CN108306022A - Electrolytic copper foil, electrode, secondary cell and its manufacturing method comprising it - Google Patents
Electrolytic copper foil, electrode, secondary cell and its manufacturing method comprising it Download PDFInfo
- Publication number
- CN108306022A CN108306022A CN201810035755.3A CN201810035755A CN108306022A CN 108306022 A CN108306022 A CN 108306022A CN 201810035755 A CN201810035755 A CN 201810035755A CN 108306022 A CN108306022 A CN 108306022A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- electrolytic copper
- electrode
- electrolyte
- protective layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Provide a kind of electrolytic copper foil substantially without ridging defect, comprising its electrode, comprising its secondary cell and its manufacturing method.The electrolytic copper foil of the present invention has first surface and the second surface relative to first surface, first surface and second surface are respectively with 4.8 to 16.1 profile high specific (PMR), and electrolytic copper foil has texture coefficient [TC (220)], the 35kgf/mm in 0.49 to 1.28 (220) face2To 58kgf/mm2Yield strength and 3% or smaller deviation of weight.
Description
Cross reference to related applications
This application claims in January in 2017 the 2017-0005857 South Korea patent applications submitted on the 13rd priority and
Equity, the disclosure of which are incorporated herein by reference in their entirety.
Technical field
The present invention relates to a kind of electrolytic copper foil there is no ridging defect, comprising its electrode, comprising the secondary of its
Battery and its manufacturing method.
Background technology
Electrolytic copper foil is used for manufacture various products, such as the cathode and flexible printed circuit board (FPCB) of secondary cell.
When in electrolytic copper foil manufacturing process working condition can not be accurately controlled, cannot prevent from occurring when manufacturing film
Typical ridging defect.
Electrolytic copper foil with ridging defect causes the yield and quality of secondary cell to decline.Specifically, due to having
The surface of the inhomogeneities on the surface of the electrolytic copper foil of ridging defect, electrolytic copper foil cannot equably be applied by negative electrode active material
It covers.The uneven coating of negative electrode active material causes the short circuit of secondary cell or the layering of negative electrode active material.Therefore, cathode copper
The ridging defect of foil is one of the reason of consumer returns goods.
The known deviation of weight for reducing electrolytic copper foil is a kind of method for the ridging defect for inhibiting electrolytic copper foil.But
In the case that the thickness of electrolytic copper foil is 8 μm or smaller (it increases use ratio to improve secondary battery capacity), even if its
Deviation of weight is controlled very low, ridging defect still occurs.
Invention content
The present invention relates to a kind of electrolytic copper foil, comprising its electrode, comprising its secondary cell and its manufacturing method,
The problem of capable of preventing from being caused by the limitation and disadvantage of the relevant technologies.
Moreover, it relates to a kind of electrolytic copper foil there is no ridging defect.
In addition, the present invention relates to a kind of by with there is no that the electrolytic copper foil of ridging defect manufactured can ensure height
The electrode of productivity.
Furthermore the present invention relates to a kind of by with there is no that the electrolytic copper foil of ridging defect manufactured can ensure that Gao Sheng
The secondary cell of yield.
In addition, the present invention relates to a kind of manufacturing methods for the electrolytic copper foil that can prevent ridging defect.
Other than aforementioned aspect of the present invention, other features and advantages of the present invention are described as follows, or are retouched according to following
It states, will become apparent to those skilled in the art.
According to an aspect of the present invention, a kind of electrolytic copper foil is provided, there is first surface and relative to first surface
Second surface, electrolytic copper foil include：Layers of copper includes the mat surface towards first surface and the gloss table towards second surface
Face；First protective layer, on mat surface；And second protective layer, on glossy surface, wherein first surface and second
Respectively with 4.8 to 16.1 profile high specific (PMR), (here, PMR indicates maximum height roughness (R on surfacemax) flat with arithmetic
Equal roughness (Ra) ratio (Rmax/Ra)) and texture coefficient [TC of the electrolytic copper foil with 0.49 to 1.28 (220) face
(220)]、35kgf/mm2To 58kgf/mm2Yield strength and 3% or smaller deviation of weight.
First surface and second surface respectively can be with 1.2 μm to 3.7 μm of maximum height roughness (Rmax) and 0.15 μm
To 0.45 μm of arithmetic average roughness (Ra)。
First protective layer and the second protective layer can respectively contain chromium (Cr).
Electrolytic copper foil can have 4 μm to 30 μm of thickness, and preferably can be with 4 μm to 8 μm of thickness.
According to another aspect of the present invention, a kind of electrode for secondary battery is provided, including：Electrolytic copper foil has the first table
Face and second surface relative to first surface；And first active material layer, on the first surface, wherein electrolytic copper foil packet
It includes：Layers of copper includes the mat surface towards first surface and the glossy surface towards second surface；First protective layer, in nothing
On glossy surface；And second protective layer, on glossy surface, first surface and second surface are respectively with 4.8 to 16.1 PMR
(here, PMR indicates maximum height roughness (Rmax) and arithmetic average roughness (Ra) ratio (Rmax/Ra)) and cathode copper
Texture coefficient [TC (220)], 35kgf/mm of the foil with 0.49 to 1.28 (220) face2To 58kgf/mm2Yield strength, with
And 3% or smaller deviation of weight.
First surface and second surface respectively can be with 1.2 μm to 3.7 μm of maximum height roughness (Rmax) and 0.15 μm
To 0.45 μm of arithmetic average roughness (Ra)。
First protective layer and the second protective layer can respectively contain chromium (Cr).
Electrolytic copper foil can have 4 μm to 30 μm of thickness, and preferably can be with 4 μm to 8 μm of thickness.
Electrode for secondary battery may also include the second active material layer on a second surface, wherein the first active material layer
With the second active material layer respectively may include from by carbon, such as Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe metal, contain
It is selected at least in the group that the alloy of the metal, the oxide of the metal and the compound of the metal and carbon are constituted
A kind of active material.
