CN106340668A - Electrolytic copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents
Electrolytic copper foil, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDFInfo
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- CN106340668A CN106340668A CN201610412852.0A CN201610412852A CN106340668A CN 106340668 A CN106340668 A CN 106340668A CN 201610412852 A CN201610412852 A CN 201610412852A CN 106340668 A CN106340668 A CN 106340668A
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- copper foil
- electrolytic copper
- collector
- ion secondary
- secondary battery
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- 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
- 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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides an electrolytic copper foil which has excellent operability in manufacturing a secondary battery and has stretching strength that does not reduce after heating at a temperature of 150 DEG C for one hour, a negative electrode for a lithium ion secondary battery with prolonged service life through using the electrolytic copper foil as a current collector, and a lithium ion secondary battery with the electrode. The electrolytic copper foil has glossiness Gs(60 DEG C) of 20-150 on a rough surface and a kinetic friction coefficient of 0.11-0.39. Furthermore after heating at a temperature of 150 DEG C for one hour, a stretching strength of the electrolytic copper foil is above 350MPa. In the lithium ion secondary battery, the electrolytic copper foil is used as the current collector.
Description
Technical field
The present invention relates to a kind of electrolytic copper foil and using this electrolytic copper foil lithium (li) ion secondary battery negative electrode and
Lithium rechargeable battery.
In addition, the invention still further relates to a kind of printed circuit board (PCB) of the electrolytic copper foil employing the present invention and electromagnetic shielding material
Material.
Background technology
Lithium rechargeable battery is for example made up of positive pole, negative pole and nonaqueous electrolyte, described negative pole negative electrode collector (with
Down be referred to as collector) surface be formed with negative electrode active material layer, this lithium rechargeable battery be mainly used in portable phone,
Notebook computer etc..
The negative pole of lithium rechargeable battery is formed as follows, i.e. not yet enter using to after being manufactured by electrolysis
So-called " the untreated Copper Foil " of the process such as row surface treatment implements the Copper Foil of antirust treatment, in the table of Copper Foil (negative electrode collector)
Face applies carbon granule as negative electrode active material layer etc. and is dried, and is suppressed further.
In order that lithium rechargeable battery obtain sufficient battery behavior it is important that reduce active material particle between away from
From and active substance and collector with a distance from, and the shape of collector carries out deformation according to the shape of active material surface.?
In the case that collector carries out deformation according to the shape of active material surface, active substance can become more with the contact of collector
Good, electrical conductivity can become much larger, thus can get desired battery behavior.In collector not according to the shape of active material surface
In the case that shape carries out deformation, active substance is reduced with the contact site branch of collector, and electrical conductivity can reduce, thus cannot get institute
Desired battery behavior.
In addition, collector surface concavo-convex big in the case of, active substance can reduce with the contact point of collector, contacts
Resistance can increase.If the big electrode of this contact resistance is repeated discharge and recharge, can be because active substance be along with discharge and recharge
Dilation and cause stress, as the binding agent of bonding agent, to be dissolved into electrolyte medium, thus makes collector and activity
The distance of material can be gradually increased, and the electrical conductivity of a part of active substance can become the electrical conductivity that cannot be used in discharge and recharge, from
And cause the reduction of battery capacity.Therefore, in negative electrode collector, preferably use tensile strength more than setting and two sides more
Plus smooth Copper Foil (patent documentation 1,2,3).
But, the high speed of the transporting velocity from the viewpoint of productivity ratio it is desirable to battery manufacturing process in recent years, if
Use the more smooth electrolytic copper foil in two sides as the negative electrode collector of lithium rechargeable battery, then the Copper Foil smoothing is in activity
Easily skid on conveying roller in material Coating Production Line, it is possible to because of skidding in Copper Foil (collector) upper generation pleat
Wrinkle, or generation problem etc. in the working procedure of coating of active substance.
In addition, in order to the small-sized/lightweight of lithium rechargeable battery is it is desirable to the electrolytic copper foil thinning as collector.
When carrying out the thinning of Copper Foil, need to bear due to the dilation of the active substance in charge and discharge process to cause
Stress, if collector cannot bear the dilation of active substance, that can bring that the cycle characteristics of battery reduces is unfavorable
Impact.Therefore, the high intensity of Copper Foil becomes important problem.In addition, the composition forming existing carbons on the current collector is born
During the active material layer of pole, make by the carbon as negative electrode active material, the polyvinylidene fluoride resin as binding agent, as molten
The paste that the n- methyl pyrrolidone of agent is constituted, is coated on the two sides of Copper Foil (collector) and is dried.In this situation
Under, in order to the temperature at 150 DEG C about is dried, as the paper tinsel of the dilation of the active substance that can bear during discharge and recharge
Intensity, preferably evaluated with the intensity after carrying out heat treated at 150 DEG C.
As its countermeasure, the tensile strength of the collector after needing to make heat treated is more than setting.
In addition, recently it is desirable to following printing in the printed circuit board (PCB)s such as printed circuit board, flexible printed circuit board
Circuit board, its Copper Foil with intermembranous there is higher adhesion strength while to have excellent high frequency required by circuit substrate special
Property.
Furthermore it is required that thickness of thin and there is the Copper Foil of intensity, particularly require the manufacture work in flexible printed circuit board
It is difficult in skill produce the Copper Foil of paper tinsel fracture, fold etc..
Even if in addition, also requiring the thermal history that experienced when manufacturing printed circuit board (PCB) to be also able to maintain that the Copper Foil of high intensity.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent No. 3742144；
Patent documentation 2: Japanese Patent No. 5255229；
Patent documentation 3: Japanese Unexamined Patent Publication 2014-224321.
Content of the invention
(1) technical problem to be solved
It is an object of the invention to, even if providing a kind of tensile strength to heat 1 hour tensile strength at 150 DEG C
Will not reduce, control glossiness and the coefficient of kinetic friction electrolytic copper foil and by this electrolytic copper foil be used as the lithium of collector from
Sub- secondary cell negative electrode and lithium rechargeable battery.
