CN116695191A - Preparation method of ultrathin composite copper foil - Google Patents
Preparation method of ultrathin composite copper foil Download PDFInfo
- Publication number
- CN116695191A CN116695191A CN202310797187.1A CN202310797187A CN116695191A CN 116695191 A CN116695191 A CN 116695191A CN 202310797187 A CN202310797187 A CN 202310797187A CN 116695191 A CN116695191 A CN 116695191A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- coiled material
- thick
- electrolytic
- composite copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000011889 copper foil Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003908 quality control method Methods 0.000 abstract 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a preparation method of an ultrathin composite copper foil, which comprises the following steps: p1, directly hot-pressing and bonding and molding the lithium battery-grade electrolytic copper foil with the thickness of 6 microns and a large-width polymer substrate to prepare a thick copper layer composite copper foil coiled material; p2, using the thick copper layer composite copper foil coiled material as an anode; p3, stripping copper layers on two sides of the anode of the thick copper layer composite copper foil coiled material to the required thickness by an electrolytic method; p4, depositing electrolytic copper foil on the cathode titanium shaft rollers at two sides; p5, ultrathin composite copper foil coiled material. The preparation method of the ultrathin composite copper foil has simple equipment, can be smoothly connected with the existing electrolytic copper foil production process, simplifies the process flow, and has easy quality control and lower cost.
Description
Technical Field
The invention relates to a composite copper foil, in particular to a preparation method of an ultrathin composite copper foil.
Background
With the development of lithium battery technology, the high energy density, light weight, battery safety and reduced battery cost of lithium ion batteries are the directions of lithium battery manufacturers. The current collector of the lithium battery cathode is traditionally made of electrolytic copper foil, at present, foreign lithium battery manufacturers mainly adopt 8-micrometer electrolytic copper foil, domestic lithium battery manufacturers mainly adopt 6-micrometer electrolytic copper foil, and the thinnest lithium battery manufacturers also use 4.5-micrometer electrolytic copper foil. The composite copper foil is used as a novel lithium battery negative electrode current collector material, is of a sandwich structure of copper-polymer material copper, is soft in texture and light in weight, and can quickly cut off a short circuit point when a short circuit occurs in a battery, so that the safety of the lithium battery is improved. At present, the domestic composite copper foil is mainly marked with 6-micrometer electrolytic copper foil and 4.5-micrometer electrolytic copper foil in terms of thickness. According to the calculation of the single-side copper layer thickness of the current domestic composite copper foil of 1 micron, the thickness of the middle polymer layer of the composite copper foil of the electrolytic copper foil of 6 microns is 4 microns; the thickness of the polymer layer in the middle of the composite copper foil of the electrolytic copper foil with the standard of 4.5 micrometers is only 2.5 micrometers. The quality of the thin polymer film is controlled under the continuous production of 1300mm wide, and the production stability is greatly tested.
The invention with the application number of CN202211707315.0 provides a preparation method of a composite copper foil for a negative current collector of a lithium battery, which comprises the following steps: s1, attaching a large-width substrate on the surface of a cooling drum, controlling the working temperature of the large-width substrate to be 20-25 ℃, and sputtering a metal layer with the thickness of 20-50 nm on two sides of the large-width substrate in a double-sided magnetron sputtering mode; s2, electroplating the metal layer by using a conductive roller to thicken the two side surfaces of the metal layer by at least 1 micron to obtain the composite copper foil with the thickness of 6-10 microns, and the composite copper foil can continuously produce 5W meter products.
However, the preparation process needs precise double-sided magnetron sputtering equipment, and the equipment investment and equipment depreciation cost of the magnetron sputtering equipment are high; the sputtered seed metal layer has small thickness, high resistivity and poor bonding force with the base material.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of an ultrathin composite copper foil, which can continuously produce a composite copper foil with a large-width polymer coiled material as a base material, wherein the thickness of a copper layer on one side of the polymer base material can be controlled within the range of 0.5-1.5 micrometers. The process does not need to use magnetron sputtering equipment and sputtering seed metal layers as conductive bottom layers, and the copper foil layers are directly bonded with the polymer base materials, so that the bonding force between the copper layers and the polymer base materials is greatly improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the ultrathin composite copper foil comprises the following steps:
p1, directly hot-pressing and bonding and molding the lithium battery-grade electrolytic copper foil with the thickness of 6 microns and a large-width polymer substrate to prepare a thick copper layer composite copper foil coiled material;
p2, using the thick copper layer composite copper foil coiled material as an anode;
p3, stripping copper layers on two sides of the anode of the thick copper layer composite copper foil coiled material to the required thickness by an electrolytic method;
p4, depositing electrolytic copper foil on the cathode titanium shaft rollers at two sides;
p5, ultrathin composite copper foil coiled material.
The invention has the following beneficial effects by adopting the process steps: according to the preparation method of the ultrathin composite copper foil, the 6-micrometer thick lithium battery-level electrolytic copper foil is directly bonded with the base material to obtain good bonding force, the thick copper-layer composite copper foil coiled material is used as an electrolytic anode, the operation speed of the coiled material is regulated, the residence time of the coiled material in electrolyte is controlled, proper voltage and current are matched, the thickness range of a copper layer on the ultrathin composite copper foil coiled material is precisely controlled to be 0.5-1.5 micrometers, the 6-micrometer thick electrolytic copper foil is generated on the cathode titanium shaft roller, the copper-layer composite copper foil is further processed and then used for preparing the next batch of thick copper-layer composite coiled material, the cyclic utilization of copper metal is realized, the copper layer thickness on two sides of the prepared ultrathin composite copper foil coiled material is uniform, the bonding force with the base material is good, the copper-layer composite copper foil coiled material can be smoothly butted with the existing electrolytic copper foil production process, expensive large-scale double-sided magnetron sputtering equipment is not used, the process flow is simplified, and the production cost is reduced.
Drawings
Figure 1 is a process flow diagram of a method for preparing an ultra-thin composite copper foil according to the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
The method comprises the steps of preparing a thick copper layer composite copper foil coiled material by hot-pressing and bonding P1 and 6-micrometer thick lithium battery-level electrolytic copper foil and a large-width macromolecule base material, preparing a thick copper layer composite copper foil coiled material, taking the P2 and the thick copper layer composite copper foil coiled material as an anode, stripping copper layers on two sides of the thick copper layer composite copper foil coiled material to required thickness by a P3 electrolytic method, depositing electrolytic copper foil on P4 and two sides of a cathode titanium shaft roller, and preparing P5 and an ultrathin composite copper foil coiled material.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, the invention provides a preparation method of an ultrathin composite copper foil, which comprises the following steps:
p1, carrying out hot-pressing bonding molding on the 6-micrometer-thick lithium battery-grade electrolytic copper foil and a large-width polymer substrate to prepare the thick copper layer composite copper foil coiled material. In this step, specifically, the thickness of the electrolytic copper foil is 3 to 50 μm; the hot-press bonding temperature is 120-350 ℃; the wide-width polymer substrate has a width of 300-1300 mm and can be polymer materials such as PET (polyethylene terephthalate), BOPP (biaxially oriented polypropylene), PI (polyimide) and the like.
P2, the thick copper layer composite copper foil coiled material is used as an anode.
And P3, stripping copper layers on two sides of the thick copper layer composite copper foil coiled material to the required thickness by an electrolytic method. In this step, specifically, when copper layers on both sides of the thick copper layer composite copper foil coiled material are electrolytically stripped, the temperature of the electrolyte is 40-60 ℃ and the current density is 3500-9000A/m 2 The advancing speed of the anode of the thick copper layer composite copper foil coiled material is 0.1-50 m/min.
And P4, depositing electrolytic copper foil on the cathode titanium shaft rollers at two sides. In this step, the cathode roller is made of stainless steel or titanium.
P5, ultrathin composite copper foil coiled material. In this step, specifically, the thickness of the copper foil on both sides of the ultra-thin composite copper foil coil is 0.5 to 1.5 μm.
The preparation method of the ultrathin composite copper foil comprises the following steps:
p1, preparing a 1300mm large-width thick copper layer composite copper foil coiled material by carrying out hot-press bonding molding on a 6 mm thick lithium battery grade electrolytic copper foil and a 1300mm large-width high polymer base material, wherein the thickness of the base material is 4 microns, and the thickness of the coiled material is 16 microns.
P2, taking the 1300mm wide and thick copper layer composite copper foil coiled material as an anode, and connecting the anode into an electrolytic tank.
P3, the mixed aqueous solution of copper sulfate and sulfuric acid is used as electrolyte, the concentration of copper is controlled to be stabilized at 80g/L, the concentration of sulfuric acid is controlled to be stabilized at 135g/L, the temperature of the electrolyte is 60 ℃, the circulation rate of the electrolyte is 18L/min, the voltage of an electrolytic tank is 0.9V, and the current density is 4500A/m 2 Thick copper layer compositeThe advancing speed of the anode of the copper foil coiled material is 8m/min, and the metal copper on the anode of the composite copper foil coiled material with the 1300mm wide and thick copper layer is electrolytically stripped.
And P4, stripping the electrolytic copper foil with the thickness of 6 microns on a cathode titanium shaft roller by adjusting the voltage, the current and the cathode area ratio, and performing water washing, treatment, drying, finishing and packaging to obtain the copper foil raw material of the next batch of thick copper layer composite copper foil coiled material.
P5, carrying out electrolytic treatment until the thickness of copper layers on two sides of the 1300mm large-width thick copper layer composite copper foil coiled material reaches 1 micron, washing, treating and drying to prepare the ultra-thin composite copper foil coiled material, wherein the thickness of the copper layers on one side is 1 micron, the thickness of the coiled material is 6 microns, and carrying out finishing and packaging to obtain the ultra-thin composite copper foil coiled material which enters a warehouse.
The invention and its embodiments have been described above with no limitation, and the actual construction is not limited to the embodiments of the invention as shown in the drawings. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Claims (6)
1. The preparation method of the ultrathin composite copper foil comprises the following steps:
p1, directly hot-pressing and bonding and molding the lithium battery-grade electrolytic copper foil with the thickness of 6 microns and a large-width polymer substrate to prepare a thick copper layer composite copper foil coiled material;
p2, using the thick copper layer composite copper foil coiled material as an anode;
p3, stripping copper layers on two sides of the anode of the thick copper layer composite copper foil coiled material to the required thickness by an electrolytic method;
p4, depositing electrolytic copper foil on the cathode titanium shaft rollers at two sides;
p5, ultrathin composite copper foil coiled material.
2. The method according to claim 1, wherein the 6-micron thick lithium battery-grade electrolytic copper foil and the large-width polymer base material are directly subjected to hot-press adhesion molding to prepare the thick copper layer composite copper foil coiled material, and the copper foil thickness on both sides of the thick copper layer composite copper foil coiled material is 3-50 microns.
3. The preparation method according to claim 1, wherein the thick copper layer composite copper foil coiled material is used as an anode, continuous electrolytic production is carried out, the temperature of electrolyte is 40-60 ℃, and the current density is 3500-9000A/m 2 The advancing speed of the thick copper layer composite copper foil coiled material is 0.1-50 m/min.
4. The preparation method according to claim 1, wherein the electrolytic copper foil is deposited on the cathode titanium shaft rollers on two sides, the thickness of the electrolytic copper foil product is adjusted according to requirements, and the cathode rollers are made of stainless steel and titanium metal.
5. The method of claim 1, wherein the ultra-thin composite copper foil web has copper layer thicknesses of 0.5 to 1.5 microns on both sides.
6. The preparation method according to claim 2, wherein the hot press bonding temperature of the 6-micron thick lithium battery-grade electrolytic copper foil and the wide-width polymer substrate is 120-350 ℃, the width of the wide-width polymer substrate is 300-1300 mm, and the wide-width polymer substrate comprises but is not limited to PET (polyethylene terephthalate), BOPP (biaxially oriented polypropylene) and PI (polyimide).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310797187.1A CN116695191A (en) | 2023-07-03 | 2023-07-03 | Preparation method of ultrathin composite copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310797187.1A CN116695191A (en) | 2023-07-03 | 2023-07-03 | Preparation method of ultrathin composite copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116695191A true CN116695191A (en) | 2023-09-05 |
Family
ID=87831156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310797187.1A Pending CN116695191A (en) | 2023-07-03 | 2023-07-03 | Preparation method of ultrathin composite copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116695191A (en) |
-
2023
- 2023-07-03 CN CN202310797187.1A patent/CN116695191A/en active Pending
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