CN112981473B - Electrolytic copper foil and preparation method thereof - Google Patents
Electrolytic copper foil and preparation method thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011889 copper foil Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000011888 foil Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 11
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 11
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 11
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229920002907 Guar gum Polymers 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000000665 guar gum Substances 0.000 claims description 10
- 229960002154 guar gum Drugs 0.000 claims description 10
- 235000010417 guar gum Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000006259 organic additive Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- -1 lanthanum ions Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012795 verification 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/08—Rinsing
-
- 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
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses an electrolytic copper foil and a preparation method thereof, belonging to the technical field of lithium ion battery copper foils, wherein the electrolytic copper foil contains more than or equal to 99.9 wt% of copper, 210-260 mu g/g of chlorine element and 300-340 mu g/g of rare earth element; the preparation method comprises the following steps: adding an additive into a sulfuric acid-copper sulfate solution to be used as an electrolyte for electrolysis, and washing and drying the obtained raw foil to obtain the electrolytic copper foil; the electrolytic copper foil disclosed by the invention is high in chlorine content, so that an organic additive in the electrolyte can be better adsorbed on a base material, and the obtained copper foil has good tensile property and folding resistance by adjusting the components and content of the electrolyte during the preparation of the electrolytic copper foil.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery copper foils, and particularly relates to an electrolytic copper foil and a preparation method thereof.
Background
Lithium ion secondary batteries have high energy and high power density, making them a technological choice for portable electronic devices, power tools, electric vehicles, energy storage systems, mobile phones, tablet computers, aerospace applications, military applications and railways, and electrolytic copper foils used as negative electrode materials for lithium ion batteries have also met with new opportunities for development. The copper foil is used as a carrier of a negative active substance and a collection and transmission body of negative electron current in the lithium battery, so that the tensile strength, extensibility, compactness, folding resistance, surface roughness, thickness uniformity, appearance quality and the like of the electrolytic copper foil have great influence on the manufacturing process of the negative electrode of the lithium ion battery and the electrochemical performance of the lithium ion battery.
Pure copper foil does not satisfy high performance requirements, and additives are generally required to be added to the electrolyte to impart corresponding properties to the copper foil, while in the case of organic additives, Cl is required for effective adsorption to the copper foil because Cl is required-Will adsorb on the surface of the copper substrate, and Cu+Complexes of organic additives electrostatically adsorbed to Cl-I.e. Cu+Complexes of organic additives via Cl-Adsorbed on the copper substrate. In addition, the addition of Cl is beneficial to the improvement of the tensile property of the copper foil, but when the Cl content exceeds 200 μ g/g, the folding endurance of the copper foil is rapidly reduced, so that the technical problem to be solved is to improve the Cl content in the copper foil, so that the Cl content in the copper foil can fully exert the adsorption effect on the organic additive and the improvement effect on the tensile property of the copper foil, and the folding endurance of the copper foil is not influenced.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides an electrolytic copper foil and a method for preparing the same.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is as follows: an electrolytic copper foil, the copper content is more than or equal to 99.9 wt%, the chlorine element content is 210-260 mug/g, and the rare earth element content is 300-340 mug/g.
Furthermore, the copper content is more than or equal to 99.9 wt%, the chlorine element content is 220-240 mu g/g, and the rare earth element content is 310-320 mu g/g.
The second technical scheme of the invention is as follows: the preparation method of the electrolytic copper foil comprises the following steps: adding an additive into a sulfuric acid-copper sulfate solution to be used as an electrolyte for electrolysis, and washing and drying the obtained raw foil to obtain the electrolytic copper foil; the additive comprises graphene oxide, guar gum, soluble salt of rare earth elements, hydroxypropyl methyl cellulose, polyethylene glycol, polyethyleneimine and chlorine-containing compounds.
Further, the rare earth element is one of lanthanum, cerium, samarium and yttrium; the chlorine-containing compound is one or more of sodium chloride, potassium chloride, ammonium chloride, hydrogen chloride, magnesium chloride and calcium chloride.
Further, the molecular weight of the polyethylene glycol is 4000-6000; the molecular weight of the polyethyleneimine is 6000-8000.
Further, in the electrolyte, Cu2+The concentration of the sulfuric acid is 50-100 g/L, and the concentration of the sulfuric acid is 120-200 g/L.
Further, in the electrolyte, the concentration of graphene oxide is 3-6 mg/L, the concentration of guar gum is 10-15 mg/L, the concentration of rare earth elements is 40-60 mg/L, the concentration of hydroxypropyl methyl cellulose is 5-10 mg/L, the concentration of polyethylene glycol is 5-10 mg/L, the concentration of polyethyleneimine is 30-40 mg/L, and Cl is-The concentration of (b) is 20-30 mg/L.