In addition, it is an object of the invention to, provide a kind of Copper Foil, this Copper Foil has in printed circuit board, flexible print
Copper Foil required by the printed circuit board (PCB) of printed circuit board etc. and intermembranous higher adhesion strength, high frequency characteristics, thickness of thin and tool
There is intensity, in addition, be particularly difficult to produce paper tinsel fracture, fold etc. in the manufacturing process of flexible printed circuit board.
In addition, it is an object of the invention to, even if providing a kind of thermal history that experienced when manufacturing printed circuit board (PCB) also can
Enough maintain the Copper Foil of high intensity.
(2) technical scheme
The electrolytic copper foil of the present invention is characterised by, glossiness gs (60 °) of hair side (m face), less than 150 more than 20, is moved
Coefficient of friction less than 0.39 more than 0.11,150 DEG C heating 1 hour after tensile strength more than 350mpa 900mpa with
Under.
(60 °) of glossiness gs represents the glossiness receiving optic angle mensure with 60 ° of transmitting.
Tensile strength after 150 DEG C of heat treatments implementing 1 hour for the electrolytic copper foil of preferred the invention described above exists
More than 400mpa.
The lithium rechargeable battery negative electrode of the present invention is using the electrolytic copper foil of the invention described above as negative electrode collector.
In addition, the lithium rechargeable battery of the present invention be including using the electrolytic copper foil of the invention described above as negative electrode collector
Negative electrode secondary cell.
In addition, the printed circuit board (PCB) of the present invention using above-mentioned electrolytic copper foil as electric conductor.
And then, the electromagnetic shielding material of the present invention is using above-mentioned electrolytic copper foil as shielding material.
(3) beneficial effect
In accordance with the invention it is possible to provide a kind of electrolytic copper foil it is characterised in that hair side glossiness gs (60 °) 20 with
Upper less than 150, less than 0.39 more than 0.11, the tensile strength after this Copper Foil heats 1 hour at 150 DEG C exists the coefficient of kinetic friction
More than 350mpa below 900mpa.
Additionally, glossiness is generally dependent on surface configuration of the following yardstick of wavelength of visible region etc., in addition, dynamic friction
Coefficient is generally dependent on surface configuration (concavo-convex), the chemical state on surface (also includes the suction of the additive component of Copper Foil most surface
Attached etc.) etc..
For the surface configuration of the following yardstick of this wavelength, the chemical state on surface etc., also it is difficult at present quantitatively represent energy
Enough scopes most preferably playing the effect of the present invention, but can be represented exactly by determining glossiness and the coefficient of kinetic friction
The scope of the effect of the present invention can be played.
In addition, according to the present invention, by using above-mentioned electrolytic copper foil as negative electrode collector, using the teaching of the invention it is possible to provide a kind of active substance
Secondary cell good with the contact of collector, that electrical conductivity is high, cycle life is good.
And then, by making glossiness gs (60 °) of the hair side of the electrolytic copper foil of composition collector less than 150 more than 20,
So as to make the small concavo-convex of collector surface play anchoring effect with active material particle when sticking, suppression is in charge and discharge
In electric cyclic process, active substance carries out active substance during dilation and comes off from collector, thus provides a kind of cycle life good
Good secondary cell.
In addition, by make the electrolytic copper foil of the composition collector tensile strength after 150 DEG C of heating 1 hour 350mpa with
Above such that it is able to provide a kind of can bearing to cause because the volume of active substance carries out dilation in charge and discharge process
Stress and the good secondary cell of cycle life.
And then, by above-mentioned electrolytic copper foil is pasted onto on dielectric film such that it is able to provide a kind of following printed circuit
Plate (printed circuit board, flexible printed circuit board etc.), its by be present in the minute asperities of copper foil surface and Copper Foil with
Insulation is intermembranous to have higher adhesion strength, and has the outstanding high frequency characteristics required by circuit substrate, for instance, it is possible to anti-
Stop delay of the resistance loss increase being led to when applying high-frequency signal and signal propagation etc. by Kelvin effect.
Additionally, the thickness of thin of the electrolytic copper foil of the present invention and there is intensity, particularly, in the manufacture of flexible printed circuit board
It is difficult in technique produce paper tinsel fracture, fold etc., flexible printed circuit board can be preferably used for.In addition, by making Copper Foil 150
Tensile strength after DEG C heating 1 hour in more than 350mpa, even if thus experienced thermal history when manufacturing printed circuit board (PCB),
It is able to maintain that high intensity.
The contact resistance of the electrolytic copper foil of the present invention is less, and high frequency characteristics is excellent, also has excellent as electromagnetic shielding material
Different effect.
In addition, in any one above-mentioned purposes, by making glossiness gs (60 °) of the hair side of electrolytic copper foil more than 20
Less than 150 and the coefficient of kinetic friction less than 0.39 more than 0.11, thus absorption exists during the small concavo-convex and manufacturing copper foil on surface
The organic additive of Copper Foil most surface becomes anti-skidding on the conveying roller in active substance Coating Production Line when manufacturing battery etc.
Thing, suppression paper tinsel skids on conveying roller, and therefore its operability is good.
Specific embodiment
(structure of electrolytic copper foil)
For the electrolytic copper foil constituting lithium rechargeable battery collector, an embodiment of the invention is said
Bright.But, the electrolytic copper foil of the present invention cannot be only used for lithium rechargeable battery collector, in the scope not changing its purport
Interior, other purposes such as electric conductor of printed circuit board (PCB), electromagnetic shielding can also be appropriately used for.
The lithium ion secondary battery negative pole collector electrolytic copper foil of present embodiment is implemented at the heat of 1 hour at 150 DEG C
Tensile strength after reason in more than 350mpa, particularly preferably in more than 400mpa such that it is able to provide one kind can bear due to
During discharge and recharge, caused stress and the good secondary cell of cycle life are shunk in the volumetric expansion of active substance.
In addition, the lithium ion secondary battery negative pole collector of present embodiment electrolytic copper foil is for example, at least in electrolytic copper foil
The surface of the side being provided with active material layer be provided with antirust treatment layer.
