CN105986288A - Electrolytic foil, electrical component containing electrolyte foil and battery - Google Patents
Electrolytic foil, electrical component containing electrolyte foil and battery Download PDFInfo
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Abstract
The invention relates to an electrolytic foil, an electrical component containing the electrolytic foil and a battery. The invention provides the electrolytic foil, wherein the average diameter of pores of an area among prominent surface elements of a separating-out surface is 1 nanometer to 100 nanometers. The electrolytic foil shows high elongation rate while maintaining low roughness and high strength, thus being applicable to semiconductor packaging substrates for tape automated bonding used in current collector and tape carrier package of large and medium lithium ion secondary batteries.
Description
Technical field
The present invention relates to electrolytic copper foil, the electric component comprising electrolytic copper foil and battery, say in more detail
Relate to that there is after high-temperature heat treatment high tensile and the low roughness of percentage elongation, height the most simultaneously
Intensity and high extension electrolytic copper foil.
Background technology
As the collector body of secondary cell, generally use Copper Foil.Above-mentioned Copper Foil mainly uses based on rolling
The rolled copper foil of system processing, but its manufacturing expense is high and is difficult to manufacture the Copper Foil of wide cut.Further, roll
Copper Foil processed adds man-hour requirement in rolling and uses lubricating oil, and the pollution of lubricating oil can cause and active substance
Adaptation reduce, it is possible to reduce battery charge/discharge cycle characteristics.
Lithium battery is when discharge and recharge, along with fever phenomenon based on change in volume and overcharge.And
And, in order to improve the adaptation with electrode active material, and make copper foil base material be less subject to based on
The impact that the dilation of the active material layer of charge and discharge cycles is relevant, prevents as current collection having
The effect produce fold in the Copper Foil of body, rupturing etc., the surface roughness of Copper Foil is low.Therefore,
Urgently be developed to bear change in volume and the fever phenomenon of lithium battery, and with active substance
High extension, high intensity and the low roughness Copper Foil of excellent adhesion.
Further, in order to cater to the compact demand to electronic device, in order to improve based on Gao Gong
The integrated level of the circuit in energyization, miniaturization, light-weighted little area, installs base for quasiconductor
The demand of the fine wiring of plate or motherboard substrate is gradually increased.When having this fine pattern
When the manufacture of printed circuit board (PCB) utilizes thick Copper Foil, become for forming the etching period of wired circuit
Long, the sidewall verticality of wiring pattern reduces.Particularly, at the wiring pattern formed by etching
Wiring live width narrower in the case of, wiring may be broken.Therefore, in order to obtain minuteness space
Circuit, it is desirable to provide the Copper Foil that thickness is thinner.But, thin copper foil is limited due to the thickness of Copper Foil
System, its mechanical strength is weak, when manufacturing printed circuit board (PCB), the frequency that fold or bending etc. are bad occurs
Rate increases.
Additionally, for the use used in TCP (carrier package (Tape Carrier Package))
Semiconductor packages in TAB (belt engages (Tape Automated Bonding) automatically)
(packaging) substrate etc. are positioned on the Hall element (device hall) of the central part of product
The inner lead (inner lead) arranged, will directly engage multiple terminals of IC chip, now,
Engagement device moment turn-on current is utilized to heat and apply certain pressure.Thus, by electrolysis
The inner lead that the etching of Copper Foil is formed, its engaged pressure pulls and extends.
Accordingly, it is desirable to provide a kind of thickness is thin, mechanical strength is high and can realize the low coarse of high extension
Degree Copper Foil.
Summary of the invention
It is an aspect of the invention to provide a kind of new electrolytic copper foil.
Another aspect of the present invention is to provide a kind of electric component comprising electrolytic copper foil.
An additional aspect of the present invention is to provide a kind of battery comprising electrolytic copper foil.
In order to realize purpose as above, the electrolytic copper foil of one aspect of the present invention, wherein,
As the average diameter of the hole (pore) in region between the surface feature of the protrusion in the face of precipitation it is
1nm to 100nm.
The sectional area of hole can be 10% to 50% relative to the area in described precipitation face, and hole can
Think 100/μm2To 1000/μm2。
The average density of the hole in precipitation face is relative to the surface feature of protrusion in precipitation face
The ratio of average density can be 10% to 50%.
Can be more than 500 relative to glossiness Gs (60 °) of the width in the face of precipitation.
Electrolytic copper foil hot strength before heat treatment can be 40kgf/mm2To 70kgf/mm2,
Hot strength after heat treatment can also be 40kgf/mm2To 70kgf/mm2.Heat treatment can be
Perform 1 hour at 180 DEG C.Further, before the hot strength after heat treatment is preferably heat treatment
The 85% to 99% of hot strength.
Electrolytic copper foil percentage elongation before heat treatment can be 2% to 15%, the elongation after heat treatment
Rate can be 4% to 15%.Heat treatment can perform 1 hour at 180 DEG C.Further, at heat
Percentage elongation after reason can be 1 times to 4.5 times of the percentage elongation before heat treatment.
The corner roll angle of electrolytic copper foil can be 0 ° to 45 °, and corner crimp height can be
0mm to 40mm, the thickness of electrolytic copper foil can be that 2 μm are to 10 μm.
According to a further aspect in the invention, it is provided that a kind of electricity including electrolytic copper foil as above
Pond.
According to another aspect of the invention, it is provided that a kind of electric component, comprising: insulating properties base material；
And, it is attached to the described electrolytic copper foil on a surface of insulating properties base material.
The electrolytic copper foil of the present invention on precipitation face to outside protrude surface feature between hole
Size and density relatively small, make also to show high gloss before aftertreatment technology, thus
There is the effect improving product quality.Further, the electrolytic copper foil of the present invention is showing high intensity
Showing high elongation rate, the pressure within electrolytic copper foil is less and is prevented from corner curling now simultaneously
As.Thus, the electrolytic copper foil of the present invention shows low roughness, high intensity and high elongation rate, from
And be conducive to performing technique and reducing product fraction defective, at PCB or the cathode current collection of secondary cell
In the case of the products such as body use, it is possible to increase product reliability.