According to another aspect of the invention, a kind of secondary cell is provided, including：Cathode including the secondary battery
It the anode of pole, the electrolyte for being configured to supply the environment for allowing lithium ion to move between a cathode and an anode and is configured as
The separator that anode and cathode are electrically insulated.
In accordance with a further aspect of the present invention, provide it is a kind of manufacture electrolytic copper foil method, including formed layers of copper and
Protective layer is formed in layers of copper, wherein formed layers of copper the step of include：Electrolyte is prepared, electrolyte includes 70g/L to 90g/L's
Copper ion, the sulfuric acid of 50g/L to 150g/L, the N- allylthioureas (ATU) of 2mg/L to 20mg/L and 2mg/L to 20mg/L
Bis- (3- sulfopropyls)-disulphide (SPS)；And by making density be 40A/dm2To 80A/dm2Electric current from electrode plate stream
Plating is executed to rotation electrode drum, wherein is polished rotation electrode using the polish brush that grain size (grit) is #800 to #3000 and is roused
Surface, and execute be electroplated when, the concentration of the silver (Ag) in electrolyte is maintained into 50mg/L or smaller.
The step of preparing electrolyte may include：Copper wire is heat-treated 30 minutes to 60 minutes at 600 DEG C to 900 DEG C；Acid
Wash heat treated copper wire；It will be in the copper wire merging sulfuric acid of pickling；And there is the sulfuric acid of copper wire to add ATU and SPS to merging.
When executing plating, electrolyte can continuously be filtered, and when executing continuous filtering, the stream of electrolyte
Speed may range from 39m3/ hr to 46m3/hr。
When executing plating, the variation of flow velocity can be 5%/sec or smaller.
Formed layers of copper the step of can also include：The chlorion that precipitated silver (Ag) is AgCl is added to electrolyte, to prevent
Only the concentration of the silver in electrolyte (Ag) is more than 50mg/L.
Formed protective layer the step of may include：Layers of copper is immersed in the rust inhibiting solution of the Cr containing 0.5g/L to 1.5g/L
In.
General description present invention as described above is intended merely to illustrate or explain the present invention, the model without limiting the present invention
It encloses.
Description of the drawings
By reference to attached drawing detailed description of the present invention exemplary embodiment, above and other objects of the present invention, feature
Those of ordinary skill in the art will be apparent with advantage, wherein：
Fig. 1 is the sectional view of electrode for secondary battery according to an embodiment of the invention；
Fig. 2 is X-ray diffraction (XRD) figure of electrolytic copper foil；
Fig. 3 is the photo of the electrolytic copper foil for the comparative example 1 that ridging defect occurs；And
Fig. 4 is the photo of the electrolytic copper foil for the comparative example 4 being torn in its manufacturing process.
Specific implementation mode
It hereinafter, will be with reference to schema detailed description of the present invention embodiment.
For the present invention, various modifications can be carried out and change, and various modifications and change are easy for those skilled in the art
Full of beard and, and all do not depart from the spirit and scope of the present invention.Therefore, the present invention include fall into belonging to claim and its
The all modifications within the scope of the present invention and change that equal objects limit.
Lithium secondary battery includes cathode, anode, the electrolysis for providing the environment that lithium ion can move between a cathode and an anode
Matter and so that cathode is electrically insulated with anode with prevent at an electrode generate electronics pass through via secondary cell inside shifting
The separator for moving another electrode and consuming with being deactivated.
Fig. 1 is the sectional view of electrode for secondary battery according to an embodiment of the invention.
As shown in Figure 1, electrode for secondary battery 100 according to the ... of the embodiment of the present invention includes：Electrolytic copper foil 110 has the
The one surface S1 and second surface S2 opposite with first surface S1；The first active material layer being formed on first surface S1
120a；And it is formed in the second active material layer 120b on second surface S2.In fig. 1 it is shown that respectively in electrolytic copper foil
Showing for the first active material layer 120a and the second active material layer 120b is formed on 110 first surface S1 and second surface S2
Example, but the invention is not restricted to this, and the electrode for secondary battery 100 of the present invention can only include the first active material layer 120a
It is used as active material layer with one in the second active material layer 120b.
In general, in the lithium secondary battery, using aluminium foil as being coupled to the anode current collector of positive electrode active materials, and make
Use electrolytic copper foil as the negative electrode current collector for being coupled to negative electrode active material.
According to an embodiment of the invention, electrode for secondary battery 100 is used as the anode of lithium secondary battery, and electrolytic copper foil 110 is used
Make negative electrode current collector, and the first active material layer 120a and the second active material layer 120b include negative electrode active material.
As shown in Figure 1, the electrolytic copper foil 110 of the present invention includes the layers of copper for having mat surface MS and glossy surface SS
111, the first protective layer 112a for being formed on the mat surface MS of the layers of copper 111 and glossy surface SS for being formed in layers of copper 111
On the second protective layer 112b.
Mat surface MS is the surface of the layers of copper 111 of the first surface S1 towards electrolytic copper foil 110, and glossy surface
SS is the surface of the layers of copper 111 of the second surface S2 towards electrolytic copper foil 110.
The layers of copper 111 of the present invention can be formed by plating on rotation electrode drum.Glossy surface SS refers to being electroplated
The surface contacted is roused with rotation electrode in journey, and mat surface MS refers to the surface opposite with glossy surface SS.
In general, glossy surface SS has the ten mean roughness (Rs lower than mat surface MSz), but the present invention is not
It is limited to this, 10 mean roughness (R of glossy surface SSz) 10 average roughness of mat surface MS can be greater than or equal to
Spend (Rz)。
First protective layer 112a and the second protective layer 112b is formed as preventing the corrosion of layers of copper 111 and improves layers of copper
111 heat resistance, and chromium (Cr) can be contained.