Antirust treatment layer be, for example, chromating layer or be ni or ni alloy layer, co or co alloy layer, zn or
Zn alloy layer, sn or sn alloy layer, to be further provided with chromating layer etc. on above-mentioned various coating inorganic antirust
Process layer, then or the organic rust preventing process layer such as benzotriazole.
And then it is also possible to it is formed with silane coupler process layer etc..
Above-mentioned inorganic antirust treatment, organic rust preventing are processed, silane coupler processes to play and improves negative electrode collector and activity
The adhesion strength of material, prevent the effect that the charge and discharge cycles efficiency of battery reduces.
In addition, lithium ion secondary battery current collector electrolytic copper foil such as being provided with electrolytic copper foil of present embodiment
Roughening treatment is implemented on the surface of the electrolytic copper foil of active material layer, and the surface implementing this roughening treatment is provided with antirust treatment
Layer, and then it has been arranged as required to silane coupler process layer.
Less than 150 more than 20, the coefficient of kinetic friction exists glossiness gs (60 °) of the hair side of the electrolytic copper foil of present embodiment
Less than more than 0.11 0.39.
Additionally, (60 °) of gs represents receives, with 60 ° of transmitting, the glossiness that optic angle measures.
Glossiness gs (60 °) why making the hair side of electrolytic copper foil less than 150 more than 20, is because, below 20
The concavo-convex of electrolytic copper foil (collector) surface will become big, thus active substance is tailed off with the contact point of collector, become contact electricity
Hinder big electrode, therefore, if discharge and recharge is repeated, because active substance is carried out caused by dilation along with discharge and recharge
Stress, be dissolved into that electrolyte is medium as the binding agent of bonding agent, collector is become larger with the distance of active substance, and having can
The electrical conductivity that a part of active substance can be made becomes the electrical conductivity that cannot be used in discharge and recharge, thus causing the capacity of secondary cell
Reduce, therefore it is not preferred.
On the other hand, make glossiness gs (60 °) below 150, be in order that electrolytic copper foil has adhesion and anchoring effect
Really.
In addition, making glossiness gs (60 °) of the hair side of the electrolytic copper foil of present embodiment less than 150 more than 20, make
Coefficient of friction is less than 0.39 more than 0.11.Arranged by such, so that active substance is good with the contact of collector, electric
Conductance improves, and can get good cycle life.
Skidding on conveying roller for the Copper Foil in battery manufacturing process, the generation of fold depend on Copper Foil surface configuration and
Chemical state.But, the measured value of the surface roughness being only representative in order to 10 points of average surface roughness rz can not be abundant
Ground is evaluated to this.This is because, generally use, when measuring rz, the contact pin type roughness gauge that top end diameter is 2 μm, in principle
Can not measure less than contact pilotage concavo-convex.In addition, for solving this problem, also there are as below methods, i.e. show using with confocal point type laser
Micro mirror is that the optical measuring method of representative is measured to comprising less concavo-convex surface configuration.But, for the method,
Although can evaluate to surface configuration, do not include the impact of surface chemistry conditions, therefore cannot be to Copper Foil in conveying
The skidding producing on roller, fold are sufficiently carried out evaluating.
In this regard, present inventors found that, evaluate more glossiness gs (60 °) of the surface configuration of microcosmic and dynamic friction
Coefficient can be sufficiently carried out evaluating to the skidding that Copper Foil produces on conveying roller, fold.Specifically, by making the hair of Copper Foil
Glossiness gs (60 °) in face is less than 150 more than 20, and makes the coefficient of kinetic friction less than 0.39 more than 0.11, thus in battery
The small concavo-convex and absorption making copper foil surface on active substance Coating Production Line in manufacturing process is in Copper Foil most surface
Organic additive becomes the anti-skidding thing on conveying roller, Copper Foil can be suppressed to skid on conveying roller, copper on battery manufacture production line
Paper tinsel will not produce fold, so that operability becomes good.In addition, this small concavo-convex is sent out between active substance and collector
Wave anchoring effect, the adhesion to raising active substance is also effective.
That is, less than 150 more than 20, the coefficient of kinetic friction is 0.39 more than 0.11 for glossiness gs (60 °) in hair side (m face)
When hereinafter, less than 0.35 more preferably more than 0.15, operability is good, draws less than 150 more than 20 in glossiness gs (60 °)
Stretch intensity (before and after heating) in more than 350mpa, battery behavior is good.
Additionally, with regard to bright finish (s face), by controlling the surface configuration of electrolysis drum, can also control with comparalive ease in the past
Glossiness, the coefficient of kinetic friction, but in the present invention, it is conceived to the glossiness of unmanageable hair side and dynamic friction system in the past
Number is it is achieved that two sides all has the glossiness of regulation and the electrolytic copper foil of the coefficient of kinetic friction.
(manufacture method of electrolytic copper foil)
The lithium ion secondary battery negative pole collector of present embodiment for example can be made by the following method with electrolytic copper foil
Make, i.e. using sulphuric acid-copper sulfate solution as electrolyte, by this electrolyte supply to insoluble anode and titanium cathode drum it
Between, this insoluble anode is constituted by with the titanium of platinum metal element or its oxide cladding, this titanium cathode drum and this anode phase
To ground setting, so that cathode drum is rotated with fixed speed, pass through DC current in two interpolars simultaneously, thus make copper precipitate into cathode drum
On surface, the copper of precipitation is peeled from cathode drum surface and continuously winds.
With regard to tensile strength, as long as being 900mpa to the maximum, it is sufficient to.
The lithium ion secondary battery negative pole collector electrolytic copper foil of present embodiment for example can be by using sulphuric acid-sulfur
The electrolysis electroplate liquid of sour copper carries out electrolysis and processes to manufacture.
As the scope of the copper concentration of sulphuric acid-copper sulfate bath electroplate liquid, such as preferably 40～120g/l, more preferably
60～100g/l.
In addition, the scope of the sulfuric acid concentration as sulphuric acid-copper sulfate bath electroplate liquid, preferably 40～60g/l.
And then, as the scope of the cl concn of sulphuric acid-copper sulfate bath electroplate liquid, preferably 50～100ppm.
It is a feature of the present invention that as electrolysis (plating) liquid in additive use organic additive a as follows,
B and c.
