and the mensuration of tensile strength described later are, by the wide electrolytic copper foil sample of 10mm is carried out the value that tension test is 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 2When above, resistance to deformation corresponding to dilation when being used for the anode collector of lithium-ion secondary cell, when discharging and recharging has the good tendency of change.On the other hand, as normality tensile strength (F 0) value be 72kgf/mm 2When following, it stably is in the scope of above-mentioned suitable normality elongation.
Below, to electrolytic copper foil of the present invention set forth at the physical features that carries out measuring after certain heat treated (below situation referred to as " heat after " is arranged.）。Said heat treated refers to herein, the electrolytic copper foil of normality is implemented 180 ℃ * 60 minutes heat treated in atmospheric environment.
Elongation (E after the heat of electrolytic copper foil of the present invention a) value in 4%～10% scope.The circuit that consists of with Copper Foil in the manufacturing processed of printed wiring board and the anode collector made from Copper Foil in the manufacturing processed of the negative pole of lithium-ion secondary cell are exposed in the various high-temperature load environment.Therefore, the rear physical properties of the heat of this electrolytic copper foil becomes the very important key element of left and right sides product quality.If elongation (E after the heat a) value be more than 4%, then be the suitable elongation in the anode collector purposes of lithium-ion secondary cell.On the other hand, when elongation after the heat is 10% when following, resistance to deformation when being used for the anode collector of lithium-ion secondary cell, that follow the dilation when discharging and recharging is in suitable scope.
And then, the hot back draft intensity (F of electrolytic copper foil of the present invention after 180 ℃ * 60 minutes heat treated a) value show as at 38kgf/mm 2～72kgf/mm 2Scope.As hot back draft intensity (F a) value be 38kgf/mm 2When above, be difficult to be subject to processing the impact of the hot resume in the process, and resistance to deformation corresponding to dilation when being used for the anode collector of lithium-ion secondary cell, when discharging and recharging also there is the good tendency of change.On the other hand, if hot back draft intensity (F a) value be 72kgf/mm 2Below, then easily keep the scope of above-mentioned suitable normality elongation, therefore preferred.
In addition, in electrolytic copper foil of the present invention, as physical features, above-mentioned normality tensile strength (F 0) value and the hot back draft intensity (F after above-mentioned 180 ℃ * 60 minutes heat treated a) value preferably satisfy relation with 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, also be difficult to soften even be subject to certain heating.In the manufacturing 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 is softening, then all deviations as the desired bending property of negative pole intensity of lithium-ion secondary cell, resistance to deformation that the dilation when discharging and recharging when being used for anode collector is corresponding will become large, can't guarantee the quality stability as lithium-ion secondary cell, therefore not preferred.Thereby, require to have the anti-softening power 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, namely after the heat after 180 ℃ * 60 minutes heat treated in the anti-pliability test, the number of bends till rupturing is more than 3000 times.If the number of bends after the heat in the anti-pliability test is more than 3000 times, resistance to deformation corresponding to dilation when then being used for the anode collector of lithium-ion secondary cell, when discharging and recharging is tremendous raising, so that the prolongation of product life becomes possibility.Anti-pliability test after the said heat herein is even in the situation of the electrolytic copper foil of printed wiring board-use, also be the important characteristic that is required.And, about this number of bends, although do not put down in writing out clearly higher limit, rule of thumb be about 6500 times.And, anti-pliability test is after the said heat herein, the flexural buckling of making based on the measuring method of JIS C 5016, with the TESTER Industry Co., Ltd (bending radius: 1mm that tests a machine, rate of bending: 100cpm, stroke: 20mm), to the electrolytic copper foil of the short strip shape of wide 10mm * long 10cm, after 180 ℃ * 60 minutes heat treated, measure the test of its number of bends till the fracture.
The form of surface treatment copper foil of the present invention: surface treatment copper foil of the present invention, it is characterized in that, various surface treatments are implemented on the surface of the above-mentioned electrolytic copper foil that contains iodine.This surface treatment refers to, the one or more kinds of processing in above-mentioned electrolytic copper foil surface enforcement roughened, antirust processing, silane coupling agent are processed.This surface treatment is to have considered the characteristic that requires of different purposes, to pay bond strength, chemical proofing, thermotolerance etc. as purpose, to the processing of electrolytic copper foil surface enforcement.In addition, process about silane coupling agent, if when being used for the electrolytic copper foil of anode collector of lithium-ion secondary cell, then preferably implement on the two sides of electrolytic copper foil, if when being used for the electrolytic copper foil of printed wiring board, then preferably implement at a face of electrolytic copper foil.