According to an embodiment of the invention, the range of chromium (Cr) adhesion amount in each of first surface S1 and second surface S2
Can be from 1mg/m2To 5mg/m2。
As described above, the electrolytic copper foil 110 with ridging defect leads to the uneven coating of negative electrode active material, and cathode
The uneven coating of active material leads to the short circuit of secondary cell and the layering of negative electrode active material.Therefore, electrolytic copper foil is manufactured
110 should be taken into account all factors for causing 110 ridging defect of electrolytic copper foil.
In accordance with the present invention, it was found that as the surface profile of electrolytic copper foil 110, the crystal structure on surface, yield strength, weight are inclined
The factors such as difference cause the ridging defect of electrolytic copper foil 110.Therefore, it in order to make the ridging defect of electrolytic copper foil 110 minimize, needs
Accurately control these key factors.
Closely related surface profile can be by arithmetic average roughness (R with crystallite dimensiona) and maximum height roughness
(Rmax) indicate, and the crystal structure on surface can indicate by the texture coefficient [TC (220)] in (220) face.
According to the present invention, in order to make the ridging defect of electrolytic copper foil 110 minimize, first surface S1 and second surface S2 are equal
With 4.8 to 16.1 profile high specific (PMR), and electrolytic copper foil has the texture coefficient [TC in 0.49 to 1.28 (220) face
(220)], 35kgf/mm2To 58kgf/mm2Yield strength and 3% or smaller deviation of weight.
PMR refers to maximum height roughness (Rmax) and arithmetic average roughness (Ra) the ratio between (Rmax/Ra).In the present invention,
Arithmetic average roughness (Ra) and maximum height roughness (Rmax) it is according to Japanese Industrial Standards (JIS) B 0601-2001 standards
It measures and [measures length：4mm (not including cut-off parts)].
When PMR is more than 16.1, air can will be wrapped in spool by the electrolytic copper foil 110 for being electrolysed plating manufacture
(bobbin) it is trapped in when between electrolytic copper foil 110, so as to cause ridging defect.On the other hand, when PMR is less than 4.8, electricity
Solution copper foil 110 can locally extend when during roll-to-roll (roll-to-roll, RTR) is handled on spool, so as to cause
Ridging defect.
According to an embodiment of the invention, first surface S1 and second surface S2 can all have 1.2 μm to 3.7 μm of maximum height
Spend roughness (Rmax) and 0.15 μm to 0.45 μm of arithmetic average roughness (Ra)。
In the present invention, the texture coefficient for measuring and calculating (220) face of electrolytic copper foil 110 is as follows.
First, X-ray diffraction (XRD) [target is executed by the angle of diffraction (2 θ) with ranging from 30 ° to 95 °：Copper K α 1,
2 intervals θ：0.01 °, 2 θ scan rate：3 °/min], the XRD diagram with the peak corresponding to n crystal face is obtained (for example, as in Fig. 2
Shown in, there is the XRD diagram at the peak corresponding to (111), (200), (220) and (311) face), and obtain each crystal face from XRD diagram
(hkl) XRD diffracted intensities [I (hkl)].In addition, obtaining by Joint Committee on Powder Diffraction Standards (Joint Committee
On Power Diffraction standards, JCPDS) as defined in standard copper powders n crystal face in each of XRD spread out
Penetrate intensity [I0(hkl)].Next, obtaining I (hkl)/I of n crystal face0(hkl) arithmetic mean of instantaneous value, then by by (220)
I (the 220)/I in face0(220) divided by arithmetic mean of instantaneous value calculates the texture coefficient [TC in (220) face of electrolytic copper foil 110
(220)].That is, the texture coefficient [TC (220)] in (220) face will be calculated based on following equation 1.
[equation 1]
When the texture coefficient [TC (220)] in (220) face is less than 0.49, the crystal structure of electrolytic copper foil 110 is not intensive enough,
And when electrolytic copper foil 110 is wound around spool, crystal structure is easily deformed, and leads to ridging defect.On the other hand, when (220) face
Texture coefficient [TC (220)] when being more than 1.28, the crystal structure of electrolytic copper foil 110 becomes overstocked and has high brittleness, as a result,
Electrolytic copper foil 110 is torn in the fabrication process.
In the present invention, yield strength is the yield strength measured at 25 DEG C of room temperature, and uses universal testing machine
(Universal testing machine, UTM) measures [Sample Width：12.7mm, the distance between fixture：50mm is measured
Speed：50mm/min).
When the yield strength of electrolytic copper foil 110 is less than 35kgf/mm2When, it is led when electrolytic copper foil 110 is wound around spool
Plastic deformation is caused, to accelerate ridging defect.On the other hand, when the yield strength of electrolytic copper foil 110 is more than 58kgf/mm2When,
The brittleness of electrolytic copper foil 110 gets higher and makes compatible reduction, and increases the wind for tearing electrolytic copper foil 110 in the fabrication process
Danger.
In the present invention, deviation of weight refers to the deviation of weight of width direction, and such as get off measurement and calculating.
After the point of the left, center, right in the width direction of electrolytic copper foil 110 takes the sample of 5cm × 5cm, three samples are measured
Each weight of product.Arithmetic average weight and standard deviation are calculated using measured value, then calculates standard deviation and calculation
The ratio (%) (that is, (standard deviation/arithmetic mean weight) × 100]) of number average weight.
When the deviation of weight of electrolytic copper foil 110 is more than 3%, electrolytic copper foil 110 is wound in electrolytic copper foil 110 around spool
When locally extend, cause to wrinkle.
The electrolytic copper foil 110 of the present invention has the elongation more than or equal to 3% under room temperature (25 DEG C)
(Elongation).When the elongation of electrolytic copper foil 110 is less than 3%, electrolytic copper foil 110 will not be because in manufacture electrolytic copper foil
The power that is applied during 110 or during manufacturing electrode for secondary battery 100 and stretch, increase electrolytic copper foil 110
The risk of tearing.