Organic additive a, for example can be using selected from Polyethylene Glycol, polypropylene glycol, starch, cellulose family water solublity high score
High molecular polysaccharide, polyethyleneimine, polyallyl, polyacrylamides such as sub (carboxymethyl cellulose, hydroxyethyl celluloses etc.)
Deng molecular weight the adding more than 100000 in the additive without the water-soluble high-molecular compound of s (sulfur) in the molecular structure
Plus agent.
Organic additive b for example can be using selected from Polyethylene Glycol, polypropylene glycol, starch, cellulose family water solublity high score
High molecular polysaccharide, polyethyleneimine, polyallyl, polyacrylamides such as sub (carboxymethyl cellulose, hydroxyethyl celluloses etc.)
Deng the molecular weight in the additive without the water-soluble high-molecular compound of s (sulfur) in the molecular structure 50000 more than 10000
Following additive.
Organic additive c for example can be using selected from Polyethylene Glycol, polypropylene glycol, starch, cellulose family water solublity high score
High molecular polysaccharide, polyethyleneimine, polyallyl, polyacrylamides such as sub (carboxymethyl cellulose, hydroxyethyl celluloses etc.)
Deng in the molecular structure do not contain s (sulfur) water-soluble high-molecular compound additive in molecular weight more than 1,000 5000 with
Under additive.
By by organic additive a (molecular weight is more than 100000) different for molecular weight, (molecular weight is more than 10000 for b
Less than 50000) and c (molecular weight is less than 5000 more than 1000) combines and is added and in specific electrolysis (plating) bar
Foliation under part is such that it is able to manufacture following electrolytic copper foil, i.e. the tensile strength after 150 DEG C of heating 1 hour 350mpa with
On, glossiness gs (60 °) less than 150 more than 20, the coefficient of kinetic friction less than 0.39 more than 0.11, more preferably 0.15 with
Upper less than 0.35 electrolytic copper foil.
In general, the little organic additive of molecular weight (low molecule or smaller macromolecule (the such as additive of molecular weight
C etc.)) it is easily guided in paper tinsel in foliation, so that the intensity of paper tinsel is increased.Now, surface typically also can be smoothened.
In addition, these impurity components importing suppress paper tinsel during heating to soften and make intensity by the pinning effect on crystal boundary
Situation about reducing.
On the other hand, above-mentioned organic additive is compared with the organic additive (such as additive a, b) that molecular weight is big, foliation
When the adsorbance (clad ratio) of Copper Foil most surface is reduced, even if therefore surface configuration is close, the coefficient of kinetic friction also has reduction
The trend of corresponding amount.
In more than 700mpa and glossiness gs (60 °) is more than 80 to Patent Document 2 discloses the tensile strength of normality
Electrolytic copper foil.It is well known, however, that the paper tinsel of this patent documentation 2 is affected greatly due to the additive by low-molecular-weight, so dynamic rub
Wipe coefficient less than 0.11, paper tinsel can produce skidding in active substance working procedure of coating, thus producing problem in terms of operability.Special
The electrolytic copper foil that tensile strength is in more than 700mpa and glossiness gs (60 °) is more than 100 of normality is disclosed in sharp document 3.
However, it is identical with the situation of patent documentation 2, less than 0.11, in active substance working procedure of coating, paper tinsel can produce the coefficient of kinetic friction
Skid, thus producing problem in terms of operability.
In the present invention, in addition to molecular weight is than relatively low additive c, also using additive a and b that molecular weight is bigger.
Especially since the molecular weight of additive a is very big, so being readily adsorbed in copper sheet when foliation is carried out to Copper Foil
Film surface and hinder the precipitation of copper, thus have make surface configuration be roughened effect.In addition, to Copper Foil most surface during foliation
Adsorbance is also many.Even if the additive of this absorption is washed, after antirust treatment, also can be remained Copper Foil is carried out with foliation carrying out
In copper foil surface.Thus, also there is the effect improving the coefficient of kinetic friction simultaneously.
But, if only adding additive a more than 100000 for the molecular weight, surface can be excessively coarse, in addition, dynamic friction
Coefficient also can exceed 0.39.Therefore, by adding effect, the molecular weight of the effect with suppressant additive a it is and additive a
Compare the additive b of smaller less than more than 10,000 50000 such that it is able to make while so that its surface is somewhat smoothed
Coefficient of friction is less than more than 0.11 0.39, so that operability during coating active substance is improved.
Above-mentioned additive a, b and c can use respectively in the range of 10～30mg/l, 5～20mg/l, 5～20mg/l.
The electrolytic copper foil (untreated Copper Foil) manufacturing is implemented at the organic rust preventings such as inorganic antirust treatment or benzotriazole
Reason, inorganic antirust treatment be, for example, chromic acid salt treatment, ni or ni alloy plated, co or co alloy plated, zn or zn alloy plated,
Sn or sn alloy plated, on above-mentioned various coating, implement chromic acid salt treatment etc. further.
And then, for example implement silane coupler process etc. and make lithium ion secondary battery negative pole collector cathode copper
Paper tinsel.
Above-mentioned inorganic antirust treatment, organic rust preventing are processed, silane coupler processes and achieves raising negative electrode collector and work
Property material adhesion strength, prevent battery charging and discharging cycle efficieny reduce effect.
In addition, before stating antirust treatment on the implementation, such as roughening treatment can also be carried out in electrolytic copper foil surface.As
Roughening treatment, for example, can suitably adopt galvanoplastic, etching method etc..
Galvanoplastic are to make surface coarsening by forming the irregular thin layer of tool on the surface of untreated electrolytic copper foil
Method.As galvanoplastic, electrolytic plating method and non-electrolytic plating method can be adopted.As the roughening being carried out using plating, excellent
The surface being selected in untreated electrolytic copper foil forms the plated film with copper as main component of copper or copper alloy etc..
As the roughening carrying out using etching method, for example, it is suitable for the method using physical etch or chemical etching.With regard to thing
Reason etching, has the method being etched using sandblasting etc., with regard to chemical etching, as treatment fluid propose multiple containing inorganic or
The liquid of organic acid, oxidant and additive.