The manufacturing 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 that contains iodine, it is characterized in that the composition of sulfuric acid based copper electrolyte used herein.And the copper concentration in the said sulfuric acid based copper electrolyte adopts the scope of 50g/L～120g/L herein, further the preferred scope that adopts 50g/L～80g/L.In addition, free sulfuric acid concentration is considered scope take 60g/L～250g/L as benchmark, further preferably considers that scope take 80g/L～150g/L is as benchmark.
Iodine concentration in this sulfuric acid based copper electrolyte is preferably in the scope of 1.5mg/L～15.0mg/L.Further preferred scope at 2.5mg/L～7.0mg/L.When the not enough 1.5mg/L of the iodine concentration in the sulfuric acid based copper electrolyte, enter the iodine quantity not sufficient in the electrolytic copper foil of being separated out by electrolysis, thereby the electrolytic copper foil that obtains can't obtain the physical propertys such as the surfaceness, elongation, tensile strength of above-mentioned optimum range, As time goes on various physical propertiess also have and change the tendency of aggravating, therefore not preferred.On the other hand, if this iodine concentration surpasses 15.0mg/L, then the iodine amount in the electrolytic copper foil increases, and foregoing problems will occur.In addition, by making this iodine concentration below 7.0mg/L, separate out the smoothness of face and good physical strength thereby can take into account electrolytic copper foil.In the interpolation of iodine at this moment, preferably use the iodide such as NaI, KI.
In addition, the following concentration of the preferred 1.0mg/L of cl concn of the copper electrolyte of the present invention's use.If this cl concn surpasses 1.0mg/L, the easy embrittlement of electrolytic copper foil that then obtains, therefore not preferred.And then, in order further to stablize the scope of the cl concn that electrolytic copper foil of the present invention contains, preferably in the scope of 0.4mg/L～0.8mg/L.By adopting the cl concn of this scope, thereby balance contains above-mentioned each composition well, and separates out the face slimming, so that the stable possibility that creates of high-intensity electrolytic copper foil.During the adjustment of the cl concn in carrying out 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, preferably the temperature at copper electrolyte is 40 ℃～60 ℃, current density 50A/dm 2～85A/dm 2Scope under carry out electrolysis.When 40 ℃ of solution temperature less thaies, lack the stability of electrolysis, the deviation of the physical strengths such as the tensile strength of the electrolytic copper foil that obtains and elongation has the tendency that becomes large.On the other hand, if solution temperature surpasses 60 ℃, the then evaporation of the moisture in solution aggravation, the stability of solution composition is not enough, thereby makes process management become numerous and diverse, and is therefore not preferred.
In addition, if the not enough 50A/dm of the current density during said electrolysis herein 2, then can't obtain the desired production efficiency of industrialness, production efficiency reduces, thereby not preferred.On the other hand, if the current density during electrolysis surpasses 85A/dm 2, the electrolytic copper foil of then making is separated out the physical property aspect such as the surfaceness, tensile strength of face deviation is easily occured, thereby not preferred.
The lithium ion secondary battery cathode that obtains with surface treatment copper foil of the present invention: the lithium ion secondary battery cathode that obtains with surface treatment copper foil of the present invention, it is characterized in that, adopted above-mentioned surface treatment copper foil as anode collector.Usually, the negative pole that lithium-ion secondary cell is used is, carries out the immobilized of negative active core-shell material on the surface as the surface treatment copper foil of anode collector, thereby obtains the negative pole with the anode collector state of negative active core-shell material.In this manufacturing process, use the surface treatment copper foil of electrolytic copper foil of the present invention by employing, thereby can improve simultaneously the good heat-resistant property of softening, bending resistance characteristic and the immobilized actually running contact bending property under " with the running contact (negative pole) of negative active core-shell material " state of negative active core-shell material.
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 the printed wiring board manufacturing (has the situation referred to as " copper clad laminate " with copper clad laminate in the context.) manufacturing in.For example, above-mentioned surface-treated electro-deposited copper foil and insulation layer constituent material are carried out stacked, thereby also can obtain printed wiring board manufacturing copper clad laminate.And, indicate at this for special for the purpose of prudent, comprise in the concept of said copper clad laminate herein rigidity copper clad laminate and flexible copper clad laminate the two.Electrolytic copper foil of the present invention is owing to being slim, thereby is applicable to contain the formation of fine-line of the level that flexible printed circuit board requires of TAB, COF etc.
Below, understand electrolytic copper foil of the present invention etc. for easy, thereby show embodiment.
Embodiment
In this embodiment, adopted the basic solution of the copper concentration 80g/L in the copper-bath, free sulfuric acid concentration 140g/L as the sulfuric acid based copper electrolyte, and be adjusted to each additive concentration shown in the table 1.The iodine of this moment adds use potassiumiodide (KI) and carries out, and has used hydrochloric acid in the adjustment of cl concn.And then, with the sulfuric acid based copper electrolyte that different additive mixing ratios forms that has shown in the table 1, produce eight kinds of electrolytic copper foils that contain iodine of sample 1～sample 8.And, this embodiment be for, thereby by comparing with comparative example so that as the clear embodiment of difference of the general physical properties of Copper Foil.
