CN104508878B - Lithium ion secondary battery negative pole collector body Copper Foil - Google Patents
Lithium ion secondary battery negative pole collector body Copper Foil Download PDFInfo
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- CN104508878B CN104508878B CN201480001959.5A CN201480001959A CN104508878B CN 104508878 B CN104508878 B CN 104508878B CN 201480001959 A CN201480001959 A CN 201480001959A CN 104508878 B CN104508878 B CN 104508878B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- 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
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Abstract
The present invention will improve the rust-preventing characteristic of the adaptation between Copper Foil (collector body) and active substance and Copper Foil, it is provided that a kind of lithium ion secondary battery negative pole collector body electrolytic copper foil and use this Copper Foil as the lithium rechargeable battery of negative electrode collector.The impurity contained in Copper Foil of the present invention, namely carbon, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, it is more preferably below 10ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm, less than 2.0nm, more preferably more than 0.2nm below 1.0nm.This Copper Foil forms organic rust preventing epithelium at copper foil surface, and NMP (N-N-methyl 2-pyrrolidone N-) contact angle is less than 15 °.
Description
Technical field
The present invention relates to a kind of lithium ion secondary battery negative pole collector body Copper Foil.
More particularly it relates to a kind of lithium ion secondary battery negative pole collector body Copper Foil forming organic rust preventing epithelium at copper foil surface.
Background technology
Lithium rechargeable battery has energy density height, can obtain the features such as high voltage, for instance be commonly used for the power supply of the miniaturized electronics such as notebook computer, videocorder, digital camera and mobile phone.Additionally, such as also begin to be used as the power supply of the main equipment such as electric motor car and general family decentralized layout type power supply.
So, owing to lithium rechargeable battery is compared with other secondary cell weight are lighter and energy density is higher, therefore just it is being widely used on the various equipment needing power supply.
As one of characteristic required for the Copper Foil as lithium ion secondary battery negative pole collector body, can enumerate and affect the adaptation between the negative electrode active material of lithium rechargeable battery cycle characteristics.
The active material layer not good with copper foil surface adaptation, when starching process, bending or rollback Copper Foil, it is possible to can active material layer is peeling-off, come off, it is impossible to reaches target capabilities, causes that durability and service life reduce.
Additionally, when active substance layer thickness is formed not uniformly, will there is lithium deposition and ingotism in this part, be easily short-circuited, it is difficult to charge at short notice.
As improving the conventional method of adaptation between active material layer, there is the physics ameliorative way that copper foil surface is carried out roughening treatment；Or copper foil surface is implemented antirust, forms the chemical ameliorative way etc. of silane coupled layer.
In patent documentation 1 (Japanese Patent Laid-Open 2012-212528 publication), as the cohesive with negative electrode active material, ultrasonic bonding and rust-preventing characteristic obtain the electrolytic copper foil for secondary battery anode collector that equilibrium improves, disclose a kind of lithium ion secondary battery negative pole collector body electrolytic copper foil, it forms the surface-treated layer with azole compounds and C=O at least some of of copper foil surface, when carrying out the analysis of depth direction side by XPS (X-ray photoelectron spectroscopic analysis), detect nitrogen (N) and carbon (C), and N and C detection limit is more than the depth bounds meansigma methods D of background value0It is 2.0～5.0nm.
But, lithium ion secondary battery negative pole collector body electrolytic copper foil disclosed in patent documentation 1, do not resolve for impurity whole content inevitable in Copper Foil, only nitrogen (N) and carbon (C) are considered as problem, other impurity, for instance sulfur (S), oxygen (O), chlorine (Cl) are not then investigated.
Additionally, the negative electrode of lithium rechargeable battery, it is that the active material slurry obtained after active material and binding agent being mixed with solvent is coated in conductive carrier (Copper Foil etc.), make it dry, if density need to be improved, then suppress bonding again, form active material layer.The surface of above-mentioned Copper Foil, by using the organic rust preventing of azole derivative to process or using the chromate of chromium compound class solution to process, implements antirust processing.