(using structure and the manufacture method of the lithium rechargeable battery of lithium rechargeable battery collector)
The lithium ion secondary battery cathode electrode of present embodiment has following structure, i.e. by above-mentioned present embodiment
Lithium ion secondary battery negative pole collector electrolytic copper foil as negative electrode collector, implements described antirust place in this collector
The face of the surface treatments such as reason layer is formed with active material layer.
For example, above-mentioned active material layer is to form pulpous state and be coated in negative pole collection active substance, binding agent, solvent mixing
Electric body is simultaneously dried, pressurizes.
Active material layer in present embodiment is the material absorbing/release lithium, enters preferably by making lithium alloyage
The active substance that row absorbs.As this active material, for example, can enumerate carbon, silicon, germanium, stannum etc. the 14th race's element etc..
In the present embodiment, preferably 4～10 μm of the thickness of collector is so thin, and active material layer is formed at collector
Single or double.Only, in the case of the bright finish coating active substance of the Copper Foil being become by cydariform, the surface of collector smooths,
Good with the adhesion of active substance.
If the thickness of collector is less than 4 μm, easily produces paper tinsel and rupture and difficult to manufacture, in the case of than 10 μ m-thick,
It is undesirable from the viewpoint of the lightweight of battery, high-energy-density.If in addition, the coefficient of kinetic friction is less than 0.11,
Then the surface of collector smooths, and therefore easily skids on the surface of Copper Foil manufacturing process and the conveying roller of battery manufacturing process and produces
Raw fold.Thus, for example by making the thickness of Copper Foil be 4～10 μm, the scope that makes the coefficient of kinetic friction be 0.11～0.39, thus
Become that operability is good, the lightweight to battery, the effective collector of high-energy-densityization (Copper Foil).
In the case of forming carbons negative electrode active material layer, make by the carbon as negative electrode active material, as bonding
The paste that the polyvinylidene fluoride resin of agent, the n- methyl pyrrolidone as solvent are constituted, is coated on collector (Copper Foil)
Single or double and so that it is dried.
The active material layer of present embodiment for example can also absorb in advance or be added with lithium.Can also formed
Add lithium during active material layer.That is, by forming the active material layer containing lithium, so that active material layer contains lithium.In addition,
Active material layer can also be made after forming active material layer to absorb or be added to lithium.As make active material layer absorb or
The method being added to lithium, can enumerate the method electrochemically absorbing or adding lithium.
In addition, the lithium rechargeable battery of present embodiment is the lithium rechargeable battery including positive pole and negative pole, negative electricity
Pole is made up of the negative electrode of the lithium rechargeable battery of above-mentioned present embodiment.
(structure of printed circuit board (PCB))
The electrolytic copper foil of embodiment of the present invention can be in the printing electricity of printed circuit board, flexible printed circuit board etc.
Road plate (in this specification, sometimes printed circuit board, flexible printed circuit board etc. being referred to as printed circuit board (PCB)), electromagnetic screen
Cover in the various field such as material and use.
Nearest printed circuit board (PCB) is typically divided into two kinds.One kind is in dielectric film (polyimides, polyester with adhering resin
Deng) attach Copper Foil, it is etched processing and implement three layer printed circuit boards of composition.On the other hand, another kind be do not use viscous
Two layer printed circuit boards connecing agent and direct for dielectric film (polyimides, liquid crystal polymer etc.) and Copper Foil being laminated.
The electrolytic copper foil of embodiment of the present invention is fitted with dielectric film as the electric conductor of these printed circuit board (PCB)s.
Printed circuit board (PCB) be mainly applicable to the flat faced displays such as liquid crystal display, plasma display, or use
Inside in photographing unit, av equipment, personal computer, computer terminal, hdd, portable phone, vehicle electronics etc.
Wiring.These wirings are installed in a device deviously, or use in the place of alternating bending, therefore as to printed circuit board (PCB)
With the requirement characteristic of Copper Foil, bendability is excellent to be an important characteristic.
The printed circuit board (PCB) of the present invention can be by attaching the electrolytic copper foil of embodiment, i.e. glossiness gs in dielectric film
(60 °) electrolytic copper foil more than 20, thus become by be present in copper foil surface small concavo-convex make Copper Foil with absolutely
There is between velum the excellent printed circuit board (PCB) of high frequency characteristics required by higher adhesion strength and circuit substrate.
Additionally, the Copper Foil fitted with dielectric film tensile strength at normal temperatures is preferably more than 450mpa, thus while being
Thin foil also has intensity, particularly, is difficult to produce paper tinsel fracture, fold etc. in the manufacturing process of flexible printed circuit board.
In addition, by the tensile strength after making the Copper Foil fit with dielectric film and heating 1 hour at 150 DEG C 350mpa with
On, even if thus experienced thermal history when manufacturing printed circuit board (PCB) it is also possible to maintain high intensity.
Many excellent specific properties of the electrolytic copper foil of the present invention, such as high frequency characteristics, low-resistance value is in terms of electromagnetic shielding
There is excellent effect, by fitting with insulated substrate, thus becoming excellent electromagnetic shielding material.
In any one purposes, by make glossiness gs (60 °) of Copper Foil more than 20 less than 150 and the coefficient of kinetic friction exist
Less than more than 0.11 0.39, so that the small concavo-convex anti-skidding thing becoming on conveying roller of copper foil surface, suppression paper tinsel is in conveying
Skid on roller, therefore its operability is good.
Embodiment
Below, based on embodiment, the present invention will be described in more detail, but the present invention is not limited to following reality
Apply example, can suitably be changed in the range of its purport and implement not changing.
(manufacture of untreated Copper Foil)
Embodiment 1～8
Copper concentration is adjusted to 65g/l, sulfuric acid concentration is adjusted to 45g/l, chloride ion concentration is adjusted to 25ppm, makes
With with the addition of the electrolyte of additive a, b and the c shown in table 1, use, in anode, the Ti electrode being coated by metal oxide containing precious metals,
Negative electrode uses titanium going barrel, is 30a/dm in electric current density2, bath temperature be 50 DEG C under conditions of, by be electrolysed foliation method make
Make the untreated Copper Foil that thickness is 10 μm.