The electrolytic copper foil 110 of the present invention can be with 4 μm to 30 μm of thickness, and preferably, can have 4 μm to 8 μm of thickness
Degree.When the thickness of electrolytic copper foil 110 is less than 4 μm, the machinability (workability) of manufacture secondary cell process reduces.
On the other hand, when the thickness of electrolytic copper foil 110 is more than 30 μm, it may be difficult to ensure enough capacity of secondary cell.
Specifically, due to being 8 μm or more by simply reducing the deviation of weight of electrolytic copper foil 110 to be difficult to prevent thickness
The ridging defect of the electrolytic copper foil 110 of small (manufacture high-capacity secondary battery needs to increase thickness), it is therefore desirable to further apply
The technical characteristic of the present invention.
Each in first active material layer 120a and the second active material layer 120b may include from by carbon；Si、Ge、
The metal of Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe；Include the alloy of the metal；The oxide of the metal；And the metal and carbon
Compound composition group in at least one that selects as negative electrode active material.
In order to increase the charge/discharge capacity of secondary cell, the first active material layer 120a and the second active material layer 120b can
It is formed by the mixture of the Si containing predetermined amount.
Hereinafter, will be described in the manufacturing method of electrolytic copper foil 110 according to an embodiment of the invention.
The method of the present invention includes form layers of copper 111 and form the first protective layer 112a and second in layers of copper 111 to protect
Sheath 112b.
First, the copper ion containing 70g/L to 90g/L, the sulfuric acid of 50g/L to 150g/L, 2mg/L are prepared to 20mg/L's
The electrolyte of bis- (3- sulfopropyls)-disulphide (SPS) of N- allylthioureas (ATU) and 2mg/L to 20mg/L.
The yield strength of electrolytic copper foil 110 can control by adjusting the concentration of ATU.With the increase of ATU concentration, electricity
The yield strength of solution copper foil 110 also substantially increases.
The texture coefficient [TC (220)] in each (220) face in the first surface S1 and second surface S2 of electrolytic copper foil 110
It can be controlled by adjusting the concentration of SPS.The texture coefficient [TC (220)] in (220) face of electrolytic copper foil 110 is also with SPS
The increase of concentration and substantially increase.
30 minutes to 60 minutes are heat-treated to burn up organic matter at 600 DEG C to 900 DEG C to high-purity copper wire, pickling carries out
The copper wire of Overheating Treatment, and the copper wire of pickling is placed in sulfuric acid to prepare a small amount of or free from foreign meter electrolyte.Then, may be used
To prepare electrolyte by adding ATU and SPS.
Then, at 50 DEG C to 60 DEG C by with density being in the electrolytic solution 40A/dm2To 80A/dm2Electric current execute plating
To form layers of copper 111 on rotation electrode drum, wherein electric current flows to the rotation electrode drum being spaced apart with electrode plate from electrode plate.
Current density influences the arithmetic average roughness (R of electrolytic copper foil 110a).Arithmetic average roughness (Ra) with electric current
The increase of density and substantially reduce.In other words, with the reduction of current density, arithmetic average roughness (Ra) substantially increase
Add.
The surface of rotation electrode drum is polished (for example, passing through execution using the polish brush that grain size (grit) is #800 to #3000
The surface of electrodeposition copper).Preferably, while water is spread in the direction of the width, by surface that rotation electrode is roused into
Row surface polishes, and the surface that rotation electrode rouses is made equably to be polished in the width direction on the surface that rotation electrode rouses.
The polishing on the surface (for example, surface by executing electrodeposition copper) of rotation electrode drum influences electrolytic copper foil
Arithmetic average roughness (the R of 110 second surface S2a), maximum height roughness (Rmax) etc..
According to the present invention, when being electroplated, the concentration of the silver (Ag) in electrolyte is maintained at 50mg/L or smaller.Silver
(Ag) concentration influences the maximum height roughness (R of electrolytic copper foil 110max).The maximum height roughness of electrolytic copper foil 110
(Rmax) as the concentration of silver-colored (Ag) reduces and substantially increases.
In plating, silver is introduced into electrolyte and the concentration of silver-colored (Ag) in electrolyte is made to be more than 50mg/L in order to prevent, can
A small amount of chlorion (for example, 15 to 25mg/L) to be added in electrolyte, silver-colored (Ag) is precipitated as AgCl by chlorion.As a result,
Electrolyte can have silver (Ag) concentration of for example, 1mg/L to 50mg/L.
It can be in 39m3/ hr to 46m3Continuous (or cycle) filtering is carried out under the flow of/hr, with while being electroplated
Solid impurity is removed from electrolyte.When flow is less than 39m3When/hr, flow velocity reduces, and overvoltage increases, and layers of copper 111 is uneven
It is formed evenly.On the other hand, when flow is more than 46m3When/hr, filter is impaired, and foreign matter enters electrolyte.The stream of electrolyte
Amount also influences the yield strength of electrolytic copper foil 110.
It is 3% or smaller electrolytic copper foil 110 to manufacture deviation of weight, preferably keeps change in flow when being electroplated
In 5%/sec or smaller.When the change in flow of electrolyte is more than 5%/sec, the copper facing efficiency of the width direction of layers of copper 111
Variation increases, and the deviation of weight of electrolytic copper foil 110 is more than 3%.
Then, by impregnated in rust inhibiting solution layers of copper 111 manufactured as described above (such as soaking at room temperature 2 seconds extremely
20 seconds) and dry layers of copper 111, it is formed every in the first protective layer 112a and the second protective layer 112b being located in layers of copper 111
One, rust inhibiting solution contains the Cr of 0.5g/L to 1.5g/L.
Rust inhibiting solution can also include at least one of silane compound and nitrogen compound.For example, rust inhibiting solution can be with
The silane compound of Cr and 0.5g/L to 1.5g/L containing 0.5g/L to 1.5g/L.