Form the solvent of described slurry, generally use N-N-methyl 2-pyrrolidone N-(NMP) and water etc..
But when solvent uses water, there is the slightly difference of the mixed proportion with binding agent, namely battery behavior the problem such as changes.
On the other hand, NMP then boiling point (202 DEG C) is relatively low, easy recycling, and belongs to the aprotic polar solvent with carbonyl, and dissolubility is high, can mix with various solvents, it is thus preferred to use.But as the Copper Foil of negative electrode carrier, the wettability between itself and NMP is poor, it is necessary to take to be coated with the special measures such as thick.
The active material contained in above-mentioned slurry and binding agent, lack the affinity with copper surface, and adaptation is low.
The negative electrode being made up of the active material layer not good with copper foil surface adaptation, when starching process, bending or rollback electrode, it is possible to can active material layer is peeling-off, come off, it is impossible to reaches target capabilities, causes that durability and service life go wrong.
As it has been described above, active substance non-uniform film thickness, when forming a layer of thinner thickness, will there is lithium deposition and ingotism in this part, be easily short-circuited, it is difficult to charge at short notice.
In patent documentation 2 (Japanese Patent Laid-Open 2008-251469 publication), as improving the method for adaptation between this Copper Foil and active substance, disclosing a kind of Copper Foil, it forms the azole compounds epithelium containing carbonyl at copper foil surface, and NMP contact angle is less than 19 °.
In patent documentation 2, describe the rolled copper foil by using more than 99.90% essence copper, in immersion isopropanol, normal alkane or its mixed liquor in the solution of interpolation ormal weight carbonyl benzotriazole after 5 seconds, air-supply is dry, then adds mono aminoethane or 1,2,3 benzotriazole, process equally.
But, in patent documentation 2, do not record the parsing for impurity inevitable in Copper Foil yet, do not investigate the copper foil surface wettability that inevitable impurity affects.That is, the Copper Foil recorded in patent documentation 2, does not inquire into when the inevitable total impurities contained in Copper Foil is more, and the wettability between Copper Foil and active material layer is poor, it is possible to cannot meet its function as collector body.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2012-212528 publication
Patent documentation 2: Japanese Patent Laid-Open 2008-251469 publication
Summary of the invention
(1) to solve the technical problem that
How the present inventor is to after improving and furtheing investigate as the adaptation between Copper Foil and the active substance of lithium ion secondary battery negative pole collector body and rust-preventing characteristic, find out the impurity contained in Copper Foil, the i.e. amount of carbon (C), sulfur (S), oxygen (O), nitrogen (N), chlorine (Cl), and the thickness of antirust epithelium, by the adaptation between appreciable impact collector body (Copper Foil) and active material layer, and complete the present invention.
The present invention is by the rust-preventing characteristic of the adaptation improved between Copper Foil and active substance and Copper Foil, it is provided that a kind of lithium ion secondary battery negative pole collector body surface treatment copper foil and use this surface treatment copper foil as the lithium rechargeable battery of collector body.
(2) technical scheme
The lithium ion secondary battery negative pole collector body surface treatment copper foil of the present invention, it is characterized in that, the carbon that contains in Copper Foil, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm, less than 2.0nm.
It addition, lithium ion secondary battery negative pole collector body Copper Foil is electrolytic copper foil.
That is, the carbon that contains in described Copper Foil, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, it is particularly preferred that for below 10ppm.
It is preferably more than 0.2nm by XPS (X-ray photoelectron spectroscopic analysis) depth bounds more than nitrogen and carbon background value detected, less than 2.0nm, it is particularly preferred that for more than 0.2nm below 1.0nm additionally, described.
(3) beneficial effect
According to Copper Foil of the present invention, using this Copper Foil as collector body, the cohesive between negative electrode active material will be improved.
Therefore, the Copper Foil of the present invention, for instance can suitably be used as the collector body of lithium rechargeable battery.
Detailed description of the invention
Hereinafter, embodiments of the present invention are illustrated.