In the manufacturing of electrolytic copper foil, adopt the sand paper effects on surface by 2000# to carry out the titanium plate electrode that grinds as negative electrode, and anode adopt DSA, and at 50 ℃ of solution temperatures, current density 75A/dm 2Condition under carry out electrolysis, thereby produce thickness 18 electrolytic copper foils μ m, that contain iodine.The surfaceness (Rzjis) of the glossy surface of these electrolytic copper foils (separating out the face of the opposition side of face) is 1.4 μ m.The assessment result of each characteristic of the electrolytic copper foil that herein obtains is summarized in the table 2, thereby can compares with following comparative example.
Here various condition determinations etc. are described.The mensuration of the normality of embodiment sample and the tensile strength after the heat, elongation is carried out based on IPC-TM-650.In addition, the mensuration of surfaceness is carried out based on JISB 0601-2001.Following comparative example is also identical.
Comparative example
The duplicate 1 of this comparative example and duplicate 2 have adopted the following copper electrolyte of iodine concentration 0.5mg/L, and this comparative example is for the comparative example that compares with above-described embodiment.And then duplicate 3 and duplicate 4 have adopted the copper electrolyte (copper electrolyte that does not contain iodine) of iodine concentration 0.0mg/L.Other has made duplicate 1～duplicate 4 with create conditions identical with embodiment.The electrolytic solution composition of above-mentioned electrolytic solution composition with embodiment is shown in the table 1 of back in the lump.
By the contrast of embodiment and comparative example can be clear and definite the result
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]
Figure BDA00002674038200121
According to this table 1, sample 1～sample 8 of embodiment has adopted and has been included in sulfuric acid copper sulfate electrolyte in the proper range of " cl concn 1.0mg/L is following, iodine concentration 1.5mg/L～15.0mg/L " as copper electrolyte of the present invention.Therewith relatively, as can be known, duplicate 1～duplicate 4 does not all adopt the sulfuric acid copper sulfate electrolyte in the scope that is included in " iodine concentration 1.5mg/L～15.0mg/L ", does not use the copper electrolyte that contains this suitable chlorine and iodine.
[table 2]
Annotate) after the heat: the situation after the heat treated of 180 ° of C * 60 minute.
Separate out the surfaceness of face: use the Rzjis mark
From this table 2 as can be known, in the manufacture method of the application's the electrolytic copper foil that contains iodine, by using copper electrolyte to satisfy the sulfuric acid copper sulfate electrolyte of the condition of " cl concn 1.0mg/L is following, iodine concentration 1.5mg/L～15.0mg/L ", thereby can obtain the electrolytic copper foil of iodine amount 0.005 quality %～0.063 quality %.As can be known, the face of separating out of this electrolytic copper foil is level and smooth, and the difference of the tensile strength after normality and the heat satisfies ［ normality tensile strength (F 0)-［ hot back draft intensity (F a) value be 10kgf/mm 2Following condition.
To the investigation 1 as the characteristic of the anode collector of lithium-ion secondary cell: investigate in 1 at this, with the data of aforementioned table 2 in the X-Y coordinate plane, Y-direction with the longitudinal axis represents " the iodine amount in the paper tinsel ", and the directions X of transverse axis represents " cl concn in the paper tinsel ", and that drafting forms is exactly Fig. 1.And then, at this Fig. 1
Figure BDA00002674038200131
Shown in the above zone of the straight line of iodine amount 0.003 quality % in, comprised the data of all embodiment.Therewith relatively, as can be known, the iodine amount less than 0.003 quality % of the duplicate of comparative example.
If look back the record content of table 2, as can be known in an embodiment, only have the iodine amount of the electrolytic copper foil of sample 7 to surpass 0.03 quality % herein.As this result, find that the number of bends of the rear anti-pliability test of heat of sample 7 is 1105 times, be the value lower than the number of bends of other samples.This has also proved effectively, if the iodine amount in the electrolytic copper foil surpasses 0.03 quality %, then the tissue of electrolytic copper foil has the tendency of embrittlement.
And then, have iodine amount in the zone at the straight line upside of Fig. 1 (above-mentioned formula 1 represented zone) and the situation of chlorine amount, because the desired characteristic of electrolytic copper foil as the anode collector purposes of using for lithium-ion secondary cell, namely the heat-resistant property of softening of heating strengthened especially, and the heat-resistant property of softening is stable, and therefore preference is arranged.Namely can think, in the electrolytic copper foil of the anode collector purposes of using for lithium-ion secondary cell, not only consider the iodine amount in the electrolytic copper foil, and consider the chlorine amount in the electrolytic copper foil, thereby satisfying the relation shown in the formula 1, is especially preferred.
