CN106558678A - The strong electrolytic copper foil of superelevation, including its electrode and secondary cell and its manufacture method - Google Patents
The strong electrolytic copper foil of superelevation, including its electrode and secondary cell and its manufacture method Download PDFInfo
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- CN106558678A CN106558678A CN201610579592.6A CN201610579592A CN106558678A CN 106558678 A CN106558678 A CN 106558678A CN 201610579592 A CN201610579592 A CN 201610579592A CN 106558678 A CN106558678 A CN 106558678A
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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
- H01M4/04—Processes of manufacture in general
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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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
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Abstract
The invention discloses one kind prevents from folding or corrugated electrolytic copper foil, a kind of electrode including the electrolytic copper foil, a kind of a kind of secondary cell and method for manufacturing the electrolytic copper foil including the electrolytic copper foil in volume to volume (RTR) technique.Electrolytic copper foil includes：Copper film, comprising 99wt% or more copper；And protective layer, it is arranged on copper film, and the electrolytic copper foil has 45kgf/mm2To 65kgf/mm2Tensile strength.
Description
Technical field
The present invention relates to a kind of electrolytic copper foil of superhigh intensity, a kind of electrode including the electrolytic copper foil, a kind of include should
The secondary cell of electrolytic copper foil and a kind of method of the manufacture electrolytic copper foil.
Background technology
Electrolytic copper foil is used to produce various products, such as produces the anode current collector of secondary cell, and flexible printing electricity
Road plate (FPCB).
In general, electrolytic copper foil is produced by volume to volume (RTR) technique, and for by volume to volume (RTR) technique
To produce anode current collector, flexible printed circuit board (FPCB) of secondary cell etc..
Known volume to volume (RTR) technique is suitable to produce in enormous quantities, because which continuously can be produced.However, in practice
In, due to the folding and/or corrugation of the recurrent electrolytic copper foil in volume to volume (RTR) technical process, volume to volume (RTR) work
The operation of skill equipment inevitably stops, and after these problems are solved, equipment will re-start operation.Process equipment it is anti-
It is production efficiency deterioration to stop and re-operate the big problem for causing again.
That is, the such as folding of recurrent, electrolytic copper foil and/or corrugated problem during volume to volume (RTR) technique
The continuous production of product is prevented, therefore is caused infringement to the intrinsic advantages of volume to volume (RTR) technique and is caused the production of product
Efficiency degradation.
The content of the invention
Therefore, in view of the problems referred to above for causing of the restriction of prior art and shortcoming and propose the present invention, the invention provides
A kind of electrolytic copper foil of superhigh intensity, a kind of electrode including the electrolytic copper foil, a kind of secondary cell including the electrolytic copper foil
And a kind of method for manufacturing the electrolytic copper foil.
It is an object of the present invention to provide a kind of high intensity electrolytic copper foil, its tensile strength is 45kgf/mm2Or it is higher,
So as to during volume to volume (RTR) technical process preventing from folding or wrinkle.
It is a further object of the present invention to provide a kind of electrode, the electrode can be using preventing in volume to volume (RTR) technique mistake
Folding or corrugated high intensity electrolytic copper foil during journey it is hereby ensured excellent production efficiency producing.
It is a further object to provide a kind of secondary cell, the secondary cell can be used at volume to volume (RTR)
Prevent from folding or corrugated high intensity electrolytic copper foil to produce during technical process, it is hereby ensured excellent production efficiency.
A further object of the present invention is to provide a kind of method of manufacture high intensity electrolytic copper foil, the high intensity electrolytic copper foil
Tensile strength be 45kgf/mm2Or it is higher, so as to during volume to volume (RTR) technical process preventing from folding or wrinkle.
Scheme of the invention as above and other features and advantages of the present invention will be described below or will be by
Those skilled in the art are expressly understood according to specification.