The lithium ion secondary battery negative pole collector body Copper Foil of the present invention, it is characterized in that, the carbon that contains in Copper Foil, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS is more than 0.2nm, less than 2.0nm.
(copper foil base material)
In the present invention, " Copper Foil " is electrolytic copper foil.Below, it is not necessary to when distinguishing these Copper Foils, be simply termed as " Copper Foil ".
Though its foliation operation of Copper Foil, as inevitable impurity, all contain carbon (C), sulfur (S), oxygen (O), nitrogen (N), chlorine (Cl) all or part of.
Worsened wettability when this impurity level increases, between Copper Foil and the organic rust preventing epithelium coating copper foil surface, it is difficult to the antirust epithelium of even spread.
In present embodiment, as required, impose roughening treatment at copper foil surface, it is coated with organic rust preventing epithelium.
One of characteristic required for the lithium ion secondary battery negative pole collector body Copper Foil of the present invention, is the adaptation between active material layer.The lithium ion secondary battery negative pole electrode of present embodiment, it is that the active material slurry obtained after active substance such as material with carbon element and binding agent being mixed with solvent is coated on collector body (Copper Foil) so that it is dry, if density need to be improved, then suppress bonding again, form active material layer.Now, problematically, make the adaptation used in the solvent of slurry between NMP (N-N-methyl 2-pyrrolidone N-) active material slurry and the copper foil surface formed afterwards.
In the collector body Copper Foil of present embodiment, it is stipulated that the impurity level contained in Copper Foil.Especially, it is stipulated that impurity C, S, O, N, Cl (following, it is possible to can by these referred to as inevitable impurity) content adds up to below 20ppm.
Although its mechanism not yet solves bright, but it is believed that, the inevitable impurity level contained in Copper Foil is controlled at below 20ppm, when being because containing more than 20ppm inevitably impurity, electric repulsion will be produced between the organic solvents such as the NMP contained in the internal inevitably impurity element of Copper Foil and active material slurry, become big relative to the copper foil surface tension force of active material slurry, therefore the wettability and between active material slurry is poor, after being processed as lithium ion secondary battery negative pole, the adaptation between collector body and active material layer is deteriorated.
Inevitable impurity content is more few more good, as feasible value, it is preferred to below 15ppm, more preferably below 10ppm.
In the organic rust preventing layer of the Copper Foil of present embodiment, it is more than 0.2nm by XPS (X-ray photoelectron spectroscopic analysis) depth bounds more than nitrogen (N) and carbon (C) background value detected, less than 2.0nm.
In present embodiment, combination uses x-ray photoelectron spectroscopy (XPS instrument) and argon sputter, carries out the elementary analysis of Copper Foil depth direction, so that it is determined that the thickness of organic rust preventing layer.That is, N and C in organic rust preventing layer is detected by XPS instrument, and with N and the C detection limit depth bounds more than background value, as the thickness of surface-treated layer.
In view of the viewpoint of adaptation and rust-preventing characteristic, surface treatment layer thickness is preferably more than 0.2nm, less than 2.0nm, more preferably more than 0.5nm below 1.0nm.
When surface treatment layer thickness reaches more than 2.0nm, in the drying process etc. after coating anti-rust agent for treatment, part antirust one-tenth branch becomes powdery and exposes, consequently, it is possible to the adaptation between infringement and active substance.
For promoting the adaptation of the upper active material layer of collector body (Copper Foil), it is preferable that coat the organic rust preventing epithelium uniform film thickness of copper foil surface, and be high density epithelium.As the method at copper foil surface even spread organic rust preventing epithelium adhesion amount, present embodiment adopts the method being coated with hydrophilic cylinder.
As the method at copper foil surface even spread organic rust preventing epithelium, it is be arranged at hydrophilic cylinder to immerse in organic rust preventing treatment fluid (such as triazole solution), thus the Copper Foil tow sides of the coated organic rust preventing treatment fluid in surface, utilize this hydrophilic cylinder to carry out smooth (process), make the solution coating copper foil surface uniform.
After so using hydrophilic cylinder, can at copper foil surface even spread organic corrosion inhibitor.