Considering foregoing can judge, in the application's the electrolytic copper foil that contains iodine, the iodine amount is 0.003 quality %～0.03 quality %, the chlorine amount is 0.0006 quality %～0.0018 quality %, and be in the scope that satisfies condition shown in the formula 1, just had the most preferred characteristic as the anode collector of lithium-ion secondary cell.
To the investigation 2 as the characteristic of the anode collector of lithium-ion secondary cell: this investigation 2 is used for illustrating the distinctive heat-resisting property of softening of electrolytic copper foil that contains iodine of the present invention, and to " the normality tensile strength and carry out heating under 350 ℃ after the relation of heating back draft intensity " set forth.That is, it is to have considered the hot environment that is applied in the manufacturing processed of negative pole of lithium-ion secondary cell, and is used for the variation of the physical property after the heating under having carried out 350 ℃, and the investigation that compares of comparative example.Investigate in 2 at this, for convenience of explanation, use the sample of from the used duplicate 1～duplicate 4 of the sample 1～sample 8 of the above embodiments and comparative example, extracting out to describe.
Table 3 expression " normality tensile strength (F 0) " and " the heating back draft intensity (F after the heating under having carried out 350 ℃ b) " relation.This is to use Copper Foil has been carried out that short strip shape sample after 350 ℃ * 60 minutes the heating, long 10cm * wide 10mm carries out tension test and the result that obtains.
[table 3]
Figure BDA00002674038200151
Annotate) after the heat (Fb): the situation after the heat treated of 350 ° of C * 60 minute.
According to table 3 also as can be known, even contain the electrolytic copper foil of iodine, do not contain the sample 3 of chlorine after 350 ℃ * 60 minutes heat treated, tensile strength also can sharply descend.In addition, duplicate 1, duplicate 2 and duplicate 4 are although the tensile strength after the heat shows as not enough 30kgf/mm 2Value, but sample 1～sample 3 has been kept 30kgf/mm 2Above value.Therewith relatively, sample 2 is arranged in the zone of satisfying the relation shown in the aforementioned formula 1, and is arranged in the shadow region of Fig. 1, even after being subject to 350 ℃ * 60 minutes heat treated, still possess 40kgf/mm 2Above high tensile strength, and the number of bends of the anti-pliability test shown in the table 2 also shows as outstanding value.
On the other hand, scope (formula shown in the above-mentioned formula 1) according to the division of the straight line A among Fig. 1, the physical properties of the electrolytic copper foil of the application after 350 ℃ as can be known * 60 minutes heat treated has obtained differentiation, and described Fig. 1 is the figure that has represented to investigate " iodine amount and chlorine in the electrolytic copper foil physical properties after the heat treated contain the relationship between quantities " shown in 1.
Namely, have iodine amount in the zone of the straight line upside of this Fig. 1 (satisfying the zone of condition shown in the formula 1) and the situation of chlorine amount, because the desired characteristic of electrolytic copper foil as the anode collector purposes of using for lithium-ion secondary cell, namely the heat-resistant property of softening for heating strengthens especially, and the heat-resistant property of softening is stable, and is therefore preferred.Thereby as can be known clear and definite, in the electrolytic copper foil of the anode collector purposes of using for lithium-ion secondary cell, not only consider the iodine amount in the electrolytic copper foil, and consider the chlorine amount in the electrolytic copper foil, thereby satisfying the relation shown in the formula 1, is especially preferred.
As from the foregoing, in electrolytic copper foil, must balance contain well iodine and chlorine.Be classified as the sample 1 of such electrolytic copper foil and the electrolytic copper foil of sample 2, strong for the anti-softening power of heating, namely be used in the negative pole manufacturing of lithium-ion secondary cell, also can the dilation phenomenon when discharging and recharging show sufficient non-deformability.
To the investigation 3 as the characteristic of the anode collector of lithium-ion secondary cell: this investigation 3 also is used for the distinctive heat-resisting property of softening of electrolytic copper foil that contains iodine of the present invention is described, and " heat-resisting bending tensile test result " is set forth.This heat-resisting bending tensile test (jus singular) has implemented to have obtained after 350 ℃ * 60 minutes the heat treated result of tension test to Copper Foil.Table 4 couple this result has carried out record.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, the Copper Foil sample of the short strip shape of the 1cm * 10cm that tension test is used with certain Heating temperature (350 ℃ of the Heating temperatures of jus singular, other 180 ℃) carries out 60 minutes heat treated, and places cooling.