A scheme of the invention, can realize above and other purpose by providing a kind of electrolytic copper foil, the electrolysis
Copper Foil includes：Copper film, comprising 99wt% or more copper；And the protective layer on copper film, wherein, the stretching of electrolytic copper foil is strong
Spend for 45kgf/mm2To 65kgf/mm2。
According to another aspect of the present invention, there is provided a kind of electrode of secondary cell, which includes：Electrolytic copper foil, which includes：
Copper film comprising 99wt% or more copper and the protective layer on copper film, the tensile strength of the electrolytic copper foil is 45kgf/
mm2To 65kgf/mm2；And the active material layer formed on electrolytic copper foil, wherein, active material layer is included from by following material
At least one active material selected in the group of material composition：Carbon；Including the gold of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe
Category (Me)；Alloy containing the metal (Me)；Oxide (the MeO of the metal (Me)X)；And the metal (Me) and carbon is compound
Thing.
According to another aspect of the present invention, there is provided a kind of secondary cell, which includes：Negative electrode, supplies electronics when charging
And lithium ion；Anode, supply electronics and lithium ion in electric discharge；Electrolyte, there is provided enable lithium ion negative electrode and anode it
Between the environment that moves；And sept, electric insulation negative electrode and anode, wherein, anode includes：Electrolytic copper foil, which includes：Comprising
The copper film and the protective layer being arranged on copper film of 99wt% or more copper, the tensile strength of electrolytic copper foil is 45kgf/mm2
To 65kgf/mm2；And the active material layer formed on electrolytic copper foil, wherein, active material layer is included from by following material
At least one active material selected in the group of composition：Carbon；Including the metal of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe
(Me)；Alloy containing the metal (Me)；Oxide (the MeO of the metal (Me)X)；And the metal (Me) and carbon is compound
Thing.
Yet another aspect of the invention, there is provided a kind of method of manufacture electrolytic copper foil, which includes：Hold in a cell
Electric current is conducted between the minus plate being spaced apart in the electrolyte received and rotary anode cylinder, to form copper on rotary anode cylinder
Film, wherein, electrolyte includes the copper ion of 50g/L to 100g/L, the sulfuric acid of 50g/L to 150g/L and 1ppm to 6.5ppm
The organic additive represented by following chemical formula 1：
[chemical formula 1]
(H2N(CH2)n)2C=S
Wherein, n is zero, or 6 or the natural number less than 6.
General remark with regard to the present invention given above is used to illustrate or the open present invention, and is not necessarily to be construed as limiting
The scope of the present invention.
Description of the drawings
With reference to accompanying drawing, by the above and other purpose that the present invention will be more clearly understood described in detail below, feature and
Further advantage, in accompanying drawing：
Fig. 1 is the sectional view of electrolytic copper foil according to an embodiment of the invention；
Fig. 2 shows the sectional view of the electrode of secondary cell according to an embodiment of the invention；And
Fig. 3 shows the device for producing electrolytic copper foil according to an embodiment of the invention.
Specific embodiment
Hereinafter, embodiments in accordance with the present invention be will be described in detail with reference to the accompanying drawings.
It will be understood by those skilled in the art that various modifications, addition can be carried out and replaced, without deviating from such as appended claims
Scope and spirit of the present invention disclosed in book.Therefore, the present invention includes the modification fallen in the range of present invention opinion and replaces
Change and its be equal to.
Fig. 1 is the sectional view for illustrating electrolytic copper foil 110 according to an embodiment of the invention.
As shown in figure 1, electrolytic copper foil of the invention 110 includes：Copper film 111, comprising 99wt% or more copper；With
And the protective layer 112 being arranged on copper film 111.In the electrolytic copper foil 110 shown in Fig. 1, protective layer 112 is formed in copper film 111
Opposing sides on, but the invention is not restricted to this, protective layer 112 can be made only on a surface of copper film 111.