Accompanying drawing explanation
Fig. 1 is that 2000 times of Flied emission scanning electrons of the electrolytic copper foil of one embodiment of the invention show
Micro mirror (Field emission scanning electron microscopy, FESEM) image.
Fig. 2 is 10000 times of FESEM images of the electrolytic copper foil of one embodiment of the invention.
Fig. 3 is 50000 times of FESEM images of the electrolytic copper foil of one embodiment of the invention.
Fig. 4 is 100000 times of FESEM images of the electrolytic copper foil of one embodiment of the invention.
Fig. 5 is 100000 times of FESEM images of the electrolytic copper foil of one embodiment of the invention.
Fig. 6 is the XRD (X-ray separating out face of the electrolytic copper foil for manufacturing in embodiment 1
Diffraction) spectrum.
Fig. 7 is the scanning electron microscope on the surface for the electrolytic copper foil manufactured in embodiment 1
(scanning electron microscopy, SEM) image.
Fig. 8 is the SEM image on the surface of the electrolytic copper foil for embodiment 2.
Fig. 9 is the SEM image on the surface of the electrolytic copper foil for embodiment 3.
Figure 10 is the SEM image on the surface of the electrolytic copper foil for embodiment 4.
Figure 11 is the SEM image on the surface of the electrolytic copper foil for comparative example 1.
Figure 12 is the SEM image on the surface of the electrolytic copper foil for comparative example 2.
Figure 13 is the SEM image on the surface of the electrolytic copper foil for comparative example 3.
Figure 14 is the SEM image on the surface of the electrolytic copper foil for comparative example 4.
Detailed description of the invention
Hereinafter, for the electrolytic copper foil of the present invention, the electric component comprising above-mentioned electrolytic copper foil and electricity
Pond and electrolytic copper foil manufacture method are described in more details.
In the electrolytic copper foil of one embodiment of the invention, as the face of precipitation (Matte side)
Between the surface feature protruded, the average diameter of the hole (pore) in region is 1nm to 100nm.
In the electrolytic copper foil of the present embodiment, as the relatively dark-part illustrated on precipitation face, i.e. as existing
The average diameter of the hole of the relatively dark-part between 2 surface feature is nm unit and less.
In this specification, " surface feature " is the relatively bright part illustrated on precipitation face, and it represents cathode copper
The part that the surface of paper tinsel protrudes above；" hole " is formed on the surface of electrolytic copper foil convex to top
The part between the surface feature gone out and internally introduced, it represents the part relatively suggested.
In the electrolytic copper foil of the present invention, for separating out the glossiness (Gs (60 of the width in face
°)) can be more than 500.That is, the glossiness separating out face of electrolytic copper foil is the highest.Cathode copper
Paper tinsel passes through to supply between negative electrode rotating cylinder and the anode impregnating in cupric electrolysis liquid bath and rotating electric current, with
Separating out Copper Foil in negative electrode drum surface and obtain, the face contacted with negative electrode rotating cylinder in electrolytic copper foil is light
Face, pool (Shiny side, S face), its opposing face is precipitation face.Precipitation face and contact with rotating cylinder
Glassy surface is different, and it is the face that Copper Foil directly separates out, thus its gloss is few in principle and rough surface
Degree height.Therefore, precipitation face reduces surface roughness by post processing, and performs as desired
Give the process of gloss.
But, the glossiness separating out face of the electrolytic copper foil of the present invention is higher.Fig. 1 is the present invention
2000 times of field emission scanning electron microscope (Field emission of the electrolytic copper foil of one embodiment
Scanning electron microscopy, FESEM) image.
Precipitation face is in operational characteristic, typically when carrying out 2000 times of FESEM and analyzing, and its surface
There will be concavo-convex and glossiness is the highest.And the precipitation face of the electrolytic copper foil of the present invention of Fig. 1, its
Show similarly such as the gloss of mirror image (mirror) with glassy surface.
By improving the resolution that FESEM analyzes, to 10000 times of FESEM images of Fig. 2,
50000 times of FESEM images of Fig. 3 and 100000 times of FESEM images of Fig. 4 are analyzed,
When more improving resolution, occur concavo-convex on surface.But, in 10000 times of FESEM images
The most difficult confirm concavo-convex, at 50000 times of FESEM and 100000 times of FESEM analyses etc
Ultrahigh resolution under, then confirm concavo-convex.
In 100000 times of FESEM images of Fig. 4, occur in that as from the precipitation of electrolytic copper foil
The hole (pore) in region between the surface feature that face is protruded.Cathode copper in the present invention of Fig. 4
In paper tinsel, separating out the size of surface feature and the high uniformity in face, the diameter of hole is little and hole big
Little ratio is more uniform.To identical sample inclination (tilt) 52 degree and carry out 100000 shown in Fig. 5
The result that times FESEM analyzes.In Fig. 5, occur in that with becoming apparent from protrusion surface feature it
Between hole.
In the case of surface has identical surface roughness, if the slightest or its number of hole
Mesh is few, and its surface gloss can improve.Such as, the feelings that the volume of the hole on precipitation face is identical
Under condition, if the depth as shallow of hole, average diameter are big, then as the darker area occurred on surface
Hole can affect glossiness larger.That is, in the case of the volume of hole is identical, if hole
The degree of depth of gap is deep and average diameter is little, then can improve glossiness.
Therefore, in terms of glossiness, the hole on the precipitation face of the electrolytic copper foil of the present invention is preferably
Make its degree of depth deep and average diameter is little.Rz in view of the surface roughness on precipitation face is 1.4 μm
Following aspect, what the average diameter of hole was that 1nm to 100nm represents is that the degree of depth of hole is deep,
So that the relatively dark-part of hole is the most more exposed to precipitation face.