2. afterwards, crooked this sample, under the state that applies the 15kg load, 180 ° of stress in bendinges of loading 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
Heat-resisting tensile strength (having omitted the heat-resisting tensile strength of heat-resisting bending tensile test step (2))
Heat-resisting bend tension intensity
Here the reason that adopts above-mentioned heat-resisting bending tensile test (jus singular) is described.When negative pole that lithium-ion secondary cell has used Copper Foil when forming active material layer in the running contact, the high temperature of having loaded.And then, in square lithium-ion secondary cell, have make this negative pole of being subject to high-temperature load and having formed active material layer with the stacked state of positive pole or pad under bending and slimming becomes square operation.Therefore, heat-resisting bending tensile test (jus singular) is, for the patience of the Copper Foil of assessing the load when having been executed such bending machining imports.
[table 4]
Figure BDA00002674038200171
By this table 4 as can be known, embodiment (sample 1, sample 2, sample 5, sample 6) compares with duplicate 1, and the bend tension intensity after the heating in 180 ℃ * 60 minutes is also relatively high.Hence one can see that, also is difficult to the characteristic of softening even the electrolytic copper foil that contains iodine of the present invention has the heat of being subject to, even and crooked, its tensile strength also reduces few, is difficult to rupture.
Herein, if with sample 5, the sample 6 of table 4, and duplicate 1 compares, and perhaps can feel and can not see that large difference exists aspect the tensile strength after 350 ℃ * 60 minutes heating.Moreover, if observe bend tension intensity after their 180 ℃ * 60 minutes the heating, then to compare with duplicate 1, the value of the bend tension intensity of sample 5 and sample 6 obviously uprises.Therefore as can be known, sample 5 and sample 6 compared to duplicate 1, also can show good tensile strength even be subject to the heating of large temperature range, even crooked, the reduction of its tensile strength is also few, is difficult to fracture.
In addition, if observe the sample 1 suitable with embodiment, sample 2, sample 5, sample 6 after 180 ℃ * 60 minutes the heating and the variation of the bend tension intensity after 350 ℃ * 60 minutes the heating, just as can be known to draw a conclusion.In sample 1 and sample 2, to compare with the bend tension intensity after 180 ℃ * 60 minutes the heating, the bend tension intensity after 350 ℃ * 60 minutes the heating uprises.Their iodine amount is respectively 0.018 quality %, 0.019 quality %, by containing the iodine of such degree, thereby has significantly improved the heat-resistant property of softening of material for heating.On the other hand, in sample 5 and sample 6, compare with the bend tension intensity after 180 ℃ * 60 minutes the heating, the bend tension intensity after 350 ℃ * 60 minutes the heating becomes especially low.Their iodine amount is 0.005 quality %, in the situation of the iodine amount of this degree, can't realize significantly improving of the heat-resistant property of softening.But can say, even sample 5 and sample 6 than comparative example, also can improve the heat-resistant property of softening of material really.
To the investigation 4 as the characteristic of the anode collector of lithium-ion secondary cell: investigate in 4 at this, comprise with the electrolytic solution beyond the composition of table 1 record and form and the electrolytic copper foil that obtains, and do to study in more detail with the paper tinsel physical properties after 350 ℃ of heat tests.In this table 5, put down in writing the paper tinsel physical properties after 350 ℃ * 60 minutes the heat test of composition correspondence of the composition of electrolytic solution, every kind of copper electrolyte.And creating conditions beyond electrolytic solution forms is identical with embodiment.Herein, according to the result of table 1 and table 2 as can be known, the S of the table 5 series (general name of " sample S-1～sample S-8 ".) be the Copper Foil suitable with electrolytic copper foil of the present invention.On the other hand as can be known, the C of the table 5 series (general name of " sample C-1～sample C-4 ".) not the Copper Foil suitable with electrolytic copper foil of the present invention.And, hereby indicating as a reference, sample S-2 is the sample 1 described in the embodiment, sample S-5 is the sample 2 described in the embodiment, sample C-1 is the duplicate 1 described in the comparative example, and sample C-2 is the duplicate 2 described in the comparative example, and sample C-4 is the duplicate 4 described in the comparative example.
[table 5]
Figure BDA00002674038200191
Annotate) 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)
By this table 5 as can be known, " S series " compares with " C is serial ", and the tensile strength of carrying out after 350 ℃ * 60 minutes the heat treated uprises.That is, observe the tendency of this tensile strength as can be known, with " S series " that the sulfuric acid copper sulfate electrolyte that contains a certain amount of iodine is made, it is 27kgf/mm that 350 ℃ * 60 minutes harsh heating have been shown tensile strength 2Above sufficient anti-softening power.And " S series " has also shown 28kgf/mm even carry out bending 2Above high tensile strength.In addition, observe preferred form in " S series ", show heat-resisting tensile strength and heat-resisting bend tension intensity simultaneously, 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 also show 40kgf/mm when showing heat-resisting tensile strength and heat-resisting bend tension intensity 2Above high tensile strength.