The electrode for secondary battery (that is, anode) of the present invention can be by being manufactured as described above with negative electrode active material coating
The electrolytic copper foil 110 of the present invention manufactures.
Negative electrode active material can be from by carbon；The metal of such as Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni or Fe；Including
The alloy of the metal；The oxide of the metal；And it is selected in the group of the compound of the metal and carbon composition.
For example, mixing 1 to 3 parts by weight butadiene-styrene rubber (SBR) and 1 to 3 parts by weight carboxymethyl fibre in the carbon of 100 parts by weight
Dimension plain (CMC) is used for negative electrode active material, then prepares slurry using distilled water as solvent.It then, will be electric using scraper
It solves copper foil 110 and coats the slurry with 20 to 100 μm of thickness, and in 110 to 130 DEG C of temperature, 0.5 to 1.5ton
cm2Pressure under suppressed.
Lithium secondary battery can use traditional cathode, electrolyte and separator and the manufactured present invention's as described above
Electrode for secondary battery (or anode) manufactures.
Hereinafter, will be with reference to example and the comparative example detailed description present invention.However, following example is only to aid in understanding originally
The example of invention, the scope of the present invention are not limited to these examples.
Example 1 to 6 and comparative example 1 to 7
In the electrolytic solution by making density be 60A/dm2Electric current flowed to from electrode plate and be set as being spaced apart with electrode plate
Rotation electrode drum forms layers of copper to be roused in rotation electrode.Electrolyte includes the copper ion of 75g/L, the sulfuric acid of 100g/L, 100g/
The SPS of the ATU and 100g/L of L, and maintain at a temperature of 55 DEG C.The flow velocity of electrolyte is 42m3/hr.ATU concentration, SPS are dense
Degree, silver-colored (Ag) concentration, electrolyte flow velocity variation and polish brush for surface polishing rotation electrode drum grain size it is as follows
Shown in table 1.It will be immersed in rust inhibiting solution, be then dried to prepare electrolytic copper foil by executing the layers of copper that plating is formed.
[table 1]
Obtain the PMR of the electrolytic copper foil of example as described above and comparative example, the texture coefficient [TC (220)] in (220) face,
Yield strength and deviation of weight, the results are shown in tables 2.In addition, table 2 shows that electrolytic copper foil manufactures in example and comparative example
Whether occur wrinkling and tearing in the process.
* profile maximum rate (PMR)
According to JIS B 0601-2001 standards electrolysis is measured using the SJ-310 illumination photometers manufactured by Mitutoyo companies
Copper foil first surface (surface adjacent with mat surface of layers of copper) and second surface (layers of copper it is adjacent with glossy surface
Surface) arithmetic average roughness (Ra) and maximum height roughness (Rmax) [measure length：4mm (not including truncation part)].
Next, by calculating maximum height roughness (Rmax) and arithmetic average roughness (Ra) the ratio between (Rmax/Ra) obtain the first table
Each PMR in face and second surface.
* the texture coefficient [TC (220)] in (220) face
By carrying out XRD [(i) targets with ranging from 30 ° to 95 ° of the angle of diffraction (2 θ)：Copper K α 1,2 intervals θ (ii)：
0.01 °, (iii) 2 θ scans rate：3 °/min] XRD diagram at the peak with corresponding n crystal face is obtained, and obtain each crystalline substance from XRD diagram
The XRD diffracted intensities [I (hkl)] in face (hkl).In addition, obtaining each brilliant in n crystal face of the standard copper powder as defined in JCPDS
XRD diffracted intensities [the I in face0(hkl)].Next, obtaining I (hkl)/I of n crystal face0(hkl) arithmetic mean of instantaneous value, then leads to
It crosses I (the 220)/I in (220) face0(220) divided by arithmetic mean of instantaneous value, come calculate electrolytic copper foil 110 (220) face texture system
Number [TC (220)].That is, the texture coefficient [TC (220)] in (220) face will be calculated based on equation 1 below.
[equation 1]
Yield strength (kgf/mm2)
In 25 DEG C of the yield strength for using UTM to measure electrolytic copper foil at room temperature.The width of sample be 12.7mm, fixture it
Between distance be 50mm, measuring speed 50mm/min.
* deviation of weight (%)
After the point of the left, center, right in the width direction of electrolytic copper foil takes the sample of 5cm × 5cm, three are measured respectively
The weight of a sample.Arithmetic average weight and standard deviation are calculated using measured value, then calculates standard deviation and arithmetic mean
The ratio (%) (that is, (standard deviation/arithmetic mean weight) × 100) of weight.
[table 2]
It is being electrolysed in the case where electrolytic copper foil includes surfaces of the PMR less than 4.8 (in comparative example 1) with reference to upper table 2
In the case of the surface that copper foil includes PMR more than 16.1 (in comparative example 2), include the texture system in (220) face in electrolytic copper foil
Include that yield strength is small on the surface of electrolytic copper foil in the case of surface of the number [TC (220)] less than 0.49 (in comparative example 6)
In 35kgf/mm2Surface in the case of (in comparative example 3), and electrolytic copper foil include deviation of weight be more than 3% table
In the case of face (in comparative example 5), wrinkle in the manufacturing process of electrolytic copper foil.Fig. 3 is that comparative example 1 wrinkles
The photo of the electrolytic copper foil of defect.
In addition, including that yield strength is more than 58kgf/mm in electrolytic copper foil2Surface in the case of (in comparative example 4),
The tearing of electrolytic copper foil has occurred.Fig. 4 be comparative example 4 manufacturing process in electrolytic copper foil tear photo.
Specifically, the case where the texture coefficient [TC (220)] that electrolytic copper foil includes (220) face is more than 1.28 surface
Under (in comparative example 7), occur corrugation and tearing.