Further, hole can show the cross section of 10% to 50% relative to the whole area in the face of precipitation
Long-pending.This represents that hole preferably shows the face of less than 50% relative to the whole area in the face of precipitation
Long-pending.Meanwhile, hole average density on precipitation face relative to protrude surface feature separate out face
On the ratio of average density can be 10% to 50%.In terms of glossiness, preferably make hole
Gap exists with number to be lacked compared with the surface feature protruded to outside.Further, hole can be
100/μm2To 1000/μm2。
The sectional area of hole can be removed by the whole area of darker area from the image of Fig. 3 or Fig. 4
Calculate with the number of hole.
In exemplary one electrolytic copper foil realizing example, surface roughness Rz separating out face is
Below 1.4 μm, heat treatment after-drawing intensity is 40kgf/mm2Above, percentage elongation is more than 4%.
Above-mentioned electrolytic copper foil be surface roughness Rz be the low roughness Copper Foil of below 1.4 μm, and
There is 40kgf/mm simultaneously2Above high tensile, therefore its mechanical strength is high.Meanwhile,
Above-mentioned electrolytic copper foil, after via high temperature, also will have the high elongation rate of more than 4%.
Further, corner curling (curl) angle of the electrolytic copper foil of the present invention is 0 ° to 45 °.
Corner roll angle refer to electrolytic copper foil is positioned over smooth ground in the case of, cathode copper
The angle of the end section of paper tinsel, i.e. corner or curved edge.The corner crimp of electrolytic copper foil is
Occur when the internal energy of electrolytic copper foil is uneven, when there is corner curling, as at PCB
In the techniques such as the lamination in technique corner be torn etc. can produce more bad, in lithium secondary battery work
In skill, corner can be produced when coating active substance and be torn or folded or produce the problems such as fold.
If the corner roll angle of electrolytic copper foil is big, it is more difficult to use in subsequent technique, therefore, corner
Roll angle is preferably 0 ° to 45 °.Further, electrolytic copper foil is deployed on smooth ground also
Cutting into X-shaped, the height that cut part tilts is referred to as corner crimp height, corner crimps
Highly preferred for 0mm to 40mm.In the case of the electrolytic copper foil of the present invention, owing to copper is tied
Intracrystalline there are impurity and intensity is higher, and its corner amount of crimp is haggled over greatly in advance, and in copper crystal boundary not
There are impurity so that its internal pressure reduces, so that corner amount of crimp reduces.
Therefore, above-mentioned electrolytic copper foil can be simultaneously as PCB (printed circuit board (PCB) (Printed Circuit
Board))/FPC (flexible printed circuit board (Flexible PCB)) purposes and the current collection of battery
Body purposes uses.
When surface roughness Rz separating out face in above-mentioned electrolytic copper foil is more than 1.4 μm, for the moon
The surface of the electrolytic copper foil of electrode current collector diminishes with the contact surface of active substance, consequently, it is possible to make charge and discharge
The life-span of electricity circulation and the capacitance of initial charge reduce.Further, thick when the surface in above-mentioned precipitation face
When rugosity Rz is more than 1.4 μm, it is more difficult to formed on a printed circuit and there is the highly dense of minuteness space
Degree circuit.
The hot strength of above-mentioned electrolytic copper foil is 40kgf/mm2To 70kgf/mm2, thus there is height
Strength characteristics.Further, after heat treatment, its hot strength is 40kgf/mm to above-mentioned electrolytic copper foil2
To 70kgf/mm2.Heat treatment such as can be 150 DEG C to 220 DEG C of execution, specifically, and can be
180 DEG C of execution.Heat treatment can perform with 30 minutes, 1 hour, 2 hours and several hours, but needs
Perform the hot strength that could keep certain more than 1 hour.Heat treatment is to measure cathode copper
The hot strength of paper tinsel, it is in the case of being preserved or render to subsequent technique by electrolytic copper foil, for
Obtain the process keeping the hot strength of constant value or percentage elongation with certain level and carry out.
Above-mentioned electrolytic copper foil after the heat treatment, if its hot strength is less than 40kgf/mm2,
Then its mechanical strength is weak and more difficult use.
Preferably, the stretching before the hot strength after the heat treatment of above-mentioned electrolytic copper foil and heat treatment is strong
Degree is similar.Hot strength after the heat treatment of above-mentioned electrolytic copper foil is preferably hot strength before heat treatment
85% to 99%, if after heat treatment also be able to keep intensity, then in follow-up technique
Easily operate and improve yield.
Percentage elongation before the heat treatment of above-mentioned electrolytic copper foil can be 2% to 15%.Further, above-mentioned
Percentage elongation after the heat treatment of electrolytic copper foil can be 4% to 15%, and heat treatment can be at 180 DEG C
Lower execution 1 hour.Or, before after heat treatment, percentage elongation can be heat treatment, 1 times of percentage elongation extremely
4.5 again.
If the percentage elongation that above-mentioned electrolytic copper foil is after heat treatment is less than 4%, it is high at subsequent technique
In the case of temperature technique, it may occur that crackle.Such as, it is used as secondary electricity at above-mentioned electrolytic copper foil
In the case of the cathode current collector in pond, technique during owing to manufacturing cathode current collector is high-temperature technology,
And the change in volume of active material layer it is attended by when discharge and recharge, it may occur that crackle also induces not
Good, therefore, need after heat treatment to keep set percentage elongation.
In the XRD spectrum for precipitation face of above-mentioned electrolytic copper foil, tie as (200)
The intensity I (200) of diffraction peak (peak) of crystal face and the diffraction peak for (111) crystal plane
Ratio I (the 200)/I (111) of intensity I (111) can be 0.5 to 1.0.