To the investigation 5 as the characteristic of the anode collector of lithium-ion secondary cell: investigate in 5 at this, with reference to table 6, the advantage during to anode collector that the electrolytic copper foil that contains iodine of the present invention is served as lithium-ion secondary cell describes.In this explanation, adopt sample 1～sample 3, duplicate 1, duplicate 2 and the duplicate 4 of comparative example, section's Ademilson Alloy Foil, the calendering copper alloy foil of embodiment, and they are compared.And, investigate in 5 at this, consider electric conductivity, and in the mensuration of electric conductivity, utilize the B1500A semiconducter device analyser of Agilent Technologies and adopted four-point probe method based on JISK7194.
[table 6]
Figure BDA00002674038200201
* after the 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 makes
* * rolls copper alloy foil: the HCL02Z that Hitachi Cable Ltd. makes
In order to prolong the cycle life of lithium-ion secondary cell, must reduce as far as possible the voltage loss that the resistance of anode collector brings, electronics is supplied with or collected to the negative active core-shell material in the battery equably, and make its reaction.Physical properties after 350 ℃ * 60 minutes the heat treated of the electrolytic copper foil that uses as anode collector is considered to and can requires characteristic to produce large impact on this.
That is, as shown in Table 6, the application's the electrolytic copper foil that contains iodine, the tensile strength that shows after 350 ℃ * 60 minutes the heat treated is 30kgf/mm 2Above high value is simultaneously no matter under the normality or all stably show high electric conductivity after the heating.On the other hand, do not contain the electrolytic copper foil of iodine, although electric conductivity is high, heating has caused the tensile strength decrease.Therefore can judge, the electrolytic copper foil that does not contain iodine can't tolerate the lithium-ion secondary cell dilation phenomenon that anode collector is subject to when discharging and recharging.
In addition, in table 6, usefulness shows section's Ademilson Alloy Foil and calendering copper alloy foil as a comparison.Although the tensile strength after section's Ademilson Alloy Foil heating is very good, alloy composition is so that electric conductivity is low.Therefore, when using as anode collector, be difficult to the reaction that anticathode integral body is supplied with equably electronics and collect equably lithium in negative active core-shell material occurs, thus not preferred.
And, in the calendering copper alloy, at first sight, can think that it has obtained the balance between tensile strength and electric conductivity.But as can be known, to be compared to the sample of the sample of embodiment of electrolytic copper foil or comparative example low for the electric conductivity of normality.When the tinsel with such physical properties is used as anode collector, it is superheat state that the heating that produces when discharging and recharging can cause anode collector local, the state of forming section annealing, only the tensile strength at this position and resistance reduce, distortion aggravation as anode collector, and be difficult to occur the reaction that anticathode integral body is supplied with equably electronics, collected equably lithium at negative active core-shell material, therefore not preferred.
As mentioned above as can be known, the electrolytic copper foil that contains iodine of the present invention even compare with the duplicate of comparative example, section's Ademilson Alloy Foil, calendering copper alloy foil, also more is applicable in the purposes as the anode collector of lithium-ion secondary cell.
Comprehensive judge: can say that electrolytic copper foil suitable with above-described embodiment, that contain iodine also is difficult to the character that ruptures even have to bend.Therefore, if such electrolytic copper foil is served as the collector materials of the coiled battery that adopts in the lithium-ion secondary cell, be difficult to then to occur that hot resume that this battery loads cause is softening in manufacturing processed, and the impact that the heating when being difficult to be subject to discharging and recharging brings, and then the non-deformability of the expansion/contraction phenomenon when discharging and recharging is also strong.Therefore can say, the electrolytic copper foil that contains iodine of the present invention is the suitable Copper Foil as the collector materials that adopts in the lithium-ion secondary cell.
Industrial applicibility
Electrolytic copper foil of the present invention is that the iodine that will not contain in the existing electrolytic copper foil contains the electrolytic copper foil more than the 0.003 quality %.Even this electrolytic copper foil chlorine amount change that contains iodine also can demonstrate the electrolytic copper foil of various stable characteristics.
And the physical properties of this electrolytic copper foil also is difficult to the characteristic of softening even have heating, and has running contact desired good the heat-resistant property of softening and the bending resistance characteristic of lithium-ion secondary cell concurrently.Thereby, if adopt this electrolytic copper foil as running contact, then can realize the market supply of high-quality and long-life lithium-ion secondary cell.

Claims (14)

1. electrolytic copper foil, it is the electrolytic copper foil that obtains by electrolytic copper electrolytic solution, it is characterized in that,
Iodine amount in the electrolytic copper foil is more than the 0.003 quality %.
2. electrolytic copper foil as claimed in claim 1 is characterized in that, aforementioned iodine amount is below the 0.03 quality %.
3. electrolytic copper foil as claimed in claim 1 or 2 is characterized in that, the scope of chlorine amount below 0.0018 quality %.