Comparative example 1～8
Using electrolyte and the electrolytic condition of the composition shown in table 2, manufactured using the equipment same with embodiment and compare
The untreated Copper Foil of example 1～8 is so as to thickness is 10 μm.Additionally, comparative example 5 is the method according to Japanese Unexamined Patent Publication 2014-224321
Manufacture, comparative example 6 is that the method according to Japanese Patent No. 3742144 manufactures, and comparative example 8 is according to Japanese Patent No.
The method of No. 5255229 manufactures.
(tensile strength of electrolytic copper foil and the mensure of elongation percentage)
By the embodiment being measured 1～8, each electrolytic copper foil tensile strength (mpa) at normal temperatures of comparative example 1～8, prolong
The result stretching rate (%) is shown in table 3.
In addition, also measured wering the tensile strength (mpa) after 150 DEG C of heat treatments implementing 1 hour, elongation percentage (%),
Its result is shown in table 3 in the lump.
With regard to tensile strength, elongation percentage, it is based on ipc-tm- using cupping machine (1122 types of Instron Corporation)
650 determine tensile strength (mpa) and elongation percentage (%) at normal temperatures.Draw direction is set to the side parallel with long dimensional directions
To.Long dimensional directions refer to the direction parallel with respect to the direction of rotation of drum during electrolysis process.
Additionally, " room temperature " being by of representing carries out as above the heat treatment of 1 hour at 150 DEG C in the present embodiment
Common temperature before, e.g. 20 DEG C about of state of temperature.
(mensure of the coefficient of kinetic friction of electrolytic copper foil)
Determine embodiment 1～8, ratio using surface property measuring machine (newly eastern science Co. Ltd. system heidon 14fw)
The coefficient of kinetic friction compared with the hair side of each electrolytic copper foil of example 1～8.Implement to measure with following condition determination, i.e. using diameter
Steel ball for 10mm to slide son apply 50gf loading, with sliding speed as 100mm/min, sliding distance as 10mm,
One way 1 time.The results are shown in table 3.
(mensure of the glossiness of electrolytic copper foil)
Connect with 60 ° of transmitting based on jis z 8741 using Grossmeters (electricity Se Industrial Co., Ltd of Japan system vg2000)
Receive glossiness gs (60 °) that optic angle determines the hair side of each electrolytic copper foil of embodiment 1～8, comparative example 1～8.To with respect to length
Parallel, the orthogonal both direction of dimensional directions is each to be implemented 3 times, and illustrates the value being averaged all these values.The results are shown in
Table 3.
[table 3]
(chromic acid salt treatment)
Implement chromic acid salt treatment and form antirust treatment in each electrolytic copper foil surface of embodiment 1～8, comparative example 1～8
Layer, as collector.
The condition of the chromic acid salt treatment of copper foil surface is as follows.
Chromate treatment conditions:
Potassium dichromate 1～10g/l
2～20 seconds impregnation process time
(evaluation of battery behavior)
1. the manufacture of positive pole
Licoo by 90 weight %2Powder, the powdered graphite of 7 weight %, the Kynoar powder of 3 weight % are carried out
Mixing, adds the solution in ethanol by the dissolving of n- methyl pyrrolidone and is kneaded, thus being adjusted to positive pole paste.Should
After paste is evenly coated at the aluminium foil that thickness is 15 μm, it is dried in nitrogen environment and so that ethanol is volatilized, then enter
Row roll-in is prolonged and is fabricated to the sheet material that integral thickness is 100 μm.This sheet cutting is width 43mm, after length 290mm,
In its one end, positive pole is used as by the lead terminal that aluminium foil is installed in ultrasonic bonding.
2. the manufacture of negative pole
The Kynoar powder of the natural graphite powder (mean diameter is 10 μm) of 90 weight %, 10 weight % is carried out
Mixing, adds the solution in ethanol by the dissolving of n- methyl pyrrolidone and is kneaded, thus making paste.Then, this is pasted
Agent is coated in the two sides of each Copper Foil of embodiment, comparative example.Copper Foil after coating is dried in nitrogen environment and makes second
Alcohol volatilizees, and then carries out roll-in and prolongs and be configured to the sheet material that integral thickness is 110 μm.This sheet cutting is width 43mm, length
After degree 285mm, in its one end, negative pole is used as by the lead terminal that nickel foil is installed in ultrasonic bonding.
3. the making of battery:
The polypropylene separator that thickness is 25 μm is clipped between the positive pole manufacturing as described above and negative pole and will be whole
Body is rolled, and is contained in and carries out in the battery case of nickel plating on mild steel surface, and the lead terminal point of negative pole is welded in shell bottom.Connect
, place the upper lid of insulant, insert liner, then carry out ultrasonic bonding by the lead terminal of positive pole and aluminum relief valve
Couple together, will be injected in battery case by the nonaqueous electrolytic solution that Allyl carbonate, diethyl carbonate and ethylene carbonate form,
Then lid is installed on described relief valve, is assembled into profile and is 14mm, is highly the sealing structure type lithium ion secondary electricity of 50mm
Pond.
4. the mensure of battery behavior
Above battery is carried out with charge and discharge cycles test, a circulation of this test is as follows, i.e. with the charging electricity of 50ma
Stream is charged, until reaching 4.2v, being discharged with 50ma, until it reaches 2.5v.By battery capacity during primary charging and following
The ring life-span is shown in table 3.Additionally, the discharge capacity that cycle life is battery falls to period during 300mah.
5. the formedness evaluation of operation
In the coating of the paper tinsel of the 1000m on active substance Coating Production Line is processed, using the paper tinsel of following situations as operation
Property good situation, be labeled as zero, i.e. can paper tinsel will not in conveying roller on produce and skid and paper tinsel will not be stuck on conveying roller
In the case of swimmingly conveyed；Generation is skidded or paper tinsel is stuck in the paper tinsel of the phenomenon causing conveying to stop on roller as operation
The bad situation of property, be labeled as ×, the results are shown in table 3.In addition, produce problem in some conveyings by although how I haven't seen you for ages but
The paper tinsel being also unlikely to the coating of active substance is thrown into question is labeled as △.