Such as, as shown in Figure 6, in the XRD spectrum for precipitation face, in angle of diffraction (2
θ) 43.0 ° ± 1.0 ° show the diffraction peak for (111) crystal plane, in the angle of diffraction
Degree (2 θ) 50.5 ° ± 1.0 ° shows the diffraction peak for (200) crystal plane, they
Strength ratio I (200)/I (111) can be more than 0.5 to 1.0.
Such as, in above-mentioned electrolytic copper foil, I (200)/I (111) can be 0.5 to 0.8.Above-mentioned
In the XRD spectrum for above-mentioned precipitation face of electrolytic copper foil, as from for (200) crystal plane
Orientation coefficient M (200) and orientation that the orientation coefficient M (111) of (111) crystal plane is drawn
The M (200) of coefficient ratio/M (111) can be 1.1 to 1.5.Above-mentioned orientation coefficient (orientation
Index) it is by the relative peak intensities of the specific crystal plane for arbitrary test portion, divided by from right
The relative peak of the characteristic crystal plane drawn in the Standard testing agent that all crystal planes are No yield point is strong
The value of degree.Such as, in above-mentioned electrolytic copper foil, M (200)/M (111) can be 1.2 to 1.4.
After above-mentioned electrolytic copper foil carries out 1 hour heat treatment at 180 DEG C, its percentage elongation can be
More than 10%.That is, above-mentioned electrolytic copper foil after high-temperature heat treatment, can have percentage elongation be 10% with
On high elongation rate.Such as, above-mentioned electrolytic copper foil is after high-temperature heat treatment, and its percentage elongation can be
10% to 20%.Such as, above-mentioned electrolytic copper foil is after high-temperature heat treatment, and its percentage elongation can be
10% to 15%.Such as, above-mentioned electrolytic copper foil is after high-temperature heat treatment, and its percentage elongation can be
10% to 13%.Before heat treatment, its percentage elongation can be more than 2% to above-mentioned electrolytic copper foil.Example
As, before heat treatment, its percentage elongation can be 2% to 20% to above-mentioned electrolytic copper foil.Such as, on
Stating electrolytic copper foil before heat treatment, its percentage elongation can be 5% to 20%.Such as, above-mentioned electrolysis
Before heat treatment, its percentage elongation can be 5% to 15% to Copper Foil.Such as, above-mentioned electrolytic copper foil exists
Before heat treatment, its percentage elongation can be 5% to 10%.Above-mentioned term " before heat treatment " represents
It is as with 25 DEG C to 130 DEG C of the temperature before condition of high temperature heat treatment.Above-mentioned percentage elongation is electrolysis
The distance that Copper Foil is extended till before disrumpent feelings is divided by the value of the initial length of electrolytic copper foil.
Surface roughness Rz separating out face of above-mentioned electrolytic copper foil can be below 0.7 μm.Above-mentioned
Electrolytic copper foil, can be simultaneously as being used for by having the low roughness that Rz is below 0.7 μm
The Copper Foil of PCB/FPC and the Copper Foil use of the cathode current collector for secondary cell.Such as, on
Surface roughness Rz separating out face stating electrolytic copper foil can be below 0.5 μm.Such as, above-mentioned
Surface roughness Rz separating out face of electrolytic copper foil can be below 0.45 μm.
The surface roughness Ra separating out face of above-mentioned electrolytic copper foil can be below 0.15 μm.Above-mentioned
Electrolytic copper foil, can be simultaneously as being used for by having the low roughness that Ra is below 0.15 μm
The Copper Foil of PCB/FPC and the Copper Foil use of the cathode current collector for secondary cell.Such as, on
The surface roughness Ra separating out face stating electrolytic copper foil can be below 0.12 μm.Such as, on
The surface roughness Ra separating out face stating electrolytic copper foil can be below 0.11 μm.
The heat treatment after-drawing intensity of above-mentioned electrolytic copper foil can be hot strength before heat treatment
More than 85%.Such as, the 1 hour after-drawing intensity of 180 DEG C of heat treatments of above-mentioned electrolytic copper foil is permissible
For before heat treatment more than the 90% of hot strength.Before above-mentioned heat treatment, hot strength is not for carry out high temperature
Heat treatment and the hot strength of Copper Foil that draws.Before the heat treatment of above-mentioned electrolytic copper foil, hot strength can
Think 40kgf/mm2To 70kgf/mm2。
In above-mentioned electrolytic copper foil, for separating out the glossiness (Gs (60 °)) of the width in face
Can be more than 500.Such as, in above-mentioned electrolytic copper foil, for separating out the width in face
Glossiness (Gs (60 °)) can be 500 to 1000.Above-mentioned glossiness is according to JIS Z 871-1997
The value measured.
The thickness of above-mentioned electrolytic copper foil can be below 35 μm.Such as, the thickness of above-mentioned electrolytic copper foil
Degree can be 6 to 35 μm.Such as, the thickness of above-mentioned electrolytic copper foil can be 6 to 18 μm.And
And, the thickness of the most above-mentioned electrolytic copper foil can be 2 to 10 μm.
Above-mentioned electrolytic copper foil is in the case of needs are bonding with insulating resin etc., for making adaptation reach
Realistic scale or its more than, can implement further surface process.Processing as the surface on Copper Foil can
Enumerate such as, heat-resisting and chemical resistance processes, chromate processes, silane coupler process in one
Plant or combinations thereof, as to how implement which kind of surface process, the technical field belonging to the present invention
Those skilled in the art can select also according to the resin utilized as insulating resin or process conditions
Perform.
Electric component according to an exemplary embodiment includes: insulating properties base material；And be attached to
The above-mentioned electrolytic copper foil on one surface of above-mentioned insulating properties base material, and include by etching above-mentioned cathode copper
Paper tinsel and the circuit that formed.
Above-mentioned electric component e.g. TAB band, printed circuit board (PCB) (PCB), flexible print circuit
Plate (FPC, Flexible PCB) etc., but it is not limited to this, as long as by above-mentioned electrolysis
Copper Foil is attached on insulating properties base material, and can use in the art.
Battery according to an exemplary embodiment comprises above-mentioned electrolytic copper foil.Above-mentioned electrolytic copper foil can
Cathode current collector as above-mentioned battery uses, but is not limited to this, and it also can be as battery
Other structural element of middle use uses.Above-mentioned battery is not particularly limited, and it comprises one
Primary cell, secondary cell etc. are whole, as long as lithium ion battery, lithium polymer battery, lithium air
The battery that electrolytic copper foil is used by battery etc. as collector body, and can use in the art
Battery.
According to the electrolytic copper foil manufacture method of an exemplary embodiment, comprising: interpolation will be comprised
The copper electrolyte of agent A, additive B, addition of C and additive D carries out the step being electrolysed,
Above-mentioned additive A is to connect to have mercapto on thiourea based compound and the heterocycle containing nitrogen
More than one in compound, above-mentioned additive B be the sulfonic acid of the compound containing sulphur atom or its
Slaine, above-mentioned addition of C is nonionic water soluble polymer；Above-mentioned additive D is fen
Piperazine(phenazinium) based compound.
Above-mentioned electrolytic copper foil manufacture method is by comprising the additive of new component, it is possible to produce thickness
Spend thin, mechanical strength is high and can realize the low roughness Copper Foil of high extension.Above-mentioned copper electrolyte can wrap
Containing the chlorine (chloride ion) that concentration is 1 to 40ppm.If there are a small amount of in copper electrolyte
Chloride ion, when electrolytic gold plating, initial nucleation position (nucleation site) increases and makes crystal grain
Become fine, the CuCl that grain boundary interfaces is formed2Precipitate suppress crystallization raw when high-temperature heating
Long such that it is able to improve the heat stability under high temperature.When the concentration of above-mentioned chloride ion is less than 1ppm
Time, owing to the concentration of chloride ion required in sulfonic acid-sulfonic acid copper electrolyte is not enough, before making heat treatment
Hot strength reduce, and make the heat stability under high temperature reduce.When the concentration of chloride ion is more than
During 40ppm, rise owing to separating out the surface roughness in face, more difficult may produce low roughness
Electrolytic copper foil, makes the hot strength before heat treatment reduce, and makes the heat stability under high temperature reduce.
In above-mentioned copper electrolyte, the content of above-mentioned additive A can be 1 to 10ppm, above-mentioned
The content of additive B can be 10 to 200ppm, and the content of above-mentioned addition of C can be 5
To 40ppm, the content of above-mentioned additive D can be 1 to 10ppm.
In above-mentioned copper electrolyte, additive A can improve the manufacture stabilisation of electrolytic copper foil, and carries
The intensity of high electrolytic copper foil.When the content of above-mentioned additive A is less than 1ppm, electrolytic copper foil
Hot strength may reduce, and when the content of above-mentioned additive A is more than 10ppm, separates out face
Surface roughness rises, consequently, it is possible to the more difficult electrolytic copper foil producing low roughness, and make stretching
Intensity reduces.
In above-mentioned copper electrolyte, additive B can improve the lustrous surface of electrolytic copper foil.When above-mentioned
When the content of additive B is less than 10ppm, the gloss of electrolytic copper foil may reduce, and adds when above-mentioned
When adding the content of agent B more than 200ppm, the surface roughness separating out face rises, consequently, it is possible to relatively
Difficulty produces the electrolytic copper foil of low roughness, and makes the hot strength of electrolytic copper foil reduce.
In above-mentioned copper electrolyte, addition of C can reduce the surface roughness of electrolytic copper foil and improve
Lustrous surface.When the content of above-mentioned addition of C is less than 5ppm, separate out the surface roughness in face
Rise, consequently, it is possible to the more difficult electrolytic copper foil producing low roughness, and make the gloss of electrolytic copper foil
Reduce, when the content of above-mentioned addition of C is more than 40ppm, the physical property of possible electrolytic copper foil or
There is no difference in appearance and uneconomical.
In above-mentioned copper electrolyte, additive D can perform to improve the flatness on the surface of electrolytic copper foil
Effect.When the content of above-mentioned additive D is less than 1ppm, separate out in the surface roughness in face
Rise, consequently, it is possible to the more difficult electrolytic copper foil producing low roughness, and make the gloss of electrolytic copper foil drop
Low, when the content of above-mentioned additive D is more than 40ppm, the precipitation state of electrolytic copper foil becomes
Instability, and hinder the hot strength of electrolytic copper foil.
Above-mentioned thiourea based compound can be selected from diethyl thiourea, ethylene thiourea, acetylene thiourea,
Dipropyl thiourea, dibutyl thiourea, N-TFA thiourea (N-trifluoroacetylthiourea),
N-ethyl thiourea (N-ethylthiourea), N-cyano-acetamide thiourea
(N-cyanoacetylthiourea), N-allylthiourea (N-allylthiourea), o-tolyl
Thiourea (o-tolylthiourea), N, N '-fourth support thiourea (N, N '-butylene thiourea), thiophene
Oxazolidine mercaptan (thiazolidinethiol), 4-Thiazolidine mercaptan (4-thioazolinethiol), 4-
Methyl-2-pyridinethiol (4-methyl-2-pyrimidinethiol), 2-thiouracil
(2-thiouracil) more than one in, but it is not limited to this, as long as the art
In the thiourea compound that can use as additive.Connect on the above-mentioned heterocycle containing nitrogen and have sulfur
The compound of alcohol radical such as may is that 2-sulfydryl-5-benzimidazole sulfonic acid sodium salt
(2-mercapto-5-benzoimidazole sulfonic acid sodium salt), 3-(5-sulfydryl-1-
Tetrazole radical) benzene sulfonic acid sodium salt (Sodium 3-(5-mercapto-1-tetrazolyl) benzene
Sulfonate), 2-mercaptobenzothiazole (2-mercapto benzothiazole).
The sulfonic acid of the above-mentioned compound containing sulphur atom or its metallic salts can be such as selected from double-(3-
Sulfapropyl)-disulphide disodium salt (SPS), 3-sulfydryl-1-propane sulfonic acid (MPS), 3-(N, N-
Dimethyl thio carbamyl)-sulfur is for sulfonic acid sodium salt (DPS), 3-[(amino-iminomethyl)
Sulfur generation]-1-propane sulfonic acid sodium salt (UPS), adjacent ethyl dithiocarbonic acids-S-(3-sulfopropyl)-ester sodium salt
(OPX), 3-(benzothiazolyl-2-sulfydryl)-propyl group-sodium sulfonate (ZPS), ethylidene dithio two
Propyl sulfonic acid sodium (Ethylenedithiodipropylsulfonic acid sodium salt), sulfydryl second
Acid (Thioglycolic acid), D2EHDTPA neighbour's ethyl-bis--(ω-sulfopropyl) ester disodium salt
(Thiophosphoric acid-o-ethyl-bis-(ω-sulfopropyl)ester disodium
Salt), D2EHDTPA-three-(ω-sulfopropyl) ester trisodium salt (Thiophosphoric acid-tris-(ω
-sulfopropyl) ester trisodium salt) in more than one, but be not limited to this,
As long as the compound containing sulphur atom that can use as additive in technical field
Sulfonic acid or its slaine.
Above-mentioned nonionic water soluble polymer can be selected from Polyethylene Glycol, polyglycereol, hydroxyl second
Base cellulose, carboxymethyl cellulose (Carboxymethylcellulose), the poly-second of nonyl phenol two
Alcohol ether (Nonylphenol polyglycol ether), octane glycol-bis--(polyalkylene glycol ethers)
(Octane diol-bis-(polyalkylene glycol ether)), capryl alcohol polyalkylene glycol ethers
(Octanol polyalkylene glycol ether), oleic acid polyglycol ether (Oleic acid
Polyglycol ether), polyethylene propylene glycol (Polyethylene propylene glycol), poly-
Ethylene glycol dimethyl ether (Polyethylene glycol dimethyl ether), polyoxypropylene diols
(Polyoxypropylene glycol), polyvinyl alcohol (Polyvinyl alcohol), betanaphthol gather
Glycol ether (β-naphthol polyglycol ether), stearic acid polyglycol ether (Stearic
Acid polyglycol ether), stearyl alcohol polyglycol ether (Stearyl alcohol polyglycol
Ether) more than one in, but it is not limited to this, as long as can in technical field
The water soluble polymer used as additive.Such as, the molecular weight of above-mentioned Polyethylene Glycol can
Think 2000 to 20000.
Above-mentioned azophenlyeneBased compound can be selected from safranin O (Safranine-O), guinea green B
More than one in (Janus Green B) etc..
The temperature of the copper electrolyte used in above-mentioned manufacture method can be 30 to 60 DEG C, but also
Being not limited to such scope, it can be capable of in the range of the purpose of the present invention suitably
Regulation.Such as, the temperature of above-mentioned copper electrolyte can be 40 to 50 DEG C.
The electric current density used in above-mentioned manufacture method can be 20 to 500A/dm2But, not
Being defined in such scope, it suitably can be adjusted being capable of in the range of the purpose of the present invention
Joint.Such as, above-mentioned electric current density can be 30 to 40A/dm2.Above-mentioned copper electrolyte can be
Sulfonic acid-sulfonic acid copper copper electrolyte.In above-mentioned sulfonic acid-sulfonic acid copper copper electrolyte, above-mentioned Cu2+Ion
Concentration can be 60g/L to 180g/L, but be not limited to such scope, it can be
It is capable of in the range of the purpose of the present invention suitably regulating.Such as, above-mentioned Cu2+Ion dense
Degree can be 65g/L to 175g/L.
Above-mentioned copper electrolyte can be manufactured by known method.Such as, Cu2+The concentration of ion can be led to
The addition overregulating copper ion or sulfonic acid copper obtains, SO4 2+The concentration of ion can be by regulation
The addition of sulfonic acid and sulfonic acid copper obtains.
The concentration of the additive comprised in above-mentioned copper electrolyte can be by adding of putting in copper electrolyte
The input amount and the molecular weight that add agent obtain, or by known methods such as column chromatographies to cupric electrolysis
The additive comprised in liquid is analyzed and obtains.
The manufacture method of above-mentioned electrolytic copper foil, can be by known in addition to using above-mentioned copper electrolyte
Method manufacture.
Such as, above-mentioned electrolytic copper foil can be by the moon on the titanium curved surface on the titanium material rotating cylinder rotated
Supply above-mentioned copper electrolyte between surface, pole and anode and be electrolysed, to separate out electricity at cathode surface
Solve Copper Foil, it is crimped continuously and produces electrolytic copper foil.
Hereinafter enumerate embodiment the present invention is described in more details, but the present invention does not limit
Due to this.
(manufacture of electrolytic copper foil)
Embodiment 1
In order to produce electrolytic copper foil by electrolysis, make use of the 3L can being circulated with 20L/min
The electrolyzer system of capacity, the temperature of copper electrolyte is that 45 DEG C of holdings are constant.Anode employs thickness
For 5mm, size is 10 × 10cm2DSE (shape steady electrode (Dimentionally Stable
Electrode)) pole plate, negative electrode employs the titanium pole plate with the size identical with anode and thickness.
For making Cu2+Ion moves smoothly, with 35A/dm2Electric current density implement gold-plated, system
Produce the electrolytic copper foil of 18 μ m thick.
The solvent of copper electrolyte is as follows:
CuSO4·5H2O:250～400g/L
H2SO4: 80～150g/L
Chloride ion and additive, the additive added and chloride ion is added in above-mentioned copper electrolyte
Component be shown in table 1 below.In table 1 below, ppm is the concentration identical with mg/L.
Manufactured electrolytic copper foil separates out the scanning electron on face (matte face, M face) surface and shows
Micro mirror photo is shown in Fig. 7.
Embodiment 2 to 4 and comparative example 1 to 4
In addition to the component of copper electrolyte is changed shown in table 1 below, with enforcement
The method that example 1 is identical has manufactured electrolytic copper foil.Embodiment 2 to 4 and comparative example 1 to 4 manufacture
The electron scanning micrograph separating out surface, face of the electrolytic copper foil gone out is shown in Fig. 8 to 14.
[table 1]
In above-mentioned table 1, initialism represents following compound.
DET: diethyl thiourea
SPS: double-(3-sulfapropyl)-disulphide disodium salt
MPS:3-sulfydryl-1-propane sulfonic acid
PEG: Polyethylene Glycol (kanto chemical Cas No.25322-68-3)
ZPS:3-(benzothiazolyl-2-sulfydryl)-propyl group-sodium sulfonate
JGB: guinea green B
2M-SS:2-sulfydryl-5-benzimidazole sulfonic acid
DDAC: diallyldimethylammonium chloride
PGL: polyglycereol (KCI, PGL 104KC)
Evaluation Example 1: scanning electron microscope is tested
The table separating out face of the electrolytic copper foil for obtaining in embodiment 1 to 4 and comparative example 1 to 4
Face, determines scanning electron microscope and its result is shown in Fig. 7 to 14.
If Fig. 7 is to shown in 14, the electrolytic copper foil of embodiment 1 to 4 and the electricity of comparative example 1 to 4
Solution Copper Foil is compared, and its surface is smooth and roughness is low.
Evaluation Example 2: measure glossiness
The table separating out face of the electrolytic copper foil for obtaining in embodiment 1 to 4 and comparative example 1 to 4
Face, determines glossiness.Above-mentioned glossiness is the value measured according to JIS Z 871-1997.
In the mensuration of glossiness, along the flow direction (MD direction) of electrolytic copper foil at this copper
The surface of paper tinsel is irradiated with angle of incidence 60 ° and is measured light, and determines and reflect with angle of reflection 60 °
The intensity of light, it is determined according to the JIS Z 8741-1997 as glossiness assay method.
Measurement result is shown in table 2 below.
[table 2]
| Glossiness [Gs (60 °)] | |
| Embodiment 1 | 700 |
| Embodiment 2 | 699 |
| Embodiment 3 | 630 |
| Embodiment 4 | 680 |
| Comparative example 1 | 438 |
| Comparative example 2 | 472 |
| Comparative example 3 | 353 |
| Comparative example 4 | 451 |
As described in above-mentioned table 2, the electrolytic copper foil of embodiment 1 to 4 and the electricity of comparative example 1 to 4
Solution Copper Foil is compared, and shows the glossiness of raising.
Evaluation Example 3:XRD is tested
The precipitation face of the electrolytic copper foil for obtaining in embodiment 1 to 4 and comparative example 1 to 4, surveys
Determine XRD (X-ray diffraction) spectrum.XRD spectrum for embodiment 1 is shown in
Fig. 6.
As shown in Figure 6, the peak strength of (111) crystal plane is the highest, is secondly (200) crystal plane.
As the intensity I (200) of the diffraction peak for above-mentioned (200) crystal plane with for (111)
Ratio I (200) of the intensity I (111) of the diffraction peak of crystal plane/I (111) is 0.605.
Further, in the XRD spectrum for above-mentioned precipitation face, determine for (111), (200),
(220), (311), the orientation coefficient (orientation index, M) of (222) crystal plane, and
The results are shown in table 3.
Orientation coefficient uses S.Yoshimura, S.Yoshihara, T.Shirakashi, E.Sato,
The orientation coefficient (M) proposed in Electrochim.Acta 39,589 (1994) is measured.
Such as, in the case of the test piece with (111) face, calculated by following method and take
To coefficient (orientation index) (M).
IFR (111)=IF (111)/{ IF (111)+IF (200)+IF (220)+IF (311) }
IR (111)=I (111)/{ I (111)+I (200)+I (220)+I (311) }
M (111)=IR (111)/IFR (111)
IF (111) is the XRD intensity in JCPDS card (Cards), and I (111) is experiment value.When
When M (111) is more than l, there is the preferred orientation being parallel to (111) face, when M is less than l,
Represent that preferred orientation reduces.
[table 3]
| Crystal plane | (111) | (200) | (220) | (311) | (922) |
| Orientation coefficient | 1.02 | 1.34 | 0.80 | 0.25 | 0.97 |
With reference to above-mentioned table 3, in the XRD spectrum for above-mentioned precipitation face, from for (200)
The orientation coefficient (M (200)) of crystal plane and the orientation coefficient (M (111)) for (111) crystal plane
Ratio M (200) of the orientation coefficient drawn/M (111) is 1.3l.
Evaluation Example 4: measure surface roughness Rz
For the precipitation face of electrolytic copper foil obtained in embodiment 1 to 4 and comparative example 1 to 4 and light
Pool face surface roughness Rz and Ra, be determined according to JISB 0601-1994 standard.Logical
Surface roughness Rz and the Ra that cross the acquisition of said determination method are shown in table 4 below.Wherein, value is more
Little expression roughness is the lowest.
Evaluation Example 5: measure room temperature hot strength, room temperature percentage elongation, high temperature tensile strength and high temperature
Percentage elongation
By the electrolytic copper foil of acquisition in embodiment 1 to 4 and comparative example 1 to 4 with width 12.7mm
After × measuring length 50mm gathers tensile test specimen, with the crosshead (cross of 50.8 mm/min
Head) speed the tension test according to IPC-TM-650 2.4.18B standard implementation, will measure
The maximum loading of the hot strength gone out is referred to as room temperature hot strength, and is referred to as by percentage elongation time disrumpent feelings
Room temperature percentage elongation.Wherein, room temperature is 25 DEG C.