4. such as each described electrolytic copper foil in the claim 1～3, it is characterized in that, chlorine amount and iodine amount satisfy the relation with following formula 1,
[formula 1]
[iodine amount (quality %)] 〉=-30 * [chlorine amount (quality %)]+0.03.
5. such as each described electrolytic copper foil in the claim 1～4, it is characterized in that having the value of Rzjis at the face of separating out of 0.70 μ m～2.0 μ m scopes.
6. such as each described electrolytic copper foil in the claim 1～5, it is characterized in that normality tensile strength (F 0) value at 48kgf/mm 2～72kgf/mm 2Scope.
7. such as each described electrolytic copper foil in the claim 1～6, it is characterized in that the hot back draft intensity (F after 180 ℃ * 60 minutes the heat treated a) value be 38kgf/mm 2～72kgf/mm 2
8. such as each described electrolytic copper foil in the claim 1～7, it is characterized in that normality tensile strength (F 0) value, with 180 ℃ * 60 minutes heat treated after hot back draft intensity (F a) value satisfy the relation of following formula 2,
[formula 2]
[normality tensile strength (F 0)]-[hot back draft intensity (F a)]≤10kgf/mm 2
9. such as each described electrolytic copper foil in the claim 1～8, it is characterized in that the hot back draft intensity (F after 350 ℃ * 60 minutes the heat treated b) value be 30kgf/mm 2Above.
10. such as each described electrolytic copper foil in the claim 1～9, it is characterized in that, when sheet metal thickness was 18 μ m ± 1.8 μ m, number of bends after 180 ℃ * 60 minutes the heat treated, in the anti-pliability test was more than 3000 times.
11. surface treatment copper foil is characterized in that, surface treatment has been implemented on each described surface of containing the electrolytic copper foil of iodine in the claim 1～10.
12. the manufacture method of electrolytic copper foil, it is the manufacture method of the electrolytic copper foil that contains iodine described in the claim 1～11, 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.
13. the manufacture method of electrolytic copper foil as claimed in claim 12 is characterized in that, adopting cl concn is the following sulfuric acid copper sulfate electrolyte of 1.0mg/L.
14. lithium ion secondary battery cathode is characterized in that, immobilized in the described surface treatment copper foil of claim 11 have a negative active core-shell material.
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KR20140041804A (en) * 2011-06-30 2014-04-04 후루카와 덴키 고교 가부시키가이샤 Electrolytic copper foil, method for producing electrolytic copper foil, and lithium ion secondary cell using electrolytic copper foil as collector
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
KR101449342B1 (en) * 2013-11-08 2014-10-13 일진머티리얼즈 주식회사 Electrolytic copper foil, electric component and battery comprising the foil
JP6855164B2 (en) * 2013-11-27 2021-04-07 三井金属鉱業株式会社 Copper foil with carrier foil and copper-clad laminate
KR102122425B1 (en) 2015-06-18 2020-06-12 케이씨에프테크놀로지스 주식회사 Electrolytic copper foil for lithium secondary battery and Lithium secondary battery comprising the same
WO2016204405A1 (en) * 2015-06-18 2016-12-22 엘에스엠트론 주식회사 Electrolytic copper foil for lithium secondary battery and lithium secondary battery including same
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
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
KR102103765B1 (en) 2018-05-16 2020-04-28 일진머티리얼즈 주식회사 Electrolytic Copper Foil and secondary battery using thereof
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
HUP2200353A2 (en) * 2020-01-30 2022-11-28 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186893A (en) * 1987-01-27 1988-08-02 Sumitomo Metal Ind Ltd Copper plating method for electric conductor coil for electromagnetic transducing device
JPH0978638A (en) * 1995-09-13 1997-03-25 Aisin Seiki Co Ltd Rainwater utilizer
JP2004035918A (en) * 2002-07-01 2004-02-05 Nippon Denkai Kk Method of producing electrolytic copper foil
JP2004339559A (en) * 2003-05-14 2004-12-02 Kobe Steel Ltd Aluminum alloy sheet for calking, and its production method
JP2005197205A (en) * 2003-12-12 2005-07-21 Mitsui Mining & Smelting Co Ltd Negative electrode current collector for nonaqueous electrolytic solution secondary battery
JP2006152420A (en) * 2004-12-01 2006-06-15 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil and method for producing the same
JP2006299320A (en) * 2005-04-19 2006-11-02 Ls Cable Ltd High strength low roughness copper foil and method of manufacturing the same