By using hydrophilic cylinder when copper foil surface is coated with organic corrosion inhibitor, when Copper Foil contacts with treatment fluid, the drop for the treatment of fluid is racked, under same adhesion amount, also can form high density organic rust preventing epithelium, even if the therefore such thin skin film of the present invention, also can give full play to rustless property.As long as it addition, the uniform organic rust preventing epithelium of the high and thick degree of density can be formed, then may be used without the coating process beyond hydrophilic cylinder.
In addition, after so becoming epithelium with hydrophilic drum-shape, leather film thickness can be made uniform, and the resistivity of copper foil surface can be reduced, even if being therefore resistance welded when assembling negative electrode, also can suppress the Joule heat consumption in antirust epithelium, make Joule heat suitably supply the inside to overlapping paper tinsel such that it is able to obtain good resistance welding.
Hydrophilic cylinder is such as rubber cylinder, by methods such as the chemical modifications of UV ozonization, plasma treatment and hydrophilic functional group, cylinder surface is implemented hydrophilicity-imparting treatment.This cylinder is used to be coated with organic antirust treatment liquid, it is possible to form the film that organic corrosion inhibitor adhesion amount is seldom uneven.
As being coated with organic corrosion inhibitor with the cylinder without hydrophilicity-imparting treatment at copper foil surface, when then Copper Foil contacts with treatment fluid, the drop size for the treatment of fluid is big, treatment fluid composition diffuses in drop, therefore, it is difficult to even spread, even if adhesion amount same in unit are, adhesion amount deviation therein is likely to bigger.The Copper Foil that adhesion amount deviation is big, at leather film thickness thin location, cavity (aperture) may occur part epithelium, thus occurring that under keeping and transportation environment (point-like is got rusty) is got rusty in local, on the other hand, at attachment thicker part, remove required heat energy or vibrational energy during epithelium bigger, therefore the ultrasonic bonding that to operation behind, may namely assemble negative electrode produces harmful effect.
As organic rust preventing epithelium, the triazole compounds such as benzotriazole, tolyl-triazole, carboxyl benzotriazole, chlorobenzotriazole, ethyl benzotriazole, aphthotriazoles and its complex can be enumerated.
By forming the triazole compounds of organic rust preventing epithelium at copper foil surface or/and the organic rust preventing compound solution (being likely to below be called triazole compounds solution) that forms of its complex, its concentration is preferably 50～1000ppm.Its reason is in that, if lower than 50ppm, then the organic rust preventing epithelium formed, its thickness is not enough to maintain antirust function, and on the other hand, if more than 1000ppm, then organic rust preventing leather film thickness is excessive, it is possible to above-mentioned supersonic welding connection function etc. can be produced harmful effect.
Additionally, when copper foil surface forms organic rust preventing epithelium, the temperature of triazole compounds solution is preferably 35 DEG C～55 DEG C.Its reason is in that, if lower than 35 DEG C, then the organic rust preventing epithelium formed, its density is not enough to maintain antirust function, and on the other hand, if higher than 55 DEG C, then organic rust preventing epithelium density is too high.
And then, for guaranteeing the stability of triazole composition, the pH value of triazole compounds solution is preferably 6.5～8.0.
Coat the soak time etc. of the conditions such as the concentration of triazole compounds solution on Copper Foil, temperature, pH value and Copper Foil, suitably can determine according to the relation between the thickness of formed organic rust preventing epithelium.It addition, usual about 0.5～30 second of soak time.
But the relevant of these antirust treatment conditions is recited as illustration, do not limit the content of description and claim.
In present embodiment, it is immerse immediately organic rust preventing agent solution is formed antirust epithelium after electrolytic copper foil foliation, but when cannot implement antirust treatment immediately after foliation, pickling or defat can be implemented as pre-treatment.
When implementing pickling, comparatively effective acid washing method is to immerse H2SO4=5～200g/l (litre), temperature=10 DEG C～80 DEG C dilute sulfuric acid in.