According to the present invention it is possible to manufacture the electrolytic copper foil that there is no ridging defect, as a result, be used for secondary electricity in manufacture
When the cathode in pond, electrolytic copper foil can be evenly coated with negative electrode active material.Therefore, according to the present invention it is possible to prevent due to
The short circuit of secondary cell caused by the uneven coating of negative electrode active material and the layering of negative electrode active material.As a result, according to this
Invention, can improve service life and the capacity retention ratio of secondary cell.
Claims (16)
1. a kind of electrolytic copper foil, with first surface and the second surface relative to first surface, the electrolytic copper foil includes：
Layers of copper includes the mat surface towards first surface and the glossy surface towards second surface；
First protective layer, on mat surface；And
Second protective layer, on glossy surface,
Wherein, first surface and second surface are respectively with 4.8 to 16.1 profile high specific PMR, wherein profile high specific indicates
Maximum height roughness RmaxWith arithmetic average roughness RaRatio Rmax/Ra, and
Texture coefficient [TC (220)], 35kgf/mm of the electrolytic copper foil with 0.49 to 1.28 (220) face2To 58kgf/mm2's
Yield strength and 3% or smaller deviation of weight.
2. electrolytic copper foil as described in claim 1, wherein first surface and second surface respectively have 1.2 μm to 3.7 μm most
Big height roughness RmaxAnd 0.15 μm to 0.45 μm of arithmetic average roughness Ra。
3. electrolytic copper foil as described in claim 1, wherein the first protective layer and the second protective layer are respectively comprising chromium Cr.
4. electrolytic copper foil as described in claim 1, wherein electrolytic copper foil has 4 μm to 30 μm of thickness.
5. a kind of electrode for secondary battery, including：
Electrolytic copper foil has first surface and the second surface relative to first surface；And
First active material layer is formed on the first surface,
Wherein, electrolytic copper foil includes：
Layers of copper includes the mat surface towards first surface and the glossy surface towards second surface；
First protective layer, on mat surface；And
Second protective layer, on glossy surface,
Wherein, first surface and second surface are respectively with 4.8 to 16.1 profile high specific PMR, wherein profile high specific indicates
Maximum height roughness RmaxWith arithmetic average roughness RaRatio Rmax/Ra, and
Texture coefficient [TC (220)], 35kgf/mm of the electrolytic copper foil with 0.49 to 1.28 (220) face2To 58kgf/mm2's
Yield strength and 3% or smaller deviation of weight.
6. electrode for secondary battery as claimed in claim 5, wherein first surface and second surface respectively have 1.2 μm to 3.7 μm
Maximum height roughness RmaxAnd 0.15 μm to 0.45 μm of arithmetic average roughness Ra。
7. electrode for secondary battery as claimed in claim 5, wherein the first protective layer and the second protective layer are respectively comprising chromium Cr.
8. electrode for secondary battery as claimed in claim 5, wherein electrolytic copper foil has 4 μm to 30 μm of thickness.
9. electrode for secondary battery as claimed in claim 5, further includes：The second active material layer on a second surface is set,
Wherein, the first active material layer and the second active material layer include respectively from by carbon, such as Si, Ge, Sn, Li, Zn, Mg, Cd,
The compound structure of the metal of Ce, Ni or Fe, the alloy containing the metal, the oxide of the metal and the metal and carbon
At group at least one active material for selecting.
10. a kind of secondary cell, including：
Cathode；
Anode includes the electrode for secondary battery according to any one of claim 5 to 9；
Electrolyte is configured to supply the environment for allowing lithium ion to move between a cathode and an anode；And
Separator is configured as anode and cathode being electrically insulated.
11. a kind of method of manufacture electrolytic copper foil, the method includes：
Form layers of copper；And
Protective layer is formed in layers of copper,
Wherein, the step of formation layers of copper includes：
Prepare electrolyte, electrolyte include the copper ion of 70g/L to 90g/L, the sulfuric acid of 50g/L to 150g/L, 2mg/L extremely
Bis- (3- sulfopropyls)-disulphide SPS of the N- allylthiourea ATU and 2mg/L to 20mg/L of 20mg/L；And
By making density be 40A/dm2To 80A/dm2Electric current flow to rotation electrode drum from electrode plate and execute plating,
Wherein, the surface of rotation electrode drum is polished using the polish brush that grain size grit is #800 to #3000, and
When executing plating, the concentration of the silver-colored Ag in electrolyte is maintained into 50mg/L or smaller.
12. method as claimed in claim 11, wherein the step of preparing electrolyte include：
Copper wire is heat-treated 30 minutes to 60 minutes at 600 DEG C to 900 DEG C；
The heat treated copper wire of pickling；
It will be in the copper wire merging sulfuric acid of pickling；And
There is the sulfuric acid of copper wire to add ATU and SPS to merging.
13. method as claimed in claim 11, wherein：
When executing plating, electrolyte is continuously filtered；And
When executing continuous filtering, the ranging from 39m of the flow velocity of electrolyte3/ hr to 46m3/hr。
14. method as claimed in claim 13, wherein when executing plating, the variation of flow velocity is 5%/sec or smaller.
15. method as claimed in claim 11, wherein formed layers of copper the step of further include：By the chlorine that precipitated silver Ag is AgCl
Ion is added to electrolyte, is more than 50mg/L to prevent the concentration of the silver-colored Ag in electrolyte.