According to table 3, in embodiment 1～8, in 1 hour tensile strength in front and back of 150 DEG C of heating in more than 350mpa, light
Damp degree gs (60 °), more than 20, therefore illustrates good battery behavior more than 500 circulations for the cycle life.And then, dynamic friction
Coefficient, less than 0.39 more than 0.11, can suppress to carry out sliding on roller when production line manufactures, operability is also good.
But, for embodiment 1 although the coefficient of kinetic friction up to 0.38, the coating to active substance does not have obstacle, but
Conveying confirms and more or less blocks, therefore its operability is labeled as △.
On the other hand, because the coefficient of kinetic friction of the paper tinsel of embodiment 8 as little as 0.12, confirm paper tinsel many on conveying roller
Rare point skids, but is also unlikely to cause obstacle to the coating of active substance, therefore, is labeled as △ similarly to Example 1.
Glossiness gs (60 °) of the hair side side of the Copper Foil of comparative example 1 below 20, very low, therefore active substance and collection
The contact difference of electric body, it is impossible to bear the stress being caused by the dilation of active substance during discharge and recharge, is formed at hair side side
Active material layer create stripping etc., therefore cycle life is below 500 circulations, very low.In addition, the dynamic friction of hair side side
Coefficient is 0.38, relatively higher, therefore there is the situation that paper tinsel is stuck on conveying roller, but and is unlikely to active substance coating is caused to ask
Topic.
Tensile strength after the heating of the Copper Foil of comparative example 2 is in more than 350mpa, and then glossiness gs (60 °) of hair side side
Also, less than 150 more than 20, therefore illustrate preferred cycle life, but the coefficient of kinetic friction of hair side side as little as 0.11 with
Under, therefore in active substance working procedure of coating, paper tinsel can produce skidding in conveying, and therefore its operability is bad.
Tensile strength after the heating of the Copper Foil of comparative example 3 in more than 350mpa, glossiness gs (60 °) also more than 20,
The active substance being therefore formed at hair side side is good with the contact of collector, shows cycle life more than 500 circulations
Good result.However, with regard to operability, because the coefficient of kinetic friction of hair side side is 0.45, very high, thus paper tinsel can be stuck in defeated
Send and stop on roller, thus the coating to active substance meeting causes problem, therefore its operability is not preferred.
In addition, the coefficient of kinetic friction of the hair side side of the Copper Foil of comparative example 4 is 0.13, operability during active substance coating is good
Good, but because glossiness gs (60 °) is more than 150, so while the dilation of the active substance in discharge and recharge and produce
The stripping of active substance, cycle life circulates less than 500, not preferably.
Comparative example 5 is the paper tinsel carrying out foliation based on the manufacture method of the embodiment (sample 8) described in patent documentation 3.
Tensile strength after heating in more than 350mpa, glossiness gs (60 °) of hair side side also less than 150 more than 20,
Therefore illustrate preferred cycle life, but the coefficient of kinetic friction of hair side side as little as less than 0.11, thus applying in active substance
In deposited operation, paper tinsel can produce skidding in conveying, and therefore its operability is not preferred.
In addition, comparative example 6 is the paper tinsel being manufactured with the method described in the embodiment of patent documentation 1.The dynamic of its hair side side rubs
Wipe coefficient to be respectively in less than more than 0.11 0.39 scope, therefore the operability in active substance working procedure of coating is preferred, and
Because glossiness gs (60 °) is also in less than more than 20 150 scope, therefore active substance is also excellent with the adhesion of collector
Choosing, but the tensile strength after heating is 320mpa, as little as less than 350mpa, therefore cannot bear active substance during discharge and recharge
Dilation and create deformation of paper tinsel etc., due to this impact, its cycle characteristics be short of, be labeled as ×.
Similarly, for comparative example 7 although its operability when active substance applies is good, but due to heating after
Tensile strength as little as less than 350mpa, so paper tinsel can produce deformation in discharge and recharge, cycle characteristics is poor.
Comparative example 8 is the paper tinsel being manufactured with the method described in the embodiment of patent documentation 2, and the tensile strength after its heating exists
More than 350mpa, glossiness gs (60 °) of hair side side, also less than 150 more than 20, therefore illustrates preferred cycle life, but
Be the coefficient of kinetic friction of its hair side side below 0.11, thus in active substance working procedure of coating paper tinsel conveying when can produce beat
Sliding, therefore its operability is bad.
As described above, the electrolytic copper foil of the present invention employs following electrolytic copper foil, it is after 150 DEG C of heating 1 hour
Tensile strength in more than 350mpa, preferably in more than 400mpa, less than 150 more than 20, move and rub by glossiness gs (60 °) of hair side
Wipe coefficient less than 0.39 more than 0.11, less than 0.35 preferably more than 0.15, a kind of good lithium is shown thus, it is possible to provide
Ion secondary battery characteristic and being difficult on manufacturing line is skidded and good carrying out operability when production line manufactures
Electrolytic copper foil.
In addition, the electrolytic copper foil of embodiments of the invention 150 DEG C heating 1 hour after tensile strength 350mpa with
On, the stress being carried out dilation and being produced by the volume of active substance during discharge and recharge can be born, can get cycle life
Good secondary cell.
And then, glossiness gs (60 °) of the hair side of the electrolytic copper foil of embodiments of the invention less than 150 more than 20, from
And active substance is good with the contact of collector, electrical conductivity is high, can get good cycle life.
And then, below 150 and the coefficient of kinetic friction is more than 0.11 for glossiness gs (60 °) of the electrolytic copper foil of the present invention
Less than 0.39, the small concavo-convex anti-skidding thing becoming on conveying roller on surface, can suppress paper tinsel to skid on roller, so that operability is become
Well.
In addition, the electrolytic copper foil of the present invention is used as collector by the lithium ion secondary battery cathode electrode of the present invention, from forming
For improve the lithium ion secondary battery cathode electrode of cycle characteristics, including this electrode lithium rechargeable battery have excellent
The battery of cycle life.