Additionally, when implementing defat, comparatively effective degreasing method be NaOH=5～200g/l, temperature=10 DEG C～80 DEG C aqueous solution in, according to electric current density=1～10A/dm2, time=condition of 0.1 minute～5 minutes, implement negative electrode and/or anode electrolysis defat.
In present embodiment, using above-mentioned Copper Foil as collector body, it is formed negative electrode active material layer, makes negative electrode, be then inserted into this negative electrode, make lithium rechargeable battery.
As negative electrode active material, and indefinite, carbon, silicon, stannum, germanium, lead, antimony, aluminum, indium, lithium, stannum oxide, lithium titanate, lithium nitride, the stannum oxide of solid solution indium, indium stannum alloy, lithium-aluminium alloy and lithium indium alloy etc. can be enumerated.
Hereinafter, by embodiment 1～9 and comparative example 1～6, the present invention is illustrated.
(foliation of Copper Foil)
(embodiment 1～9)
(comparative example 1～4)
Embodiment 1～9 and comparative example 1～4 are that anode uses the Ti electrode covering metal oxide containing precious metals according to condition shown below, and negative electrode uses titanium rotary drum, makes electric current density 50～100A/dm2, thickness 10 μm electrolytic copper foil.
Copper: 70～130g/l
Sulphuric acid: 80～140g/l
Additive: 3-mercaptopropanesulfonic acid sodium salt=1～10ppm
Hydroxyethyl cellulose=1～100ppm
Low-molecular-weight glue (molecular weight 3,000)=1～50ppm
Chloride ion concentration=10～50ppm
Temperature: 50～60 DEG C
(comparative example 5～6)
Comparative example 5～6 is by the low molecule glue (molecular weight 3 of embodiment 1～9 and comparative example 1～4,000) addition changes into more than 50ppm and the scope lower than 500ppm, anode uses the Ti electrode covering metal oxide containing precious metals, and negative electrode uses titanium rotary drum, makes electric current density 50～100A/dm2, thickness 10 μm electrolytic copper foil.
(formation of organic rust preventing epithelium)
(embodiment 1～9)
Embodiment 1～9 is that the Copper Foil that electrolysis foliation is formed is immersed more than concentration 50ppm immediately, in benzotriazole rust inhibiting solution less than 1000ppm, use 2 commercially available SUS304 cylinders (diameter 120mm, face length 1000mm, wall thickness 15mm) carrying out plasma treatment with the NVC-R1500 of Co., Ltd.'s day electric discharge son production, coating two sides, and control organic coating amount to be fixed amount, form organic rust preventing epithelium at copper foil surface.It addition, liquid temperature is 35～55 DEG C, pH value is 6.5～8.0.
(comparative example 1～2)
Comparative example 1～2 is to immerse in the benzotriazole rust inhibiting solution of concentration 10～50ppm immediately by the Copper Foil that electrolysis foliation is formed, use 2 commercially available SUS304 cylinders (diameter 120mm, face length 1000mm, wall thickness 15mm) carrying out plasma treatment with the NVC-R1500 of Co., Ltd.'s day electric discharge son production, coating two sides, and control organic coating amount to be fixed amount, form organic rust preventing epithelium at copper foil surface.It addition, liquid temperature is 35～55 DEG C, pH value is 6.5～8.0.
(comparative example 3～4)
Comparative example 3～4 is to immerse in the benzotriazole rust inhibiting solution of concentration 1000～5000ppm immediately by the Copper Foil that electrolysis foliation is formed, use 2 commercially available SUS304 cylinders (diameter 120mm, face length 1000mm, wall thickness 15mm) carrying out plasma treatment with the NVC-R1500 of Co., Ltd.'s day electric discharge son production, coating two sides, and control organic coating amount to be fixed amount, form organic rust preventing epithelium at copper foil surface.It addition, liquid temperature is 35～55 DEG C, pH value is 6.5～8.0.