16. method as claimed in claim 11, wherein formed protective layer the step of include：Layers of copper is immersed in containing 0.5g/
In the rust inhibiting solution of the Cr of L to 1.5g/L.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0005857 | 2017-01-13 | ||
| KR1020170005857A KR20180083515A (en) | 2017-01-13 | 2017-01-13 | Electrolytic Copper Foil Substantially Free Of Wrinkle Problem, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108306022A true CN108306022A (en) | 2018-07-20 |
| CN108306022B CN108306022B (en) | 2021-09-21 |
Family
ID=62868754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810035755.3A Active CN108306022B (en) | 2017-01-13 | 2018-01-15 | Electrolytic copper foil, electrode comprising same, secondary battery and method for manufacturing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6545300B2 (en) |
| KR (1) | KR20180083515A (en) |
| CN (1) | CN108306022B (en) |
| TW (1) | TWI659827B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699715A (en) * | 2019-10-21 | 2020-01-17 | 湖北中科铜箔科技有限公司 | Composite additive composition for preparing electrolytic copper foil and preparation method thereof |
| WO2020156158A1 (en) * | 2019-02-01 | 2020-08-06 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode, and lithium ion secondary battery having same |
| CN113490770A (en) * | 2019-11-08 | 2021-10-08 | Sk纳力世有限公司 | Electrolytic copper foil capable of preventing tearing or wrinkle failure, electrode comprising the electrolytic copper foil, secondary battery comprising the electrode, and method for manufacturing the electrolytic copper foil |
| CN113661587A (en) * | 2019-11-21 | 2021-11-16 | Sk纳力世有限公司 | Electrolytic copper foil capable of preventing tearing or wrinkling failure, method of manufacturing the same, electrode including the electrolytic copper foil, and secondary battery including the electrode |
| CN113924669A (en) * | 2019-11-21 | 2022-01-11 | Sk纳力世有限公司 | Copper foil preventing occurrence of wrinkles, electrode including the same, secondary battery including the same, and method of manufacturing the same |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR102439621B1 (en) | 2017-09-01 | 2022-09-01 | 에스케이넥실리스 주식회사 | Copper Film, Manufacturing Methods Thereof, And Anode For Li Secondary Battery Comprising The Same |
| JP7087760B2 (en) * | 2018-07-18 | 2022-06-21 | 住友金属鉱山株式会社 | Copper-clad laminate |
| HUE058062T2 (en) * | 2018-08-08 | 2022-06-28 | Sk Nexilis Co Ltd | Copper foil with minimized bagginess and tear, electrode comprising the same, secondary battery comprising the same and method for manufacturing the same |
| JP6700347B2 (en) * | 2018-08-09 | 2020-05-27 | 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 minimal sagging and tearing, electrode including the same, secondary battery including the same, and manufacturing method thereof |
| TWI679311B (en) * | 2018-08-10 | 2019-12-11 | 南韓商Ｋｃｆ科技有限公司 | Copper foil with minimized bagginess, wrinkle or tear, electrode including the same, secondary battery including the same and method for manufacturing the same |
| EP3608447B1 (en) * | 2018-08-10 | 2021-10-06 | SK Nexilis Co., Ltd. | Copper foil with minimized bagginess, wrinkle and tear, electrode including the same, secondary battery including the same and method for manufacturing the same |
| 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. |
| TWI669032B (en) * | 2018-09-26 | 2019-08-11 | 金居開發股份有限公司 | Micro-rough electrolytic copper foil and copper foil substrate |
| TWI700393B (en) * | 2019-08-27 | 2020-08-01 | 長春石油化學股份有限公司 | Electrolytic copper foil and electrode and lithium ion cell comprising the same |
| US20220102730A1 (en) * | 2020-09-28 | 2022-03-31 | Industrial Technology Research Institute | Electrolytic copper foil and negative current collector of lithium secondary battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101669237A (en) * | 2007-04-20 | 2010-03-10 | 日矿金属株式会社 | Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil |
| 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 |
| 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 |
| CN105705329A (en) * | 2013-11-08 | 2016-06-22 | 日进材料股份有限公司 | Electrodeposited copper, and electrical component and battery comprising same |
| WO2016208858A1 (en) * | 2015-06-26 | 2016-12-29 | 엘에스엠트론 주식회사 | Electrolytic copper foil for lithium secondary battery and lithium secondary battery including same |
| TW201700739A (en) * | 2015-06-24 | 2017-01-01 | Ｌｓ美創有限公司 | Electrolytic copper foil, current collector comprising the same, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100389061B1 (en) * | 2002-11-14 | 2003-06-25 | 일진소재산업주식회사 | Electrolytic copper foil and process producing the same |
| JP2007294923A (en) * | 2006-03-31 | 2007-11-08 | Nikko Kinzoku Kk | Manufacturing method of copper strip or copper foil having excellent strength, electric conductivity, and bendability, and electronic component using the same |
| JP5588607B2 (en) * | 2007-10-31 | 2014-09-10 | 三井金属鉱業株式会社 | Electrolytic copper foil and method for producing the electrolytic copper foil |
| TWI542739B (en) * | 2014-03-21 | 2016-07-21 | 長春石油化學股份有限公司 | Electrolytic copper foil |
| KR20180080514A (en) * | 2017-01-04 | 2018-07-12 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil Having High Corrosion Resistance and Excellent Adhesiveness with Active Material, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
| KR20180080512A (en) * | 2017-01-04 | 2018-07-12 | 케이씨에프테크놀로지스 주식회사 | Electrolytic Copper Foil with Optimized Peak Roughness, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
-
2017
- 2017-01-13 KR KR1020170005857A patent/KR20180083515A/en active Search and Examination
-
2018
- 2018-01-12 TW TW107101278A patent/TWI659827B/en active
- 2018-01-12 JP JP2018003348A patent/JP6545300B2/en active Active
- 2018-01-15 CN CN201810035755.3A patent/CN108306022B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101669237A (en) * | 2007-04-20 | 2010-03-10 | 日矿金属株式会社 | Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil |
| 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 |
| CN105705329A (en) * | 2013-11-08 | 2016-06-22 | 日进材料股份有限公司 | Electrodeposited copper, and electrical component and battery comprising same |
| 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 |
| TW201700739A (en) * | 2015-06-24 | 2017-01-01 | Ｌｓ美創有限公司 | Electrolytic copper foil, current collector comprising the same, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same |