By the electricity identical with the electrolytic copper foil used when measuring hot strength and percentage elongation under room temperature
Solve Copper Foil heat treatment at 180 DEG C, after 1 hour, to take out and measure in the same way as described above and draw
Stretch intensity and percentage elongation, and referred to as high temperature tensile strength and high temperature percentage elongation.
By the room temperature hot strength obtained by said determination method, room temperature percentage elongation, drawing by high temperature
Intensity, high temperature percentage elongation are shown in table 4 below.
[table 4]
As shown in Table 4 above, surface roughness Rz of the electrolytic copper foil of embodiment 1 to 4 is less than
0.5 μm and relatively low, the hot strength after high-temperature heat treatment is 40kgf/mm2Above, at high-temperature hot
Percentage elongation major part after reason is more than 10% and higher.
In contrast to this, the electrolytic copper foil phase of the electrolytic copper foil of comparative example 1 to 4 and embodiment 1 to 4
Ratio, its surface roughness is higher, and the percentage elongation after high-temperature heat treatment is relatively low, thus is not suitable as
Secondary cell cathode current collector and/or PCB/FPC low roughness Copper Foil use.
Evaluation Example 6: measure corner curling (curl) degree
By in embodiment 1 to 4 and comparative example 1 to 4 obtain electrolytic copper foil with width 10cm ×
After length 10cm gathers test piece, it is placed on smooth ground, measures corner parts bending
Angle (corner roll angle) and cut part tilts after cutting with X-shaped height (corner
Crimp height), and it is shown in table 5 below.
[table 5]
| Corner roll angle (°) | Corner crimp height (mm) | |
| Embodiment 1 | 5 | 4 |
| Embodiment 2 | 15 | 12 |
| Embodiment 3 | 8 | 6 |
| Embodiment 4 | 30 | 26 |
| Comparative example 1 | 52 | 48 |
| Comparative example 2 | 48 | 44 |
| Comparative example 3 | 46 | 43 |
| Comparative example 4 | 50 | 46 |
As shown in table 5, the corner roll angle of the electrolytic copper foil of embodiment 1 to 4 is 5 to 30
°, it is less than 45 °.But, the curling of the corner of the electrolytic copper foil of comparative example 1 to comparative example 4
Angle is 46 ° to 52 °, more than 45 °, shows the more difficult state of operation in subsequent technique.
Meanwhile, the corner crimp height of the electrolytic copper foil of comparative example 1 to comparative example 4 is more than 40mm, table
Reveal the state that quality is bad.Thus, the electrolytic copper foil of the present invention be high intensity and internal pressure low
And less corner crimp occurs, show the performance of excellence.
The present invention is not limited to above-mentioned embodiment and appended accompanying drawing, but should be by this
Bright scope of the claimed explains.Further, the those skilled in the art of the art should manage
Solve, at the technological thought without departing from the present invention described in invention which is intended to be protected
In the range of, the present invention can be carried out the displacement of variform, deform and change.
Claims (18)
1. an electrolytic copper foil, wherein, as region between the surface feature of the protrusion in the face of precipitation
The average diameter of hole be 1nm to 100nm.
Electrolytic copper foil the most according to claim 1, wherein, the sectional area phase of described hole
Area for described precipitation face is 10% to 50%.
Electrolytic copper foil the most according to claim 1, wherein, described hole is 100/μm2
To 1000/μm2。
Electrolytic copper foil the most according to claim 1, wherein, described in described precipitation face
The average density of hole is the average density of the surface feature of the described protrusion in described precipitation face
10% to 50%.
Electrolytic copper foil the most according to claim 1, wherein, relative to the width in the face of precipitation
The glossiness in direction i.e. Gs (60 °) is more than 500.
Electrolytic copper foil the most according to claim 1, wherein, the hot strength before heat treatment
For 40kgf/mm2To 70kgf/mm2。
Electrolytic copper foil the most according to claim 1, wherein, the hot strength after heat treatment
For 40kgf/mm2To 70kgf/mm2。
Electrolytic copper foil the most according to claim 1, wherein, heat treatment 1 at 180 DEG C
Hot strength after hour is 40kgf/mm2To 70kgf/mm2Above.
Electrolytic copper foil the most according to claim 1, wherein, the hot strength after heat treatment
For the hot strength before heat treatment 85% to 99%.
Electrolytic copper foil the most according to claim 1, wherein, the percentage elongation before heat treatment is
2% to 15%.
11. electrolytic copper foils according to claim 1, wherein, the percentage elongation after heat treatment is
4% to 15%.
12. electrolytic copper foils according to claim 1, wherein, heat treatment 1 at 180 DEG C
Percentage elongation after hour is 4% to 15%.
13. electrolytic copper foils according to claim 1, wherein, the percentage elongation after heat treatment is
1 times of percentage elongation before heat treatment is to 4.5 times.
14. electrolytic copper foils according to claim 1, wherein, corner roll angle is 0 °
To 45 °.
15. electrolytic copper foils according to claim 1, wherein, the corner of described electrolytic copper foil
Crimp height is 0mm to 40mm.
16. electrolytic copper foils according to claim 1, wherein, the thickness of described electrolytic copper foil
It is that 2 μm are to 10 μm.
17. 1 kinds of batteries, wherein, including the cathode copper according to any one of claim 1～16
Paper tinsel.
18. 1 kinds of electric components, wherein, including:
Insulating properties base material；And
Institute any one of the described claim 1～16 on the surface being attached to described insulating properties base material
The electrolytic copper foil stated.
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| KR101449342B1 (en) * | 2013-11-08 | 2014-10-13 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil |
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| KR101449342B1 (en) * | 2013-11-08 | 2014-10-13 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil |
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