The thickness of electrolytic copper foil 110 is 4 μm to 35 μm according to an embodiment of the invention.Cathode copper of the thickness less than 4 μm
The product of paper tinsel 110 causes the deterioration of processing characteristics.On the other hand, thickness is the secondary cell of 35 μm of the production of electrolytic copper foil 110
There can not be high power capacity as electrolytic copper foil 110 is too thick.
Copper film 111 can by plating be formed on rotary anode cylinder, and with during plating with rotary anode cylinder
The glassy surface of contact and the non-glassy surface relative with glassy surface.
Protective layer 112 is formed by the electro-deposition anticorrosive on copper film 111.Anticorrosive may include chromate,
At least one in BTA (BTA) and/or silane compound.Protective layer 112 prevents the oxidation of copper film 111 and corrodes and carry
High-fire resistance, therefore extend the life-span of electrolytic copper foil 110 and the life-span of the final products including the electrolytic copper foil.
In order to prevent the folding and curling (that is, wrinkling) of electrolytic copper foil 110, electrolytic copper foil of the invention 110 has
45kgf/mm2Or higher high tensile.When the tensile strength of electrolytic copper foil 110 is less than 45kgf/mm2When, electrolytic copper foil 110
It is folded between two adjacent rollers during volume to volume production technology, or the left end and right-hand member of electrolytic copper foil 110 is rolling up right
Wrinkle during volume production technology.
On the other hand, when the tensile strength of electrolytic copper foil 110 is more than 65kgf/mm2When, electrolytic copper foil 110 has flatness long
Rate, therefore in the production of the final products of the anode current collector and flexible printed circuit board (FPCB) of such as secondary cell, tool
There is the risk for causing 110 breakage of electrolytic copper foil.
Therefore, electrolytic copper foil of the invention 110 has 45kgf/mm2To 65kgf/mm2Tensile strength and 3% arrive
13% elongation.
Hereinafter, only for being better understood from, electrolytic copper foil of the invention 110 is will be described in for secondary electricity
The embodiment of the production in pond.However, as described above, electrolytic copper foil of the invention 110 can be used for producing various other
Product, such as flexible printed circuit board (FPCB), the flexible printed circuit board can by volume to volume (RTR) technique using Copper Foil come
Production.
Lithium rechargeable battery includes：Negative electrode, supply electronics and lithium ion when charging；Anode, the supply electricity in electric discharge
Son and lithium ion；Electrolyte, there is provided enable the environment that lithium ion is moved between negative electrode and anode；And sept, electricity
Insulating cathode and anode, so that the electronics produced in an electrode in preventing due to secondary cell moves to another electrode,
Cause unnecessary electronics consumption.
Fig. 2 is the sectional view of the electrode of secondary cell according to an embodiment of the invention.
As shown in Fig. 2 the electrode of secondary cell 100 includes a reality of the invention according to an embodiment of the invention
Apply the electrolytic copper foil 110 in example, and active material layer 120.
Fig. 2 illustrates the active material layer 120 being formed in the upper and lower surface of electrolytic copper foil 110, but of the invention
Not limited to this, active material layer 120 can be made only on a surface of electrolytic copper foil 110.
In general, with regard to lithium secondary battery, aluminium foil is used as the cathode collector for being connected to active material of cathode, Copper Foil
110 are used as being connected to the anode current collector of active material of positive electrode.
Embodiments in accordance with the present invention, the electrode of secondary cell 100 are used as anode, and electrolytic copper foil 110 is used as anode
Current collector, active material layer 120 include active material of positive electrode.
Active material layer 120 include as active material of positive electrode, from including following material group in select at least one
Plant active material：Carbon；Metal (Me) including Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe；Conjunction containing the metal (Me)
Gold；Oxide (the MeO of the metal (Me)x)；And the compound of the metal (Me) and carbon.
In order to increase the charging/discharging capacity of secondary cell, active material layer 120 can use the anode containing scheduled volume Si
The mixture of active material is formed.