| WO2016208858A1 (en) * | 2015-06-26 | 2016-12-29 | 엘에스엠트론 주식회사 | Electrolytic copper foil for lithium secondary battery and lithium secondary battery including same |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788727A (en) * | 2019-02-01 | 2020-10-16 | 长春石油化学股份有限公司 | Electrolytic copper foil, current collector, electrode, and lithium ion secondary battery comprising same |
| US11145867B2 (en) | 2019-02-01 | 2021-10-12 | Chang Chun Petrochemical Co., Ltd. | Surface treated copper foil |
| US10765010B2 (en) | 2019-02-01 | 2020-09-01 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil for printed circuit board with low transmission loss |
| US10772199B2 (en) | 2019-02-01 | 2020-09-08 | Chang Chun Petrochemical Co., Ltd. | Low transmission loss copper foil and methods for manufacturing the copper foil |
| US10787751B2 (en) | 2019-02-01 | 2020-09-29 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil with low profile |
| TWI707063B (en) * | 2019-02-01 | 2020-10-11 | 長春石油化學股份有限公司 | Surface-treated copper foil, laminate, and device comprising the copper foil |
| WO2020156158A1 (en) * | 2019-02-01 | 2020-08-06 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode, and lithium ion secondary battery having same |
| US11362337B2 (en) | 2019-02-01 | 2022-06-14 | Chang Chun Petrochemical Co., Ltd. | Electrodeposited copper foil and electrode, and lithium-ion secondary battery comprising the same |
| US11283080B2 (en) | 2019-02-01 | 2022-03-22 | Chang Chun Petrochemical Co., Ltd. | Electrodeposited copper foil, current collector, electrode, and lithium ion secondary battery comprising the same |
| CN111788727B (en) * | 2019-02-01 | 2022-02-08 | 长春石油化学股份有限公司 | Electrolytic copper foil, current collector, electrode, and lithium ion secondary battery comprising same |
| CN110699715A (en) * | 2019-10-21 | 2020-01-17 | 湖北中科铜箔科技有限公司 | Composite additive composition for preparing electrolytic copper foil and preparation method thereof |
| CN113490770A (en) * | 2019-11-08 | 2021-10-08 | Sk纳力世有限公司 | Electrolytic copper foil capable of preventing tearing or wrinkle failure, electrode comprising the electrolytic copper foil, secondary battery comprising the electrode, and method for manufacturing the electrolytic copper foil |
| CN113661587A (en) * | 2019-11-21 | 2021-11-16 | Sk纳力世有限公司 | Electrolytic copper foil capable of preventing tearing or wrinkling failure, method of manufacturing the same, electrode including the electrolytic copper foil, and secondary battery including the electrode |
| CN113924669A (en) * | 2019-11-21 | 2022-01-11 | Sk纳力世有限公司 | Copper foil preventing occurrence of wrinkles, electrode including the same, secondary battery including the same, and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI659827B (en) | 2019-05-21 |
| CN108306022B (en) | 2021-09-21 |
| TW201825285A (en) | 2018-07-16 |
| JP6545300B2 (en) | 2019-07-17 |
| JP2018111882A (en) | 2018-07-19 |
| KR20180083515A (en) | 2018-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108306022A (en) | Electrolytic copper foil, electrode, secondary cell and its manufacturing method comprising it | |
| CN108075098B (en) | Electrolytic copper foil, electrode for secondary battery, and method for producing electrolytic copper foil | |
| JP7343474B2 (en) | Copper foil in which wrinkles are prevented, electrodes containing the same, secondary batteries containing the same, and manufacturing method thereof | |
| TWI661597B (en) | Easily handleable electrolytic copper foil, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same | |
| TWI624986B (en) | Electrolytic copper foil capable of improving capacity retention rate of secondary battery, electrode including the same, secondary battery including the same, and method of manufacturing the same | |
| CN106973570B (en) | Electrolytic copper foil, electrode comprising the electrolytic copper foil, secondary battery comprising the electrolytic copper foil, and method for manufacturing the electrolytic copper foil | |
| TWI682075B (en) | Electrolytic copper foil having optimized peak roughness, electrode including the same, secondary battery including the same, and method of manufacturing the same | |
| KR102413056B1 (en) | Copper foil free from wrinkle and having improved charge discharge property, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same | |
| CN108270016A (en) | Electrolytic copper foil, electrode, secondary cell and its manufacturing method | |
| KR102446550B1 (en) | Copper foil for high capacity secondary battery, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same | |
| KR102546687B1 (en) | Copper foil capable of manufacturing high capacity secondary battery, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same | |
| CN111316486B (en) | Electrolytic copper foil, method for producing same, and negative electrode for high-capacity lithium secondary battery comprising same | |
| JP2020508399A (en) | Copper foil having excellent adhesive strength, electrode including the same, secondary battery including the same, and method of manufacturing the same | |
| TW202121717A (en) | Copper foil free from generation of wrinkle, electrode comprising the same, secondary battery comprising the same and method for manufacturing the same | |
| KR102405236B1 (en) | Method for manufacturing electrolytic copper foil | |
| KR20180083512A (en) | Electrolytic Copper Foil of High Reliability, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same | |
| JP2013256712A (en) | Electrolytic copper foil for secondary battery collector | |
| JP6700347B2 (en) | Copper foil with minimal sagging and tearing, electrode including the same, secondary battery including the same, and manufacturing method thereof | |
| CN110880601B (en) | Copper foil with minimized swelling and tearing, electrode including the same, secondary battery including the same, and method of manufacturing the same | |
| KR20180100939A (en) | Copper foil with minimized wringkle, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180823 Address after: Gyeonggi Do, South Korea Applicant after: KCF Technology Co., Ltd. Address before: South Korea Gyeonggi Do Anyang Applicant before: Ls Megtron Co. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Han Guoquanluobeidao Applicant after: Sk Nashi Co.,Ltd. Address before: Han Guojingjidao Applicant before: KCF Technology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |