CN108505076A - Electrolytic solution, electrolytic copper foil and method for producing same - Google Patents
Electrolytic solution, electrolytic copper foil and method for producing same Download PDFInfo
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- CN108505076A CN108505076A CN201710161342.5A CN201710161342A CN108505076A CN 108505076 A CN108505076 A CN 108505076A CN 201710161342 A CN201710161342 A CN 201710161342A CN 108505076 A CN108505076 A CN 108505076A
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- copper foil
- electrolytic copper
- electrolyte
- foil
- electrolytic
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000011889 copper foil Substances 0.000 title claims abstract description 203
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000008151 electrolyte solution Substances 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 92
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 15
- 239000011888 foil Substances 0.000 claims description 61
- 239000000654 additive Substances 0.000 claims description 33
- 230000000996 additive effect Effects 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 238000013021 overheating Methods 0.000 claims description 8
- 102000004169 proteins and genes Human genes 0.000 claims description 8
- 108090000623 proteins and genes Proteins 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 8
- 241000370738 Chlorion Species 0.000 claims description 7
- 238000009434 installation Methods 0.000 claims description 7
- 208000000260 Warts Diseases 0.000 claims description 6
- 230000002596 correlated effect Effects 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 201000010153 skin papilloma Diseases 0.000 claims description 6
- 230000000875 corresponding effect Effects 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- -1 sulfhydryl Compound Chemical class 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007788 roughening Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 206010028980 Neoplasm Diseases 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 20
- 239000013078 crystal Substances 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
Abstract
the invention discloses an electrolyte, an electrolytic copper foil and a manufacturing method thereof, wherein the electrolyte is used for manufacturing the electrolytic copper foil, and the electrolyte comprises 50-90 g/L of copper ions, 50-120 g/L of sulfuric acid and chloride ions with the concentration not more than 1.5ppm, the surface of the electrolytic copper foil manufactured after the electrolyte is electrolyzed has ten-point average roughness not more than 2 mu m on the side contacting with the electrolyte, the electrolytic copper foil has an elongation difference generated by heat treatment, and the elongation difference is in negative correlation with an initial grain size of the electrolytic copper foil.
Description
Technical field
The present invention relates to a kind of electrolyte, electrolytic copper foil and its manufacturing methods, are used for manufacturing having more particularly to one kind
The electrolyte of low roughness electrolytic copper foil uses the electrolytic copper foil and its manufacturing method manufactured by electrolyte out.
Background technology
In recent years, since the packing density of printing distributing board is continuously improved and minimizes so that reduce inside equipment
Volume becomes project.In order to the fine circuitry in response to conducting wire densification, the copper foil using low rugosity is needed.
In patent document 1 (Japanese Patent Laid-Open 2005-154815 bulletins), a kind of electrolytic copper foil manufacture cupric electrolysis is provided
The manufacturing method of liquid and electrolytic copper foil using copper electrolyte, substantially without by protein etc. molecular weight and concentration manage
Under the yield variation of caused isolation foil, and mountain (bump) form and dimension that can obtain isolation foil rough surface is neat, low coarse
The copper foil of degree, announcement have that " electrolytic copper foil manufacture copper electrolyte is characterized in the number for the protein being contained in the copper electrolyte
Average molecular weight (Mn) is 1000~2300, and concentration is 2ppm~4.5ppm.Copper ion (Cu in copper electrolyte2+) concentration is
60g/L~100g/L.The free SO of copper electrolyte4 2-Concentration is 60g/L~250g/L.Chlorion (the Cl of copper electrolyte-) concentration
It is 0.5ppm~2.0ppm.」.
However, in the copper electrolyte of patent document 1, include protein, copper ion, free sulfate ion and chlorine from
Son, and the number-average molecular weight (Mn) of protein must be controlled 1000~2300, therefore it is complex in processing procedure management.
In addition, in traditional processing procedure, the electrolytic copper foil with low rugosity is generated, glue must be added in copper electrolyte
(such as:SPS, tertiary amine compounds etc.), protein and high molecular polysaccharide (such as:HEC etc.) additive, to make electrolytic copper foil
10 mean roughness (Rz) are reduced to 2.0 μm.
Since the concentration of additive is difficult to detect, prepared in a manner of above-mentioned processing procedure with low roughness electrolytic copper foil
It can cause the managerial difficulty of processing procedure.And in the fabrication process, the accumulation of additive needs to remove by a large amount of active carbon filtration,
And then the considerations of increasing managerial degree of difficulty, the doubt of environmental protection aspect and cost aspect.If however, not in copper electrolyte
Using additive, the roughness of prepared electrolytic copper foil can be significantly increased.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of electrolyte, cathode copper in view of the deficiencies of the prior art
Foil and its manufacturing method.
In order to solve the above technical problems, a wherein technical solution of the present invention is to provide a kind of electrolyte,
, to manufacture electrolytic copper foil, electrolyte includes that 50 to 90g/L copper ion, 50 to 120g/L sulfuric acid and concentration are less than for it
The chlorion of 1.5ppm.
Preferably, electrolyte includes the additive that concentration is no more than 1ppm.
Preferably, additive is glue, protein, the compound with sulfhydryl or high molecular polysaccharide.