Simultaneously as the charge/discharge repeatedly of secondary cell, active material layer 120 alternately shrinks and expands, and this causes
Active material layer 120 is separated with electrolytic copper foil 110, causes the deterioration of the charge/discharge efficiency of secondary cell.Therefore, in order that
Second electrode guarantees the capacity maintenance degree of predeterminated level and life-span (that is, in order to prevent the bad of the charge/discharge efficiency of secondary cell
Change), electrolytic copper foil 110 active material should be had it is excellent can coating so that electrolytic copper foil 110 and active material layer
Adhesion strength between 120 can strengthen.
In a broad sense, with electrolytic copper foil 110 surface 10 points of mean roughness RzJISReduction, secondary cell fills
The deterioration of electricity/discharging efficiency is reduced.
Therefore, 10 points of mean roughness R on the surface of electrolytic copper foil 110 according to an embodiment of the inventionzJISFor 3.5 μm
Or it is less.As 10 points of mean roughness R on the surface of electrolytic copper foil 110zJISDuring more than 3.5 μm, electrolytic copper foil 110 and active material
Contact uniformity between the bed of material 120 is not up to desirable level, therefore secondary cell can not meet needed for this area 90%
Or higher capacity maintenance degree.
Hereinafter, the manufacture method of electrolytic copper foil 110 according to an embodiment of the invention will be described with reference to Fig. 3 in detail.
The method according to the invention is included in conduction between minus plate and rotary anode cylinder, and minus plate is existed with rotary anode cylinder
It is spaced apart in the electrolyte 20 accommodated in electrolytic cell 10, so that copper film 111 is formed on rotary anode cylinder 40.
As shown in figure 3, minus plate 30 may include the first minus plate 31 insulated from each other and the second minus plate 32.
The formation of copper film 111 may include：Seed is formed by the conduction between the first minus plate 31 and rotary anode cylinder 40
Crystal layer；Then by the conduction between the second minus plate 32 and rotary anode cylinder 40 growing inculating crystal layer.
The current density for being fed to the first minus plate 31 and the second minus plate 32 can be 40A/dm respectively2To 80A/dm2。
Embodiments in accordance with the present invention, by the current density supplied by the first minus plate 31 is set higher than by second
The current density (that is, by applying higher current density when inculating crystal layer is formed) of the supply of minus plate 32, the crystal grain of inculating crystal layer
Size can be reduced, as a result, the glassy surface of copper film 111 and non-glassy surface can have same or similar crystallite dimension.
As the glassy surface and non-glassy surface of copper film 111 can have same or similar crystallite dimension, so further can press down
Make the folding/curling of electrolytic copper foil of the invention 110.
According to the present invention, electrolyte 20 include the copper ion of 50g/L to 100g/L, the sulfuric acid of 50g/L to 150g/L and
The organic additive represented by following chemical formula 1 of 1ppm to 6.5ppm：
[chemical formula 1]
(H2N(CH2)n)2C=S
Wherein, n is zero, or 6 or the natural number less than 6.
The organic additive of chemical formula 1 is a kind of additive, is giving 45kgf/ for the electrolytic copper foil 110 according to the present invention
mm2Or play a significant role in terms of higher high tensile.
Therefore, when the content of organic additive is less than 1ppm, the tensile strength of electrolytic copper foil 110 can not reach 45kgf/
mm2, and when final products are produced by electrolytic copper foil 110 by volume to volume (RTR) technique, cause folding/curling (wrinkling)
The risk of problem increases.
On the other hand, when the content of organic additive is more than 6.5ppm, electrolytic copper foil 110 has more than 65kgf/mm2
Tensile strength and the low elongation less than 3%.When the elongation of electrolytic copper foil 110 is less than 3%, by electrolytic copper foil 110
During production final products, electrolytic copper foil 110 may be damaged.
Meanwhile, if in the chemical formula 1 of organic additive, n is 7 or the natural number more than 7, then when organic additive
Measure for 1ppm to 6.5ppm when, it is impossible to produce tensile strength for 45kgf/mm2To 65kgf/mm2Electrolytic copper foil 110.
(for example, electrolyte 20 may also include (as additive) gelatin, hydroxyethyl cellulose (HEC), organic sulfur compound
SPS), at least one in organic nitrogen compound and thiocarbamide based compound.
Alternatively, electrolyte may also include 50ppm or less chlorion.
When copper film 111 is formed, electrolyte 60 is maintained at 40 DEG C to 60 DEG C, and is supplied to the electrolyte of electrolytic cell 10
20 flow velocity can be 30m3/ h (that is, 30m3/ hour) to 50m3/h。
The surface of rotary anode cylinder 40 affects 10 points of mean roughness R of the glassy surface of copper film 111zJIS.According to the present invention
Embodiment, the surface of rotary anode cylinder 40 can be polished with the sand grains polish brush of #800 to #1500.
The method according to the invention may also include and copper film 111 is immersed in anti-corrosion solution 60.When copper film 111 it is impregnated
When in anti-corrosion solution 60, the copper film can be directed by the guide reel 70 being arranged in anti-corrosion solution 60.
As described above, anti-corrosion solution 60 may include chromate, BTA and/or silane compound.For example, copper film
111 can be submerged in 2 seconds to 20 seconds in the potassium bichromate solution of 1g/L to 10g/L at room temperature.
One surface or two surfaces of the electrolytic copper foil 110 produced by the method according to the invention can be coated with from by with
At least one active material of positive electrode selected in the group of lower material composition：Carbon；Including Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni
Or the metal (Me) of Fe；Alloy containing the metal (Me)；Oxide (the MeO of the metal (Me)x)；And the metal (Me) is multiple
Compound, so as to produce the electrode (that is, anode) of the secondary cell for the present invention.
For example, the carbon of 100 parts of weight is used as active material of positive electrode, the butadiene-styrene rubber (SBR) and 1 to 3 of 1 to 3 parts of weight
The carboxymethylcellulose calcium (CMC) of part weight is mixed and is made into slurry using distilled water as solvent.Subsequently, the slurry is made
It is coated on current collector 110 with 20 μm to 60 μm of thickness with scraping blade, and at 110 DEG C to 130 DEG C and 0.5t/cm2(that is, ton/
cm2) to 1.5t/cm2Pressure under be pressed.
Using the electrode (anode) of the secondary cell of the present invention produced by method as above, with reference to common cloudy
Pole, electrolyte and sept, can produce lithium secondary battery.
Hereinafter, the present invention will be more fully described with reference to the example below and comparative example.Following example is only used for
The present invention is more fully understood, and is not necessarily to be construed as limiting the scope of the present invention.
Example 1
Conduct electric current between the minus plate being spaced apart in electrolyte in electrolytic bath and rotary anode cylinder, so as to
Copper film is formed on rotary anode cylinder.The sulfuric acid of copper ion of the electrolyte comprising 85g/L and 98g/L.Electrolyte is included as addition
[double (3- sulfopropyls) disulphide] of the 5.6ppm of agent (SPS), the collagen A (mean molecule quantities of 6.2ppm：3000g/
Mol to 20000g/mol) and 1.1ppm (H2N)2C=S.When copper film is formed, electrolyte is maintained into about 50 DEG C, and with
40m3The flow velocity of/h is by electrolyte supply in electrolytic bath.The current density provided to form copper film is 55A/dm2.Copper film exists
It is submerged under room temperature 10 seconds in the potassium bichromate solution of 1g/L to 10g/L, and is subsequently dried to two tables in copper film
Protective layer is formed on face, so as to complete the electrolytic copper foil with 4 μ m thicks.
Example 2
Except by (H2N(CH2)6)2C=S is added in electrolyte to replace (H with the amount of 1.1ppm2N)2Outside C=S, with
Electrolytic copper foil is produced with identical mode in example 1.
Example 3
Except (the H being added in electrolyte2N)2The amount of C=S is, outside 6.4ppm, to give birth in the same manner as in Example 1
Produce electrolytic copper foil.
Example 4
Except by (H2N(CH2)6)2C=S is added to replace (H with the amount of 6.4ppm2N)2Outside C=S, with example
In 1, identical mode produces electrolytic copper foil.
Reference examples 1
Except (the H being added in electrolyte2N)2The amount of C=S is, outside 0.9ppm, to give birth in the same manner as in Example 1
Produce electrolytic copper foil.
Reference examples 2
Except by (H2N(CH2)6)2C=S is added in electrolyte to replace (H with the amount of 6.7ppm2N)2Outside C=S, with
Electrolytic copper foil is produced with identical mode in example 1.
Reference examples 3
Except by (H2N(CH2)7)2C=S is added in electrolyte to replace (H with the amount of 1.1ppm2N)2Outside C=S, with
Electrolytic copper foil is produced with identical mode in example 1.
Reference examples 4
Except by (H2N(CH2)7)2C=S is added in electrolyte to replace (H with the amount of 6.4ppm2N)2Outside C=S, with
Electrolytic copper foil is produced with identical mode in example 1.
Reference examples 5
Except (H is not contained in electrolyte2N)2Outside C=S, electrolytic copper foil is produced in the same manner as in Example 1.
The tensile strength of the electrolytic copper foil produced by example and comparative example according to following methods measurement and rising for generation
Wrinkle/damaged, as a result illustrates in table 1.
The tensile strength and elongation of electrolytic copper foil
The tensile strength and elongation of electrolytic copper foil is measured according to IPC-TM-650 method of testing handbooks.
Corrugation/the breakage of generation
When by volume to volume (RTR) technique with electrolytic copper foil produce electrode for secondary battery when, see whether occur corrugation or
It is damaged.
Table 1
From above-mentioned table 1, in reference examples 5, i.e., structure is not contained for (H in electrolyte2N(CH2)6)2C=S (its
In, n be zero, or 6 or the natural number less than 6) additive in the case of, and in reference examples 1, i.e., contain in electrolyte
(the H having2N(CH2)6)2Less than in the case of 1ppm, electrolytic copper foil has less than 45kgf/mm the amount of C=S2Low tensile strength,
As a result, these electrolytic copper foils wrinkle during volume to volume (RTR) technique.
In reference examples 3 and 4, i.e., contain structure for (H in electrolyte2N(CH2)n)2(wherein, n is additive 7) to C=S
In the case of, electrolytic copper foil has less than 45kgf/mm2Tensile strength, as a result, these electrolytic copper foils are in volume to volume
(RTR) wrinkle during technique.
Meanwhile, contain structure for (H in electrolyte2N(CH2)n)2C=S (wherein, n be zero, or 6 or less than 6 from
Right number) and measure more than 6.5ppm additive in the case of, i.e. in reference examples 2, electrolytic copper foil has higher than 65kgf/mm2
Tensile strength and the elongation less than 3%, as a result, the electrolytic copper foil wrinkles during volume to volume (RTR) technique.
According to the present invention it is possible to produce prevent from folding or corrugated high intensity during volume to volume (RTR) technique
Electrolytic copper foil, and the intermediate species of flexible printed circuit board (FPCB), secondary cell etc. can be lifted using high intensity electrolytic copper foil
With the production efficiency of final products.
Although disclosed the preferred embodiments of the present invention for illustrative purposes, it should be understood by those skilled in the art that
Various modifications, addition and replacement be all it is feasible, without deviating from such as the scope of following claims present invention disclosed with
Spirit.
Claims (11)
1. a kind of electrolytic copper foil, which includes：
Copper film, which includes 99wt% or more copper；And
Protective layer on the copper film,
Wherein, the tensile strength of the electrolytic copper foil is 45kgf/mm2To 65kgf/mm2。
2. electrolytic copper foil according to claim 1, wherein, the elongation of the electrolytic copper foil is 3% to 13%.
3. electrolytic copper foil according to claim 1, wherein, the thickness of the electrolytic copper foil is 4 μm to 35 μm.
4. electrolytic copper foil according to claim 1, wherein, the protective layer includes chromate, BTA and silanization
At least one in compound.
5. a kind of electrode of secondary cell, which includes：
Electrolytic copper foil, which includes：Copper film comprising 99wt% or more copper and the protective layer on the copper film, it is described
The tensile strength of electrolytic copper foil is 45kgf/mm2To 65kgf/mm2；And
Active material layer on the electrolytic copper foil,
Wherein, the active material layer includes from the group being made up of following material at least one active material selected：Carbon；Bag
Include the metal of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe；Alloy containing the metal；The oxide of the metal；With
And the compound of the metal and carbon.
6. a kind of secondary cell, which includes：
Negative electrode；
Anode；
Electrolyte, enables lithium ion to move between the negative electrode and the anode；And
Sept, be electrically insulated the negative electrode and the anode,
Wherein, the anode includes：
Electrolytic copper foil, which includes：Copper film comprising 99wt% or more copper and the protective layer on the copper film, it is described
The tensile strength of electrolytic copper foil is 45kgf/mm2To 65kgf/mm2；And
Active material layer on the electrolytic copper foil,
Wherein, the active material layer includes from the group being made up of following material at least one active material selected：Carbon；Bag
Include the metal of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe；Alloy containing the metal；The oxide of the metal；With
And the compound of the metal and carbon.
7. it is a kind of manufacture electrolytic copper foil method, the minus plate which is spaced apart in including the electrolyte for accommodating in a cell with
Electric current is conducted between rotary anode cylinder, to form copper film on the rotary anode cylinder,
Wherein, the electrolyte includes that the copper ion of 50g/L to 100g/L, the sulfuric acid of 50g/L to 150g/L and 1ppm are arrived
The organic additive represented by following chemical formula 1 of 6.5ppm：
Chemical formula 1 is：
(H2N(CH2)n)2C=S
Wherein, n is zero, or 6 or the natural number less than 6.
8. method according to claim 7, wherein, the electrolyte also includes gelatin, hydroxyethyl cellulose (HEC), has
At least one in machine sulfide, organic nitrogen compound and thiocarbamide based compound.
9. method according to claim 7, wherein, the electrolyte is maintained at 40 DEG C to 60 DEG C, and by the negative electrode
The current density of Plate supplying is 40A/dm2To 80A/dm2。
10. method according to claim 7, also includes：The copper film is immersed in anti-corrosion solution.
11. methods according to claim 9, wherein, when the copper film is formed, with 30m3/ h to 50m3The flow velocity of/h will
The electrolyte is fed in the electrolytic cell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150135207A KR20170036262A (en) | 2015-09-24 | 2015-09-24 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| KR10-2015-0135207 | 2015-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106558678A true CN106558678A (en) | 2017-04-05 |
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| CN201610579592.6A Pending CN106558678A (en) | 2015-09-24 | 2016-07-21 | The strong electrolytic copper foil of superelevation, including its electrode and secondary cell and its manufacture method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI643393B (en) * | 2017-05-23 | 2018-12-01 | 輝能科技股份有限公司 | Battery structure |
| TWI643386B (en) * | 2017-05-23 | 2018-12-01 | 輝能科技股份有限公司 | Battery structure |
| CN109183081A (en) * | 2018-08-24 | 2019-01-11 | 邵武永太高新材料有限公司 | A kind of preparation method of additive for electrolytic copper foil and dual light electrolytic copper foil |