(comparative example 5～6)
Comparative example 5～6 is that the Copper Foil that electrolysis foliation is formed is immersed more than concentration 50ppm immediately, in benzotriazole rust inhibiting solution less than 1000ppm, use 2 commercially available SUS304 cylinders (diameter 120mm, face length 1000mm, wall thickness 15mm) carrying out plasma treatment with the NVC-R1500 of Co., Ltd.'s day electric discharge son production, coating two sides, and control organic coating amount to be fixed amount, form organic rust preventing epithelium at copper foil surface.It addition, liquid temperature is 35～55 DEG C, pH value is 6.5～8.0.
(formation of active material layer and the assessment of adaptation)
For the surface of the surface treatment copper foil made in the various embodiments described above, each comparative example, use the active material slurry being made up of following material with carbon element, the adaptation between following assessment Copper Foil and active substance.
Shown in its result such as table 1 (embodiment) and table 2 (comparative example).
As material with carbon element, use engineered stone ink, by this engineered stone ink with dissolved 8%PVDF (Kynoar) powder in NMP after the solution of acquisition mix, form pulp-like, by this slurry coating about 50 μ m thick to copper foil surface, carry out prolonging pressure after dry 3 hours at 80 DEG C, then vacuum drying again.
Sticking double faced adhesive tape at this active substance coated face, gripper shoe also sticks double faced adhesive tape these two pieces of double faced adhesive tapes of fitting.Then, according to the JISC6471 method specified, peel strength is measured with peel angle 90 degree.
In table 1 and table 2, bonding strength is ◎, more than 3000g/cm more than 4000g/cm person, is zero less than 4000g/cm person, more than 1000g/cm, is △ less than 3000g/cm person, less than 1000g/cm person be ×.
(the detection depth bounds of nitrogen and carbon measures)
The detection depth bounds of nitrogen and carbon, is the XPS determinator 5600MC using ULVAC-PHI Co., Ltd. to produce, is measured according to following condition.
Arrive vacuum: 1 × 10-10Torr (import argon time 1 × 10-8Torr)
X ray: X ray monochromatization Al-k alpha ray
Output: 300W
Area of detection:
Ion line: ionic species Ar+
Accelerating potential: 3kV
Scan area: 3 × 3mm2
Test portion angle of incidence: 45 ° (angle between test portion and detector)
Sputter rate: 2.3nm/ minute (SiO2Conversion)
(mensuration of impurity level)
The impurity element contained in Copper Foil, is use following assay method and determinator to be measured.
C, S: burning-infrared absorption, CS844 (LECO company system)
O, N: inert gas fusion-thermal conductivity method, ONH836 (LECO company system)
Cl: hot hydrolyzable-ion chromatography, DX-500 (Dionex company of Japan system)
(assessment of non-oxidizability)
According to following methods, the non-oxidizability of assessment Copper Foil.
(1) Copper Foil (70mm × 300mm) is wrapped on polyvinyl chloride pipe (internal diameter 32mm, external diameter 38mm, long 10cm), makes test portion.
(2) test portion made in (1) being processed is located on constant temperature and humidity machine (60 DEG C, 90RH%), keeps 5 days (120 hours).
(3) by test portion from carrying out taking-up the testing machine that (2) process, the tone of Copper Foil and Copper Foil lap on copper foil surface is confirmed.
(4) appraisal procedure is, compared with before test, the unchanged person of tone is zero, hence it is evident that become blue or purpling person into ×.
(table 1)
Embodiment
(table 2)
Comparative example
In embodiment 1～5, impurity level amounts to and controls at below 10ppm, and the detection depth bounds of nitrogen and carbon controls at more than 0.2nm, and less than in the scope of 2.0nm, therefore the adaptation of active substance is good.
In embodiment 6～9, although impurity level amounts to more than 10ppm, but still controlling at below 20ppm, and the detection depth bounds of nitrogen and carbon controls at more than 0.2nm, less than in the scope of 2.0nm, therefore the adaptation of active substance is better.
In comparative example 1～2, although use the cylinder carrying out hydrophilicity-imparting treatment with plasma, but antirust composition epithelium only 0.1nm, thickness is not enough.Therefore, in the drying process after coat activated material, the oxide-film of copper foil surface increases substantially, and therefore the adaptation of active substance is slightly poor.