(making of printed circuit board (PCB) and evaluation)
The electrolytic copper foil of embodiment 5 is fitted with polyimide film, manufacture 3 layer printed circuit boards, to manufacturing process,
The performance of the circuit board being completed is evaluated.
(1) adhesion of Copper Foil and film
With regard to the adhesion of Copper Foil and film, polyimide film be embedded into be present in copper foil surface small concavo-convex in, tool
There is gratifying intensity.
(2) high frequency characteristics
With regard to the high frequency characteristics of printed circuit board (PCB) because glossiness gs (60 °) more than 90, copper foil surface concavo-convex micro-
Little, so being gratifying.
(3) generation of the intensity of Copper Foil and fold
Copper Foil tensile strength at normal temperatures is 668mpa, due in more than 450mpa, even so thin foil, its with absolutely
The intensity of velum laminating is also enough, does not produce paper tinsel fracture, fold etc. in the manufacturing process of printed circuit board (PCB).
(4) thermal history
In heating when making Copper Foil fit with dielectric film, almost no the intensity of the Copper Foil that discovery causes because of thermal history does not become
Change, even if experienced thermal history when manufacturing printed circuit board (PCB) it is also possible to maintain high intensity.
As described above, the present invention is very excellent with Copper Foil especially as the secondary cell collector having extended cycle life, and
There is excellent operability, therefore Copper Foil will not produce fold on active substance Coating Production Line, according to such characteristic, this
Invention has following excellent effect, i.e. can easily provide a kind of lithium ion secondary battery cathode that improve cycle characteristics
Electrode is additionally it is possible to provide a kind of lithium rechargeable battery having extended cycle life including this lithium ion secondary battery cathode electrode.
In addition, as described above, the present invention has following excellent effect, i.e. the print with excellent characteristic can be provided
Printed circuit board and electromagnetic shielding material.
Claims (7)
1. a kind of electrolytic copper foil it is characterised in that glossiness gs (60 °) of hair side less than 150 more than 20, the coefficient of kinetic friction exists
Less than more than 0.11 0.39, the tensile strength after heating 1 hour at 150 DEG C is in more than 350mpa below 900mpa.
2. electrolytic copper foil according to claim 1 is it is characterised in that the tensile strength after heating 1 hour at 150 DEG C exists
More than 400mpa.
3. electrolytic copper foil according to claim 1 and 2 is it is characterised in that the thickness of this electrolytic copper foil is 10 μm more than 4 μm
Below.
4. a kind of lithium rechargeable battery negative electrode is it is characterised in that by the electricity described in any one of claims 1 to 3
Solution Copper Foil is as collector.
5. a kind of lithium rechargeable battery is it is characterised in that usage right requires the lithium ion secondary as collector described in 4
Battery negative electrode.
6. a kind of printed circuit board (PCB) is it is characterised in that by the electrolytic copper foil described in any one of claims 1 to 3 and insulation
Film is laminated and is constituted.
7. a kind of electromagnetic shielding material is it is characterised in that by the electrolytic copper foil described in any one of claims 1 to 3 and absolutely
Edge substrate is laminated and is constituted.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-135702 | 2015-07-06 | ||
| JP2015135702A JP2017014608A (en) | 2015-07-06 | 2015-07-06 | Electrolytic copper foil, lithium ion secondary battery negative electrode and lithium ion secondary battery, printed wiring board, and electromagnetic wave-shielding material |
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| Publication Number | Publication Date |
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| CN106340668A true CN106340668A (en) | 2017-01-18 |
| CN106340668B CN106340668B (en) | 2020-10-23 |
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| Country | Link |
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| JP (1) | JP2017014608A (en) |
| KR (1) | KR101782737B1 (en) |
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| TW (1) | TWI609995B (en) |
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| CN110093635A (en) * | 2019-04-24 | 2019-08-06 | 福建清景铜箔有限公司 | High-intensitive electrolytic copper foil and its various products for using the copper foil |
| CN111081978A (en) * | 2018-10-19 | 2020-04-28 | 通用汽车环球科技运作有限责任公司 | Negative electrode for lithium-ion electrochemical cell and method of forming same |
| CN115198319A (en) * | 2021-12-15 | 2022-10-18 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising electrolytic copper foil and lithium ion battery |
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| KR102399930B1 (en) * | 2017-08-29 | 2022-05-18 | 에스케이넥실리스 주식회사 | Method for manufacturing copper foil having nodule layer, copper foil manufactured by the method, electrode for secondary battery the same and secondary battery |
| KR102492813B1 (en) * | 2017-09-15 | 2023-01-26 | 에스케이넥실리스 주식회사 | Copper foil for high capacity secondary battery with improved handling property, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| JP6582156B1 (en) * | 2018-02-23 | 2019-09-25 | 古河電気工業株式会社 | Electrolytic copper foil, and negative electrode for lithium ion secondary battery, lithium ion secondary battery, copper clad laminate and printed wiring board using the electrolytic copper foil |
| JP6778291B1 (en) * | 2019-03-04 | 2020-10-28 | ナミックス株式会社 | Negative current collector of copper foil and lithium ion battery containing it and its manufacturing method |
| TWI705160B (en) | 2019-12-09 | 2020-09-21 | 長春石油化學股份有限公司 | Electrolytic copper foil and electrode and copper-clad laminate comprising the same |
| JP7164766B2 (en) | 2020-07-16 | 2022-11-01 | 東洋鋼鈑株式会社 | electrolytic iron foil |
| US20230265575A1 (en) | 2020-07-16 | 2023-08-24 | Toyo Kohan Co., Ltd. | Electrolytic iron foil |
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| CN115198319A (en) * | 2021-12-15 | 2022-10-18 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising electrolytic copper foil and lithium ion battery |
| CN115198319B (en) * | 2021-12-15 | 2023-11-17 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising same and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI609995B (en) | 2018-01-01 |
| KR101782737B1 (en) | 2017-09-27 |
| TW201702434A (en) | 2017-01-16 |
| KR20170005764A (en) | 2017-01-16 |
| JP2017014608A (en) | 2017-01-19 |
| CN106340668B (en) | 2020-10-23 |
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