| CN110880602A (en) * | 2018-09-05 | 2020-03-13 | Kcf技术有限公司 | Copper foil with minimized swelling, wrinkling or tearing, electrode including the same, secondary battery including the same, and method of manufacturing the same |
| CN111316486A (en) * | 2017-09-01 | 2020-06-19 | Kcf技术有限公司 | Electrolytic copper foil, method for producing same, and negative electrode for high-capacity lithium secondary battery comprising same |
| CN112779569A (en) * | 2020-12-30 | 2021-05-11 | 铜陵市华创新材料有限公司 | Method for improving laser die cutting molten beads of electrolytic copper foil for lithium ion battery |
| TWI745864B (en) * | 2019-03-04 | 2021-11-11 | 日商Ｊｘ金屬股份有限公司 | Rolled copper foil for secondary battery negative current collector, secondary battery negative current collector and secondary battery using the copper foil, and manufacturing method of rolled copper foil for secondary battery negative current collector |
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| KR101992840B1 (en) * | 2017-06-20 | 2019-06-27 | 케이씨에프테크놀로지스 주식회사 | Copper foil with minimized bagginess and tear, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| KR101992841B1 (en) | 2017-07-13 | 2019-06-27 | 케이씨에프테크놀로지스 주식회사 | Copper foil with minimized bagginess, wrinkle and tear, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| KR102302184B1 (en) | 2018-02-01 | 2021-09-13 | 에스케이넥실리스 주식회사 | Copper Film With Dimensional Stability And Texture Stability At High Temperature, And Manufacturing Methods Thereof |
| JP6767441B2 (en) * | 2018-08-16 | 2020-10-14 | ケイシーエフ テクノロジース カンパニー リミテッド | Copper foil with minimized sagging, wrinkles and tearing, electrodes containing it, secondary batteries containing it, and methods for manufacturing them. |
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| CN104805478A (en) * | 2014-01-29 | 2015-07-29 | 金居开发铜箔股份有限公司 | Electrolytic copper foil for negative current collector and manufacturing method thereof |
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| EP1167581A4 (en) * | 2000-01-06 | 2005-06-08 | Mitsui Mining & Smelting Co | Electrolytic copper foil and method for inspecting physical property thereof, and copper clad laminate using the electrolytic copper foil |
| CN103314474A (en) * | 2010-12-27 | 2013-09-18 | 古河电气工业株式会社 | Lithium-ion secondary battery, electrode for secondary battery, and electrolytic copper foil for secondary battery electrode |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI643393B (en) * | 2017-05-23 | 2018-12-01 | 輝能科技股份有限公司 | Battery structure |
| TWI643386B (en) * | 2017-05-23 | 2018-12-01 | 輝能科技股份有限公司 | Battery structure |
| CN111316486A (en) * | 2017-09-01 | 2020-06-19 | Kcf技术有限公司 | Electrolytic copper foil, method for producing same, and negative electrode for high-capacity lithium secondary battery comprising same |
| CN109183081A (en) * | 2018-08-24 | 2019-01-11 | 邵武永太高新材料有限公司 | A kind of preparation method of additive for electrolytic copper foil and dual light electrolytic copper foil |
| CN110880602A (en) * | 2018-09-05 | 2020-03-13 | Kcf技术有限公司 | Copper foil with minimized swelling, wrinkling or tearing, electrode including the same, secondary battery including the same, and method of manufacturing the same |
| TWI745864B (en) * | 2019-03-04 | 2021-11-11 | 日商Ｊｘ金屬股份有限公司 | Rolled copper foil for secondary battery negative current collector, secondary battery negative current collector and secondary battery using the copper foil, and manufacturing method of rolled copper foil for secondary battery negative current collector |
| CN112779569A (en) * | 2020-12-30 | 2021-05-11 | 铜陵市华创新材料有限公司 | Method for improving laser die cutting molten beads of electrolytic copper foil for lithium ion battery |
| CN112779569B (en) * | 2020-12-30 | 2022-01-18 | 铜陵市华创新材料有限公司 | Method for improving laser die cutting molten beads of electrolytic copper foil for lithium ion battery |
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