In comparative example 3～4, antirust composition epithelium is blocked up, more than 2.0nm, even if using the cylinder carrying out hydrophilicity-imparting treatment with plasma, also cannot guarantee the uniformity of epithelium, it is impossible to even spread active material slurry.Therefore, the adaptation of active substance is slightly poor.
In comparative example 5～6, in paper tinsel, impurity level is too much, reaches more than 55ppm, even if therefore optimizing the leather film thickness of the antirust composition of copper foil surface, and use the cylinder enforcement process carrying out hydrophilicity-imparting treatment with plasma, also cannot guarantee the uniformity of epithelium, it is impossible to even spread active material slurry.Therefore, the adaptation of active substance is slightly poor.
In sum, the copper foil surface of the present invention has the surface treatment copper foil of surface treatment epithelium, the impurity contained in its Copper Foil, namely carbon, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm, less than 2.0nm, the cohesive therefore and between negative electrode active material promotes.
In addition, the impurity contained in Copper Foil, namely carbon, sulfur, oxygen, nitrogen, chlorine content add up to below 10ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm, less than 2.0nm, the cohesive therefore and between negative electrode active material promotes.
In addition, the carbon that contains in Copper Foil, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm below 1.0nm, the cohesive therefore and between negative electrode active material promotes.
In addition, the impurity contained in Copper Foil, namely carbon, sulfur, oxygen, nitrogen, chlorine content add up to below 10ppm, and the depth bounds more than nitrogen and carbon background value detected by XPS (X-ray photoelectron spectroscopic analysis) is more than 0.2nm below 1.0nm, the cohesive therefore and between negative electrode active material promotes.
Industrial applicibility
The Copper Foil of the present invention such as can be suitable as the collector body of lithium rechargeable battery.
Claims (5)
1. a lithium ion secondary battery negative pole collector body surface-treated electro-deposited copper foil, it has surface treatment epithelium at electrolytic copper foil surface, the carbon that contains in this electrolytic copper foil, sulfur, oxygen, nitrogen, chlorine content add up to below 20ppm, and by XPS and X-ray photoelectron spectroscopic analysis, the depth bounds more than nitrogen and carbon background value detected is more than 0.2nm, less than 2.0nm.
2. lithium ion secondary battery negative pole collector body surface-treated electro-deposited copper foil according to claim 1, it is characterised in that the carbon that contains in this electrolytic copper foil, sulfur, oxygen, nitrogen, chlorine content add up to below 10ppm.
3. lithium ion secondary battery negative pole collector body surface-treated electro-deposited copper foil according to claim 1, it is characterized in that, by described XPS and X-ray photoelectron spectroscopic analysis, the depth bounds more than nitrogen and carbon background value detected is more than 0.2nm below 1.0nm.
4. lithium ion secondary battery negative pole collector body surface-treated electro-deposited copper foil according to claim 3, it is characterised in that the carbon that contains in described electrolytic copper foil, sulfur, oxygen, nitrogen, chlorine content add up to below 10ppm.
5. lithium ion secondary battery negative pole collector body electrolytic copper foil according to any one of claim 1 to 4, it is characterised in that at described electrolytic copper foil surface, formed the organic rust preventing epithelium of uniform film thickness by hydrophilization process.