A wherein technical solution of the present invention is to provide a kind of manufacturing method of electrolytic copper foil comprising provides
One electrolysis installation comprising electrolytic cell, the cathode wheel and one being arranged corresponding to electrolytic cell for containing an electrolyte
The anode plate being set in electrolytic cell, wherein electrolyte include 50 to 90g/L copper ion, 50 to 120g/L sulfuric acid and
Concentration is less than the chlorion of 1.5ppm；Apply electric current in electrolyte by anode plate and cathode wheel；And electrolytic copper foil is formed,
Wherein, electrolytic copper foil include all one's life layers of foil and one be located at foil layer wherein side coarse structure, coarse structure be it is multiple
Multiple graininess protrusions of foil layer surface are formed in, electrolytic copper foil has the elongation difference generated by heat treatment,
And elongation difference and an Initial Grain Size of foil layer are negatively correlated.
Preferably, it in applying the step of electric current is in electrolyte, still further comprises：Sustainable supply flow be 15 to
30m3In the electrolyte to electrolytic cell of/hr.
Preferably, it in applying the step of electric current is in electrolyte, still further comprises：Maintain electrolyte temperature in 30 to
Between 80 DEG C.
Preferably, electrolyte further includes an additive, and the concentration of additive is less than 1ppm.
Preferably, it before the step of forming electrolytic copper foil, still further comprises：A surface treatment is executed, and at surface
Reason include roughening treatment, antirust treatment and silane coupling agent handle three at least one of, wherein electrolytic copper foil also wraps
A copper wart layer being located on foil layer is included, and the thickness of copper wart layer is between 0.1 to 3 μm.
Preferably, between 0.1 to 10 μm, initial grain has less than 180 DEG C the Initial Grain Size of foil layer
Growth temperature again, and heat treatment temperature is more than growth temperature again.
Preferably, heat treatment temperature is between 125 DEG C to 180 DEG C.
A wherein technical solution of the present invention, which is to provide, provides a kind of electrolytic copper foil comprising all one's life layers of foil and
One is located at the coarse structure of the wherein side of foil layer, and coarse structure is prominent for multiple multiple graininess for being formed in foil layer surface
It rises, an elongation difference of the electrolytic copper foil with generation by heat treatment, and an initial crystalline substance of elongation difference and foil layer
Particle size is negatively correlated.
Preferably, between 0.1 to 10 μm, initial grain has less than 180 DEG C the Initial Grain Size of foil layer
Growth temperature again, and the temperature being heat-treated is more than growth temperature again.
Preferably, heat treatment temperature is between 125 DEG C to 180 DEG C.
Preferably, electrolytic copper foil is through having an initial elongation rate, electrolytic copper foil to have after Overheating Treatment before Overheating Treatment
Elongation after one heat treatment, elongation is 1.5 to 6.5 times of initial elongation rate after heat treatment.
Preferably, there is foil layer one first side and a second side opposite with the first side, coarse structure to be located at second
On side, and foil layer is less than or equal to 2 μm in 10 mean roughness of the second side.
Preferably, the thickness of electrolytic copper foil is between 6 to 400 μm.
Preferably, the thickness of electrolytic copper foil is between 6 to 70 μm, and the initial grain size of foil layer is between 0.1 to 5
Between μm.
Preferably, the thickness of electrolytic copper foil is between 70 to 210 μm, and the initial grain size of foil layer between 5 to
Between 10 μm.
Preferably, electrolytic copper foil is through having an initial elongation rate, electrolytic copper foil to have after Overheating Treatment before Overheating Treatment
Elongation after one heat treatment, the initial elongation rate of electrolytic copper foil are stretched between 5% to 30% after the heat treatment of electrolytic copper foil
Long rate is between 25% to 42%.
The beneficial effects of the present invention are by the chlorine ion concentration in electrolyte by being reduced to 1.5ppm hereinafter, making
When making the electrolytic copper foil that the embodiment of the present invention is provided, the additive amount in electrolyte can be reduced to 1ppm hereinafter, even
In the case of the additive that any organic or inorganic can not used completely, it can still produce with low roughness and there is special machine
The electrolytic copper foil of tool property.
For the enabled feature and technology contents for being further understood that the present invention, please refer to below in connection with the present invention specifically
Bright and attached drawing, however the attached drawing provided is only for reference and description, the person of being not intended to limit the present invention.
Description of the drawings
Fig. 1 is the flow chart of the manufacturing method of the electrolytic copper foil of the embodiment of the present invention.
Fig. 2 is the schematic diagram of the electrolysis installation of the embodiment of the present invention.
Fig. 3 A are the partial enlarged view of the electrolytic copper foil of the embodiment of the present invention.
Fig. 3 B are the partial enlarged view of the electrolytic copper foil of another embodiment of the present invention.
Fig. 4 be the embodiment of the present invention electrolytic copper foil before the heat treatment with elongation difference and crystallite dimension later
Relational graph.
Fig. 5 A are X-ray (X-ray) difraction spectrum of the electrolytic copper foil of embodiment 1 before heat treatment.
Fig. 5 B are X-ray (X-ray) difraction spectrum of the electrolytic copper foil of embodiment 3 before heat treatment.
Fig. 6 A are X-ray (X-ray) difraction spectrum of the electrolytic copper foil of embodiment 1 after heat treatment.
Fig. 6 B are X-ray (X-ray) difraction spectrum of the electrolytic copper foil of embodiment 3 after heat treatment.
Fig. 7 is photo of the electrolytic copper foil in scanning electron microscope (SEM) of embodiment 5.
Fig. 8 is photo of the electrolytic copper foil in scanning electron microscope (SEM) of reference examples 2.
Fig. 9 is photo of the electrolytic copper foil in scanning electron microscope (SEM) of embodiment 3.
Figure 10 is photo of the electrolytic copper foil in scanning electron microscope (SEM) of reference examples 4.
Figure 11 is the partial cutaway schematic of the electric component of the embodiment of the present invention.
Specific implementation mode
Be below illustrated by particular specific embodiment it is presently disclosed it is related " electrolyte, electrolytic copper foil and its
The embodiment of manufacturing method ".In the electrolyte that the embodiment of the present invention is provided the concentration of additive can be reduced to 1ppm with
Under, to reduce the managerial degree of difficulty of processing procedure.The manufacturing method of electrolytic copper foil can get the electrolytic copper foil with low roughness.Separately
Outside, the electrolytic copper foil manufactured by manner described above has special machine property, and can be used for the current-collector of battery and for printing
Printed circuit board (printed circuit board, PCB) or flexible printed wiring board (FPC).
Fig. 1 is please referred to, shows the flow chart of the manufacturing method of the electrolytic copper foil of the embodiment of the present invention.As shown in Figure 1, in step
In rapid S100, an electrolysis installation is provided comprising for the electrolytic cell for containing electrolyte, the cathode wheel being arranged corresponding to electrolytic cell
And it is set to the anode plate in electrolytic cell.It please coordinate the schematic diagram for the electrolysis installation that the embodiment of the present invention is shown with reference to figure 2.
As shown in Figure 1, electrolysis installation 1 includes at least an electrolytic cell 10, an anode plate 11, a cathode wheel 12 and a roller 13.
Electrolytic cell 10 is containing electrolyte L1.Anode plate 11 is arranged in electrolytic cell 10, and is electrically connected to a power supply
The cathode output end of feeding mechanism 2.Anode plate 11 is to be coated in titanium plate by iridium or its oxide and formed.Cathode wheel 12 is then
It is arranged corresponding to electrolytic cell 10, and positioned at 11 top of anode plate.In addition, cathode wheel 12 is electrically connected to power supply device 2
Cathode output end.In embodiments of the present invention, cathode wheel 12 is titanium roller.
In addition, in the present embodiment, electrolysis installation 1 further includes the diversion pipe 14 of one and the fluid communication of electrolytic cell 10.It is aforementioned
Electrolyte L1 be by diversion pipe 14 inject electrolytic cell 10 in, flood anode plate 11, and part cathode wheel 12 is made to be immersed in electricity
It solves in liquid L1.
In embodiments of the present invention, it may include copper ion (Cu in electrolyte L12+), sulfuric acid and chlorion (Cl-), wherein
Copper ion concentration is 50 to 90g/L, and sulfuric acid concentration is 50 to 120g/L, and chlorine ion concentration is no more than 1.5ppm.
It should be noted that if sulfuric acid concentration is too low, be easy to causeing copper and influencing following process, if sulfuric acid concentration is higher than
120g/L, then copper foil surface roughness can get higher.Therefore, in a preferred embodiment, sulfuric acid concentration is between 90 to 120g/L.
Specifically, in embodiments of the present invention, electrolyte L1 has low concentration additive even completely not
Including additive.In one embodiment, the additive concentration in electrolyte L1 is no more than 1ppm.Additive above-mentioned can be had
Machine or inorganic additive, such as：Glue, the compound with sulfhydryl, protein and high molecular polysaccharide (HEC), thio propane
Additive known to sodium sulfonate (MPS), polyethylene glycol (polyethylene glycol, PEG) etc., wherein glue is, for example, ox
Glue, sodium polydithio-dipropyl sulfonate (SPS) and tertiary amine compounds.In another embodiment, electrolyte L1 does not include completely
Any additive.
Then, referring again to Fig. 1.In step s 200, electric current is applied in electrolyte by anode plate and cathode wheel.It connects
It, in step S300, forms electrolytic copper foil.Specifically, as shown in Fig. 2, power supply device 2 is to anode plate 11 and cathode
12 output direct current of wheel makes the copper ion in electrolyte L1 be precipitated in the table of cathode wheel 12 to apply electric current to electrolyte L1
Face.
In addition, in the electrolyte L1 the step of, still further comprise in lasting supply electrolyte L1 to electrolytic cell 10.
Specifically, electrolyte L1 can be flowed by diversion pipe 14 in electrolytic cell 10, to maintain the electrolyte L1's in electrolytic cell 10
Copper ion concentration.
If the flow of electrolyte L1 is too low, also the roughness of electrolytic copper foil 3 can be caused to be significantly increased.It is primarily due to be electrolysed
The flow of liquid L1 can influence the copper ion concentration of the electrolyte L1 in electrolytic cell 10, and copper ion concentration can further influence to be electrolysed
The crystal grain-growth speed of copper foil 3 and the surface roughness of electrolytic copper foil 3.In one embodiment, continue supply flow between 15
To 30m3In the electrolyte L1 to electrolytic cell 10 of/hr.
In embodiments of the present invention, in the electrolyte L1 the step of, the temperature for maintaining electrolyte L1 is still further comprised
It spends between 30 to 80 DEG C.The temperature of electrolyte L1 can be related to the Initial Grain Size of electrolytic copper foil 3.Usual electrolytic copper foil 3
Initial Grain Size can with the temperature of electrolyte L1 increase and increase.Furthermore, the initial grain ruler of electrolytic copper foil 3
The very little engineering properties that can influence electrolytic copper foil 3.For example, the Initial Grain Size 3 of electrolytic copper foil 3 is bigger, electrolytic copper foil 3
Initial elongation rate can be higher, but tensile strength can be relatively low.Therefore, the temperature that electrolyte L1 can be adjusted according to different requirements, into
And adjust the engineering properties of electrolytic copper foil 3.
Referring again to Fig. 1, the electrolytic copper foil 3 of precipitation understands the sur-face peeling by cathode wheel 12, and by roller 13, to carry out
Follow-up process.
Please refer to Fig. 3 A, the partial enlarged view of the display present invention wherein electrolytic copper foil of an embodiment.Implemented with the present invention
Electrolytic copper foil 3 prepared by the manufacturing method of the electrolytic copper foil of example is located at foil layer 30 wherein including at least all one's life layers of foil 30 and one
The coarse structure 300 of side, and coarse structure 300 is multiple multiple graininess protrusions for being formed in 30 surface of foil layer.
As shown in Figure 3A, foil layer 30 has the one first side 3a and the second side 3b opposite with the first side 3a, wherein first
Side 3a refers to the side of electrolytic copper foil 3 and the contact of 12 surface of cathode wheel in electrolytic process.Usual foil layer 30 is in the first side 3a
Roughness be roughness depending on 12 surface of cathode wheel, therefore the roughness of the first side 3a is relatively fixed.
Coarse structure 300 above-mentioned is the second side 3b positioned at foil layer 30, that is, in electrolytic process, electrolytic copper foil
Contact the side of electrolyte L1.Therefore, compared to the first side 3a, foil layer 30 is typically larger than in the roughness of the second side 3b the
The roughness of side 3a.In other words, the surface of the first side 3a of foil layer 30 is relatively smooth, and the surface of the second side 3b is more thick
It is rough.But coarse structure 300 does not make foil layer 30 in 10 mean roughness of the second side 3b be more than 2 μm.In other words, foil layer
30 are no more than 2 μm in 10 mean roughness of the second side 3b, such as between 0.9 μm to 1.9 μm.
As previously mentioned, flow of the foil layer 30 in the roughness of the second side 3b and the composition of electrolyte L1 and electrolyte L1
It is related.After the chlorine ion concentration to 1.5ppm or less in reducing electrolyte L1, even if by the additive concentration in electrolyte L1
1ppm is reduced to hereinafter, still can get the electrolytic copper foil with 10 mean roughness (Rz) no more than 2.0 μm.In addition, this hair
In the manufacturing method for the electrolytic copper foil that bright embodiment is provided, the flow of electrolyte L1 maintains 15 to 30m3/ hr can also drop
Roughness of the low foil layer 30 in the second side 3b.
Referring again to Fig. 1, in another embodiment, the manufacturing method for the electrolytic copper foil that the embodiment of the present invention is provided also is wrapped
It includes before step S300, in step S400, executes a surface treatment.Surface treatment above-mentioned includes roughening treatment, antirust
Processing, silane coupling agent processing at least one of.
Fig. 3 B are please referred to, show the partial enlarged view of the electrolytic copper foil of another embodiment of the present invention.The electrolysis of the present embodiment
Copper foil 3 ' is by follow-up process such as surface treatment and cutting formings.When executing surface treatment step, cathode copper can be adjusted
Adhesion (adhesion), heat resistance or the corrosion resistance of foil 3 ', wherein surface treatment is, for example, heat-resisting and anti-chemical treatment, chromium
One of hydrochlorate (chromate) processing, silane (silane) coupling processing and combinations thereof, can be by those skilled in the art according to reality
Border demand selection.
In the embodiment of Fig. 3 B, electrolytic copper foil 3 ' includes all one's life layers of foil 30 and the copper wart layer on foil layer 30
31.The Initial Grain Size of foil layer 30 can be identical with previous embodiment.In the present embodiment, copper wart layer 31 is to be covered in foil layer
30 the second side 3b, and the thickness of copper wart layer 31 can be between 0.1 to 3 μm.The thickness T of electrolytic copper foil 3 in above-mentioned Fig. 3 A and
The thickness T ' of electrolytic copper foil 3 ' in Fig. 3 B can be between 6 μm to 400 μm, depending on practical application request.
In addition, passing through focused ion beam and electron beam microscopic system (Focused ion beam and electron
Beam system FIB/SEM) electrolytic copper foil 3,3 ' of the embodiment of the present invention is analyzed, the initial grain ruler of foil layer 30
Very little is between 0.1 μm to 10 μm.
In addition, the electrolytic copper foil 3,3 ' of the present embodiment has an initial elongation rate, and initial elongation rate can be with foil layer 30
Initial Grain Size it is related.Elongation herein is to indicate electrolytic copper foil being about to the distance extended before rupturing divided by electrolysis
The obtained value of initial length of copper foil.Specifically, the initial elongation rate of electrolytic copper foil 3,3 ' can be initial with foil layer 30
Crystallite dimension increases and increases.That is, the initial elongation rate of electrolytic copper foil 3,3 ' is the initial grain ruler with foil layer 30
It is very little to be positively correlated.
More specifically, the initial grain of the electrolytic copper foil 3,3 ' of the present embodiment has a temperature of growing up again for being less than 180 DEG C
Degree.Furthermore, the growth temperature again of the initial grain of the electrolytic copper foil 3,3 ' of the present embodiment is about 125 DEG C.It is above-mentioned
Growth temperature refers to that crystal grain in electrolytic copper foil 3,3 ' can be made to start (the grain that grows up after continuous heating 1 hour again
Growth minimum temperature).
It should be noted that in existing electrolytic copper foil processing procedure, the additive containing rather high concentration in electrolyte.But
It is the element in additive, such as：When carbon, nitrogen, sulphur are largely remained in electrolytic copper foil, the crystal boundary (grain of crystal grain can be limited
Boundary), to limit to the crystal grain-growth of electrolytic copper foil.Therefore, existing electrolytic copper foil needs are heated at least 180
DEG C, even at higher temperature, the crystallite dimension of existing electrolytic copper foil can just gradually increase.
In comparison, the electrolyte used in the manufacturing method for the electrolytic copper foil that the embodiment of the present invention is provided containing only
There is a small amount of (being less than 1ppm) additive that can be greatly decreased and remain between crystal grain, limit crystal boundary even wholly without additive
Element.Therefore, have compared to the electrolytic copper foil 3,3 ' of the electrolytic copper foil prepared by existing manufacturing method, the embodiment of the present invention
Lower growth temperature again.
Accordingly, under lower heat treatment temperature, you can the elongation of the electrolytic copper foil 3,3 ' of the embodiment of the present invention is made to increase
Add.Terms used herein " heat treatment " refer to continuous heating at least 1 hour under a heat treatment temperature, and aforementioned heat treatment is warm
Degree is greater than the growth temperature again of the initial grain of electrolytic copper foil.Due to the initial crystalline substance of the electrolytic copper foil 3,3 ' of the embodiment of the present invention
Grain growth temperature again be about 125 DEG C, as long as therefore heat treatment temperature more than 125 DEG C, you can make the crystalline substance of electrolytic copper foil 3,3 '
Particle size changes.In one embodiment, heat treatment temperature is between 125 DEG C to 180 DEG C.
The electrolytic copper foil 3,3 ' of the embodiment of the present invention the variation for be heat-treated front and back engineering properties also can and foil
The Initial Grain Size of layer 30 is related.Please refer to Fig. 4, be the embodiment of the present invention electrolytic copper foil before the heat treatment with later
The trend relational graph of elongation difference and Initial Grain Size.
As shown in figure 4, horizontal axis is Initial Grain Size, and the longitudinal axis is elongation difference, and wherein elongation difference is at heat
Difference after reason between elongation and initial elongation rate.Elongation difference is into Initial Grain Size it can be seen from Fig. 4
It is negatively correlated, that is to say, that the elongation difference that electrolytic copper foil 3,3 ' is generated by heat treatment, it can be with Initial Grain Size
Increase and reduces.
For example, it is assumed that the Initial Grain Size of the foil layer 30 of electrolytic copper foil 3,3 ' is 0.1 μm to 0.2 μm, in heat
After processing, crystal grain can grow up (regrowth) again, that is, can increase as the time increases, until reaching a stabilization ruler
It is very little, about 8 μm to 10 μm.Since crystallite dimension (grain size) greatly improves, also make electrolytic copper foil that there is larger stretch
Long rate difference.
In comparison, if the Initial Grain Size of the foil layer 30 of electrolytic copper foil 3,3 ' has approached a stable dimensions, example
Such as：Between 8 μm to 10 μm, even if then after Overheating Treatment, the limited extent of crystal grain-growth, and be heat-treated after elongation compared to
Therefore the increasing degree (elongation difference) of initial elongation rate can be also limited.
In summary, the Initial Grain Size and electrolytic copper foil of electrolytic copper foil 3,3 ' can be adjusted according to actual demand
3,3 ' thickness T, T '.For example, as thickness T, T of electrolytic copper foil 3,3 ' ' it is relatively thin when, usually require that electrolytic copper foil 3,3 ' have
There are higher hardness and lower elongation, in case electrolytic copper foil 3,3 ' is easy to deform or bend because of stress.But it is processing
Certain ductility is needed again when electrolytic copper foil 3,3 '.
Therefore, in one embodiment, as thickness T, T of electrolytic copper foil 3,3 ' ' be between 6 to 70 μm, foil layer 30 just
Beginning crystallite dimension is can be controlled in the range of 0.1 μm to 5 μm.In that case, the initial elongation rate of electrolytic copper foil 3,3 ' is situated between
Between 1% to 20%, and elongation is between 25% to 42% after being heat-treated.
On the contrary, when the thickness T of electrolytic copper foil 3,3 ' is thicker, usually require that the hardness of electrolytic copper foil 3,3 ' is softer, and
With larger elongation.In another embodiment, as thickness T, T of electrolytic copper foil 3,3 ' ' it is the life between 70 μm to 210 μm
The Initial Grain Size of layers of foil 30 can be between 5 μm to 10 μm.In that case, the initial elongation rate of electrolytic copper foil 3,3 ' is to be situated between
Between 5% to 30%, and be heat-treated after elongation between 25% to 42%.
Please refer to the following table 1.Table 1 shows the electrolytic copper foil of different embodiments of the invention and the electrolytic copper foil of different reference examples
Process conditions, surface roughness and engineering properties.As shown in table 1, the process conditions of Examples 1 to 5 and reference examples 1~4
In, the copper ion concentration in electrolyte is all 70g/L, and the concentration of sulfate ion is all 105g/L.In addition, " the table in table 1
Surface roughness " refers to the foil layer of electrolytic copper foil at 10 points of the second side the side of electrolyte (in electrolytic process contact) surface
Mean roughness.
Table 1
As shown in table 1, in the process conditions of the embodiment of the present invention 1~3, any addition is not all added in the electrolytic solution
Agent, and chlorine ion concentration is 1ppm.The surface roughness of the electrolytic copper foil of Examples 1 to 3 is both less than 2 μm.In addition, embodiment 1
The initial elongation rate of~3 electrolytic copper foil is all more than 3%, for example, being between 4% to 14%.And elongation after being heat-treated
25% or more is can reach, for example, being between 25% to 34%.That is, the elongation after heat treatment can be initial elongation rate
1.5 to 6.5 times.Heat treatment above-mentioned refers to the continuous heating 1 hour at 180 DEG C.
It is noted that when preparing the electrolytic copper foil of embodiment 1, used electrolyte temperature is 65 DEG C, higher than preparation
40 DEG C of electrolyte temperature when the electrolytic copper foil of embodiment 3.Therefore, the Initial Grain Size meeting in the electrolytic copper foil of embodiment 1
It can be more than more than the initial elongation rate of the Initial Grain Size in the electrolytic copper foil of embodiment 3, and the electrolytic copper foil of embodiment 1 real
Apply the initial elongation rate of the electrolytic copper foil of example 3.
But the difference (27.9) before the heat treatment of the electrolytic copper foil of embodiment 3 with elongation later, hence it is evident that be more than real
The electrolytic copper foil of example 1 is applied before the heat treatment with the difference of elongation later (11.6), is the electrolytic copper foil because of embodiment 3
The larger reason of amplitude of crystallite dimension growth.
In addition, please coordinate with reference to Fig. 5 A and Fig. 5 B, show that embodiment 1 and the electrolytic copper foil of embodiment 3 are being heat-treated respectively
Preceding X-ray (X-ray) difraction spectrum.
As shown in Fig. 5 A and Fig. 5 B, electrolytic copper foil all has (111), (200) and (220) crystal plane.But compare Fig. 5 A
With Fig. 5 B, it can be seen that compared to embodiment 3, the crystallinity of the electrolytic copper foil of embodiment 1 is relatively low.In addition, in fig. 5a, it is shown that
(220) the diffraction peak intensity of crystal plane is high compared to the diffraction peak intensity of (111), (200) crystal plane.In figure 5B, it shows
Show that embodiment 3 is high compared with the diffraction peak intensity of (200) and (220) crystal plane in the diffraction peak intensity of (111) crystal plane.Cause
This, the temperature of electrolyte can influence the crystallization direction of electrolytic copper foil.
Then, Fig. 6 A and Fig. 6 B are please referred to, show the X of the electrolytic copper foil of embodiment 1 and embodiment 3 after heat treatment respectively
Ray (X-ray) difraction spectrum.Specifically, Fig. 6 A and Fig. 6 B are to show that embodiment 1 and the electrolytic copper foil of embodiment 3 pass through respectively
After crossing 190 DEG C of heating, X-ray (X-ray) difraction spectrum for measuring.It can be seen from Fig. 6 A and Fig. 6 B at through overheat
After reason, embodiment 1 and the electrolytic copper foil of embodiment 3 still have (111), (200) and (220) crystal plane.But compare figure
5A, after Overheating Treatment, the electrolytic copper foil of embodiment 1 (111), (200) and (220) crystal plane diffraction peak intensity compared with
It is low.Similarly, compared to Fig. 5 B, after Overheating Treatment, the electrolytic copper foil of embodiment 3 is in (111), (200) and (220) crystal plane
Diffraction peak intensity similarly reduce.
Please continue to refer to table 1, it is added 1ppm's when preparing the electrolytic copper foil of embodiment 4 and embodiment 5, in electrolyte
Additive, and the about 1ppm of the chlorine ion concentration in electrolyte.In addition, when preparing the electrolytic copper foil of reference examples 1, nothing in electrolyte
Additive.When preparing the electrolytic copper foil of reference examples 2 and reference examples 3, the additive of 1ppm is then separately added into electrolyte.Separately
Outside, the chlorine ion concentration in the electrolyte of reference examples 1~3 is all about 5ppm.
It can also be seen that, the surface roughness of the electrolytic copper foil of embodiment 4 and embodiment 5 is also both less than 2 μm by table 1,
It is 1.3 μm and 1.9 μm respectively.In comparison, the surface roughness of the electrolytic copper foil of reference examples 1, reference examples 2 and reference examples 3
It is then significantly increased, respectively to 6.9 μm, 5.2 μm and 3.4 μm.
Fig. 7 and Fig. 8 is please referred to, the electrolytic copper foil of the electrolytic copper foil and reference examples 2 that show embodiment 5 respectively is in scan-type
The photo of electron microscope (SEM).From SEM images, it is also seen that the surface roughness of the electrolytic copper foil of embodiment 5 is certain
Less than the surface roughness of reference examples 2.
Based on above-mentioned, as long as the concentration of chlorion is no more than 1.5ppm, even if the additive concentration in electrolyte lowers, very
To additive is free of, the surface roughness of electrolytic copper foil can also be made to be less than 2 μm or less.On the contrary, when chlorine ion concentration is more than
In the case of 1.5ppm (reaches 5ppm), and additive concentration is lower, the roughness of electrolytic copper foil is all more than 3 μm, is unable to reach
The specification of ultralow rugosity (Ultra-low profile, ULP).
In addition, please continue to refer to table 1, in the process conditions of embodiment 3 and reference examples 4, chlorine ion concentration is all 1ppm,
And in the electrolytic solution all that additive is not added.However, the flow of electrolyte of embodiment 3 is 22.5m3/ hr, and reference examples 4
Flow of electrolyte is 7.5m3/hr。
Fig. 9 and Figure 10 is please referred to, shows the electrolytic copper foil of embodiment 3 and reference examples 4 in scanning electron microscope respectively
(SEM) photo.As seen from Figure 10, the surface roughness of the electrolytic copper foil of reference examples 4 significantly increases.By Fig. 9 and
It is found that the surface roughness of the electrolytic copper foil of embodiment 3 only has 0.9 μm in table 1.
Therefore, in electrolyte, the flow of electrolyte cannot be too low.Flow of electrolyte is too low, the electricity in electrolytic cell
Copper ion concentration in solution liquid is unable to maintain that in predetermined value, to influence the roughness of electrolytic copper foil.In the preferred embodiment, electric
The flow of solution liquid is at least 15m3/hr。
In conclusion the beneficial effects of the present invention are in the electrolyte provided using the embodiment of the present invention, and passed through
When the manufacturing method of the electrolytic copper foil of the embodiment of the present invention makes electrolytic copper foil, the additive amount in electrolyte can reduce to
1ppm hereinafter, even can completely do not use any organic or inorganic additive in the case of, can still produce with low coarse
Degree and the electrolytic copper foil with special machine property.In this way, can not only reduce the difficulty of processing procedure management, it is also beneficial to environmental protection.But
10 mean roughness (Rz) of prepared electrolytic copper foil can still be less than 2.0 under the process conditions for reducing or omitting additive
μm。
In addition, the electrolytic copper foil with the prior art is compared, the crystal grain of the electrolytic copper foil of the embodiment of the present invention, which has, is less than 180
DEG C growth temperature again (regrowth temperature), about 125 DEG C.Therefore, compared to existing electrolytic copper foil, originally
The electrolytic copper foil of inventive embodiments can be heat-treated at relatively low temperature, to improve elongation after electrolytic copper foil heat treatment.
In addition, the Initial Grain Size of the elongation difference for the electrolytic copper foil that the embodiment of the present invention is provided and foil layer at
It is negatively correlated.It therefore, can be according to the difference of application field, to make electrolytic copper foil that there is different crystallite dimensions, to adjust electrolysis
The engineering properties of copper foil.
The foregoing is merely the preferable possible embodiments of the present invention, the protection model of non-therefore the limitation present invention claim
The equivalence techniques variation enclosed, therefore description of the invention and accompanying drawing content is used to be done such as, the right for being both contained in the present invention are wanted
In the protection domain asked.
Claims (19)
1. a kind of electrolyte, to manufacture electrolytic copper foil, which is characterized in that the electrolyte include 50 to 90g/L copper ion,
50 to 120g/L sulfuric acid and concentration is no more than the chlorion of 1.5ppm.
2. electrolyte as described in claim 1, which is characterized in that the electrolyte further includes the addition that concentration is no more than 1ppm
Agent.
3. electrolyte as claimed in claim 2, which is characterized in that the additive is glue, protein, with sulfhydryl
Compound or high molecular polysaccharide.
4. a kind of manufacturing method of electrolytic copper foil, which is characterized in that the manufacturing method of the electrolytic copper foil includes：
There is provided an electrolysis installation comprising one is used to contain the electrolytic cell of an electrolyte, one corresponding to electrolytic cell setting
Cathode wheel and one be set to anode plate in the electrolytic cell, wherein the electrolyte include 50 to 90g/L copper ion,
50 to 120g/L sulfuric acid and concentration is less than the chlorion of 1.5ppm；
Apply electric current in the electrolyte by the anode plate and the cathode wheel；And
Form the electrolytic copper foil, wherein the electrolytic copper foil includes that all one's life layers of foil and one are located at the wherein side of foil layer
Coarse structure, the coarse structure be multiple multiple graininess protrusions for being formed in the foil layer surface, the cathode copper
Foil has the elongation difference generated by heat treatment, and an initial grain of the elongation difference and the foil layer
Size is negatively correlated.
5. the manufacturing method of electrolytic copper foil as claimed in claim 4, which is characterized in that applying electric current in the electrolyte
In step, still further comprise：Sustainable supply flow is 15 to 30m3In the electrolyte to the electrolytic cell of/hr.
6. the manufacturing method of electrolytic copper foil as claimed in claim 4, which is characterized in that applying electric current in the electrolyte
In step, still further comprise：Maintain the temperature of the electrolyte between 30 to 80 DEG C.
7. the manufacturing method of electrolytic copper foil as described in claim 1, which is characterized in that the electrolyte further includes an addition
The concentration of agent, the additive is less than 1ppm.
8. the manufacturing method of electrolytic copper foil as claimed in claim 4, which is characterized in that in the step of forming the electrolytic copper foil
Before, it still further comprises：A surface treatment is executed, and the surface treatment includes roughening treatment, antirust treatment and silane
At least one of couplant processing three, wherein the electrolytic copper foil further includes a copper tumor being located on the foil layer
Layer, and the thickness of the copper wart layer is between 0.1 to 3 μm.
9. the manufacturing method of electrolytic copper foil as claimed in claim 4, which is characterized in that the initial grain of the foil layer
For size between 0.1 to 10 μm, the initial grain, which has, is less than 180℃Growth temperature again, and the heat treatment temperature is big
In the growth temperature again.
10. the manufacturing method of electrolytic copper foil as claimed in claim 9, which is characterized in that the heat treatment temperature is between 125℃
To 180℃Between.
11. a kind of electrolytic copper foil, which is characterized in that it include all one's life layers of foil and one be located at foil layer wherein side coarse knot
Structure, the coarse structure are multiple multiple graininess protrusions for being formed in the foil layer surface, and the electrolytic copper foil has logical
Overheating Treatment and the elongation difference generated, and an Initial Grain Size of the elongation difference and the foil layer is at negative
It is related.
12. electrolytic copper foil as claimed in claim 11, which is characterized in that the Initial Grain Size of the foil layer between
Between 0.1 to 10 μm, the initial grain, which has, is less than 180℃Growth temperature again, and the temperature of the heat treatment be more than it is described
Growth temperature again.
13. electrolytic copper foil as claimed in claim 12, which is characterized in that the heat treatment temperature is between 125℃To 180℃It
Between.
14. electrolytic copper foil as claimed in claim 11, which is characterized in that the electrolytic copper foil has before passing through the heat treatment
One initial elongation rate, the electrolytic copper foil have elongation after a heat treatment after the heat treatment, are stretched after the heat treatment
Long rate is 1.5 to 6.5 times of the initial elongation rate.
15. electrolytic copper foil as claimed in claim 11, which is characterized in that the foil layer have one first side and with it is described
The opposite the second side in first side, the coarse structure are located in the second side, and the foil layer is in the second side
10 mean roughness are less than or equal to 2 μm.
16. electrolytic copper foil as claimed in claim 11, which is characterized in that the thickness of the electrolytic copper foil between 6 to 400 μm it
Between.
17. electrolytic copper foil as claimed in claim 11, which is characterized in that the thickness of the electrolytic copper foil between 6 to 70 μm it
Between, and the initial grain size of the foil layer is between 0.1 to 5 μm.
18. electrolytic copper foil as claimed in claim 11, which is characterized in that the thickness of the electrolytic copper foil is between 70 to 210 μm
Between, and the initial grain size of the foil layer is between 5 to 10 μm.
19. electrolytic copper foil as claimed in claim 18, which is characterized in that the electrolytic copper foil has before passing through the heat treatment
One initial elongation rate, the electrolytic copper foil have elongation after a heat treatment after the heat treatment, the electrolytic copper foil
Initial elongation rate between 5% to 30%, and after the heat treatment of the electrolytic copper foil elongation between 25% to 42%.
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| TW106106453A TWI619850B (en) | 2017-02-24 | 2017-02-24 | Electrolyte solution, electrolytic copper foil and manufacturing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894616A (en) * | 2019-12-30 | 2020-03-20 | 中国科学院青海盐湖研究所 | High-density copper foil and preparation method thereof |
| CN113444990A (en) * | 2021-06-02 | 2021-09-28 | 清远市进田企业有限公司 | Electrolytic copper recrystallization heat treatment process |
| CN115198319A (en) * | 2021-12-15 | 2022-10-18 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising electrolytic copper foil and lithium ion battery |
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| US10581081B1 (en) * | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
| CN109881221A (en) * | 2019-03-04 | 2019-06-14 | 深圳市汇美新科技有限公司 | A kind of ultrathin film electroplating technology of high fracture elongation |
| TWI731330B (en) | 2019-04-30 | 2021-06-21 | 南亞塑膠工業股份有限公司 | Electrolytic copper foil, method for producing the same, and lithium ion secondary battery |
| CN114481233A (en) * | 2021-11-29 | 2022-05-13 | 龙岩学院 | Foil generating device for preparing ultrathin electrolytic copper foil and application thereof |
| KR102435606B1 (en) * | 2021-12-15 | 2022-08-23 | 장 춘 페트로케미컬 컴퍼니 리미티드 | Electrolytic copper foil, electrode and lithium ion battery comprising the same |
| CN114318429A (en) * | 2021-12-29 | 2022-04-12 | 浙江花园新能源股份有限公司 | Nano coarsening electrolyte, method and product of ultralow-profile electrolytic copper foil |
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Also Published As
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| CN108505076B (en) | 2020-04-28 |
| TWI619850B (en) | 2018-04-01 |
| JP2018141230A (en) | 2018-09-13 |
| TW201831732A (en) | 2018-09-01 |
| JP6595548B2 (en) | 2019-10-23 |
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