CN101669237A (en) * 2007-04-20 2010-03-10 日矿金属株式会社 Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5236494B2 (en) * 1972-12-05 1977-09-16
JPH08335607A (en) * 1995-06-05 1996-12-17 Hitachi Cable Ltd One-layer wiring tcp tape
JP3521074B2 (en) * 2000-01-06 2004-04-19 三井金属鉱業株式会社 Method for testing physical properties of electrolytic copper foil
CN1195395C (en) * 2001-01-30 2005-03-30 日鉱金属股份有限公司 Copper alloy foil for integrated board
KR100975491B1 (en) * 2005-03-31 2010-08-11 미쓰이 긴조꾸 고교 가부시키가이샤 Electrolytic copper foil and process for producing electrolytic copper foil
TW200714666A (en) * 2005-07-29 2007-04-16 Sumitomo Chemical Co Laminate of liquid crystalline polyester with copper foil
CN1972557A (en) * 2005-10-14 2007-05-30 三井金属矿业株式会社 Flexible copper clad laminate, film carrier tape manufactured using the same, and method for manufacturing same, and flexible printed circuit board, and semiconductor device
JP2007146289A (en) * 2005-10-31 2007-06-14 Mitsui Mining & Smelting Co Ltd Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad laminate manufactured using the electrolytic copper foil or surface-treated copper foil
TW200728515A (en) * 2005-10-31 2007-08-01 Mitsui Mining & Smelting Co Method for manufacture of electrolytic copper foil, electrolytic copper foil manufactured by the method, surface-treated copper foil manufactured using the electrolytic copper foil, and copper-clad laminate manufactured using the electrolytic copper
KR101154203B1 (en) * 2006-04-28 2012-06-18 미쓰이 긴조꾸 고교 가부시키가이샤 Electrolytic copper foil, surface treated copper foil using the electrolytic copper foil, copper-clad laminated plate using the surface treated copper foil, and method for manufacturing the electrolytic copper foil
US20080012462A1 (en) * 2006-07-12 2008-01-17 Kabushiki Kaisha Toshiba Electron emission element, method of manufacturing electron emission element, and display device with electron emission element
US20080174016A1 (en) * 2006-12-28 2008-07-24 Mitsui Mining & Smelting Co., Ltd. Flexible Printed Wiring Board and Semiconductor Device
JP2008285727A (en) * 2007-05-18 2008-11-27 Furukawa Circuit Foil Kk Electrolytic copper foil with high tensile-strength, and manufacturing method therefor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186893A (en) * 1987-01-27 1988-08-02 Sumitomo Metal Ind Ltd Copper plating method for electric conductor coil for electromagnetic transducing device
JPH0978638A (en) * 1995-09-13 1997-03-25 Aisin Seiki Co Ltd Rainwater utilizer
JP2004035918A (en) * 2002-07-01 2004-02-05 Nippon Denkai Kk Method of producing electrolytic copper foil
JP2004339559A (en) * 2003-05-14 2004-12-02 Kobe Steel Ltd Aluminum alloy sheet for calking, and its production method
JP2005197205A (en) * 2003-12-12 2005-07-21 Mitsui Mining & Smelting Co Ltd Negative electrode current collector for nonaqueous electrolytic solution secondary battery
JP2006152420A (en) * 2004-12-01 2006-06-15 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil and method for producing the same
JP2006299320A (en) * 2005-04-19 2006-11-02 Ls Cable Ltd High strength low roughness copper foil and method of manufacturing the same
CN101669237A (en) * 2007-04-20 2010-03-10 日矿金属株式会社 Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106536791A (en) * 2014-07-10 2017-03-22 Ls美创有限公司 Electrolytic copper foil and manufacturing method therefor, current collector for lithium secondary battery comprising electrolytic copper foil, and lithium secondary battery
TWI639731B (en) * 2014-07-10 2018-11-01 南韓商Ｋｃｆ科技有限公司 Electrolytic copper foil and method for producing the same, and current collector for lithium secondary battery and secondary battery comprising the electrolytic copper foil
CN108350588A (en) * 2015-09-25 2018-07-31 古河电气工业株式会社 Electrolytic copper foil and the various products for using the electrolytic copper foil
CN108350588B (en) * 2015-09-25 2020-03-17 古河电气工业株式会社 Electrolytic copper foil and various products using the same
TWI707062B (en) * 2015-09-25 2020-10-11 日商古河電氣工業股份有限公司 Electrolytic copper foil and various products using the electrolytic copper foil
CN108505076A (en) * 2017-02-24 2018-09-07 南亚塑胶工业股份有限公司 Electrolytic solution, electrolytic copper foil and method for producing same
CN108505076B (en) * 2017-02-24 2020-04-28 南亚塑胶工业股份有限公司 Electrolytic solution, electrolytic copper foil and method for producing same
CN110740580A (en) * 2018-07-18 2020-01-31 住友金属矿山株式会社 Copper-clad laminated board
CN110740580B (en) * 2018-07-18 2023-04-18 住友金属矿山株式会社 Copper-clad laminated board

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