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| JP2013-095164 | 2013-04-30 | ||
| JP2013095164 | 2013-04-30 | ||
| PCT/JP2014/061567 WO2014178327A1 (en) | 2013-04-30 | 2014-04-24 | Copper foil for lithium-ion secondary battery negative electrode collector |
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| CN104508878A CN104508878A (en) | 2015-04-08 |
| CN104508878B true CN104508878B (en) | 2016-06-29 |
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| JP (1) | JP5625141B1 (en) |
| KR (1) | KR20150086222A (en) |
| CN (1) | CN104508878B (en) |
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| JP6440656B2 (en) * | 2016-07-12 | 2018-12-19 | 古河電気工業株式会社 | Electrolytic copper foil |
| KR102136794B1 (en) | 2017-03-09 | 2020-07-22 | 케이씨에프테크놀로지스 주식회사 | Copper foil having improved adheshion property, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| JP6963606B2 (en) * | 2017-05-18 | 2021-11-10 | 富士フイルム株式会社 | Manufacturing method of perforated metal foil |
| KR102184170B1 (en) | 2017-07-25 | 2020-11-27 | 주식회사 엘지화학 | Copper foil for secondary battery, method thereof and Secondary battery comprising the same |
| KR102473030B1 (en) | 2017-08-30 | 2022-11-30 | 에스케이넥실리스 주식회사 | Copper Film, Manufacturing Methods Thereof, And Anode For Li Secondary Battery Comprising The Same |
| JP2019175802A (en) * | 2018-03-29 | 2019-10-10 | Ｊｘ金属株式会社 | Rolled copper foil for lithium ion battery current collector and lithium ion battery |
| US11365486B2 (en) | 2018-10-16 | 2022-06-21 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil, electrode comprising the same, and lithium ion battery comprising the same |
| JP7100560B2 (en) * | 2018-10-29 | 2022-07-13 | Ｊｘ金属株式会社 | Lithium-ion battery Rolled copper foil for collector and lithium-ion battery |
| KR102528069B1 (en) | 2018-12-10 | 2023-05-03 | 닛폰 덴카이 가부시키가이샤 | Electrolytic copper foil and its manufacturing method |
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| CN102498600A (en) * | 2009-09-11 | 2012-06-13 | Jx日矿日石金属株式会社 | Copper foil for lithium ion battery current collector |
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| JP3850155B2 (en) * | 1998-12-11 | 2006-11-29 | 日本電解株式会社 | Electrolytic copper foil, copper foil for current collector of secondary battery and secondary battery |
| JP3850321B2 (en) * | 2002-03-19 | 2006-11-29 | 日本電解株式会社 | Secondary battery |
| JP5081481B2 (en) * | 2007-03-30 | 2012-11-28 | Ｊｘ日鉱日石金属株式会社 | Copper foil with excellent wettability and method for producing the same |
| JP4943370B2 (en) * | 2008-04-09 | 2012-05-30 | 日本電信電話株式会社 | Impression degree estimation method and apparatus and program and program for content viewing and computer-readable recording medium |
| JP5219952B2 (en) * | 2009-07-17 | 2013-06-26 | Ｊｘ日鉱日石金属株式会社 | Copper foil for lithium-ion battery current collector |
| JP2012051768A (en) * | 2010-09-02 | 2012-03-15 | Toshimichi Ito | Diamond semiconductor |
| JP5427752B2 (en) * | 2010-11-02 | 2014-02-26 | Ｊｘ日鉱日石金属株式会社 | Copper foil for lithium-ion battery current collector |
| JP5148726B2 (en) * | 2011-03-30 | 2013-02-20 | Ｊｘ日鉱日石金属株式会社 | Electrolytic copper foil and method for producing electrolytic copper foil |
| JP5512585B2 (en) * | 2011-03-30 | 2014-06-04 | Ｊｘ日鉱日石金属株式会社 | Copper foil, anode current collector and anode material for lithium ion secondary battery using the same, and lithium ion secondary battery |
| JP2012212558A (en) * | 2011-03-31 | 2012-11-01 | Panasonic Corp | Battery module |
| JP2013133514A (en) * | 2011-12-27 | 2013-07-08 | Furukawa Electric Co Ltd:The | Copper foil, electrode for secondary battery, secondary battery, and printed circuit board |
| JP5981165B2 (en) * | 2011-12-27 | 2016-08-31 | 古河電気工業株式会社 | Copper foil, negative electrode of secondary battery, secondary battery, and printed circuit board |
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| JPWO2014178327A1 (en) | 2017-02-23 |
| TWI593826B (en) | 2017-08-01 |
| JP5625141B1 (en) | 2014-11-12 |
| KR20150086222A (en) | 2015-07-27 |
| TW201510277A (en) | 2015-03-16 |
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| WO2014178327A1 (en) | 2014-11-06 |
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