Further, the temperature of the electrolyte is 50-60 ℃, and the average current density of the cathode electrode surface is 50-65A/dm2。
Furthermore, the washing is carried out by washing with water, and then washing with dilute hydrochloric acid and water in sequence.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrolytic copper foil has the copper content of more than or equal to 99.9 wt%, the chlorine content of 210-260 mug/g, the rare earth element content of 300-340 mug/g and the chlorine content of high, so that an organic additive in an electrolyte can be better adsorbed on a base material, and the components and the content of the electrolyte during the preparation of the electrolytic copper foil are adjusted, so that the obtained copper foil has good tensile property and folding resistance;
(2) the invention has simple preparation process, easily obtained raw materials and low production cost, and is suitable for popularization.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are in parts by weight unless otherwise specified.
Example 1
The preparation of the electrolytic copper foil comprises the following steps:
the concentration of the prepared sulfuric acid is 160g/L, Cu2+Adding graphene oxide, guar gum, lanthanum sulfate, hydroxypropyl methyl cellulose, polyethylene glycol with the molecular weight of 5000, polyethyleneimine with the molecular weight of 7000 and sodium chloride into the solution as electrolyte for electrolysis, wherein the concentration of graphene oxide is 5mg/L, the concentration of guar gum is 12mg/L, the concentration of lanthanum ions is 50mg/L, the concentration of hydroxypropyl methyl cellulose is 8mg/L, the concentration of polyethylene glycol is 7mg/L, the concentration of polyethyleneimine is 35mg/L and the concentration of chloride ions is 25 mg/L; the temperature of the electrolyte was 55 ℃ and the average current density on the cathode electrode surface was 60A/dm2And continuously stripping the raw foil from the cathode roller after the raw foil on the cathode roller rotates out of the liquid level along with the roller, washing with water, washing with dilute hydrochloric acid, washing with water again, and drying to obtain the electrolytic copper foil. The contents of copper, chlorine and lanthanum in the obtained electrolytic copper foil were measured, and the results are shown in table 1.
Example 2
The preparation of the electrolytic copper foil comprises the following steps:
the concentration of the prepared sulfuric acid is 120g/L, Cu2+Adding graphene oxide, guar gum, cerium sulfate, hydroxypropyl methyl cellulose, polyethylene glycol with the molecular weight of 4000, polyethyleneimine with the molecular weight of 8000 and ammonium chloride into the solution as electrolyte for electrolysis, wherein the concentration of the graphene oxide is 3mg/L, the concentration of the guar gum is 15mg/L, the concentration of cerium ions is 40mg/L, the concentration of the hydroxypropyl methyl cellulose is 10mg/L, the concentration of the polyethylene glycol is 5mg/L, the concentration of the polyethyleneimine is 30mg/L and the concentration of chloride ions is 30 mg/L; the temperature of the electrolyte was 50 ℃ and the average current density on the cathode electrode surface was 50A/dm2And continuously stripping the raw foil from the cathode roller after the raw foil on the cathode roller rotates out of the liquid level along with the roller, washing with water, washing with dilute hydrochloric acid, washing with water again, and drying to obtain the electrolytic copper foil. The contents of copper, chlorine and lanthanum in the obtained electrolytic copper foil were measured, and the results are shown in table 1.
Example 3
The preparation of the electrolytic copper foil comprises the following steps:
the concentration of the prepared sulfuric acid is 200g/L, Cu2+Adding graphene oxide, guar gum, samarium sulfate, hydroxypropyl methyl cellulose, polyethylene glycol with the molecular weight of 6000, polyethyleneimine with the molecular weight of 6000 and magnesium chloride into the solution as electrolyte for electrolysis, wherein the concentration of the graphene oxide in the electrolyte is 6mg/L, the concentration of the guar gum is 10mg/L, the concentration of samarium ions is 60mg/L, the concentration of the hydroxypropyl methyl cellulose is 5mg/L, the concentration of the polyethylene glycol is 10mg/L, the concentration of the polyethyleneimine is 40mg/L and the concentration of chloride ions is 20 mg/L; the temperature of the electrolyte was 60 ℃ and the average current density on the cathode electrode surface was 65A/dm2And continuously stripping the raw foil from the cathode roller after the raw foil on the cathode roller rotates out of the liquid level along with the roller, washing with water, washing with dilute hydrochloric acid, washing with water again, and drying to obtain the electrolytic copper foil. The contents of copper, chlorine and lanthanum in the obtained electrolytic copper foil were measured, and the results are shown in table 1.
Comparative example 1
The difference from example 1 is that hydroxypropylmethylcellulose was not added to the electrolyte.
Comparative example 2
The difference from example 1 is that the concentration of lanthanum ions in the electrolyte was 80 mg/L.
Comparative example 3
The difference from example 1 is that the electrolyte solution contains 10mg/L of chloride ions.
Comparative example 4
The difference from example 1 is that the molecular weight of the polyethylene glycol used is 8000.
Comparative example 5
The difference from example 1 is that the polyethyleneimine used has a molecular weight of 10000.
TABLE 1
| Group of | Copper content/wt% | Cl content/(μ g/g) | Content of rare earth element/(μ g/g) |
| Example 1 | 99.93 | 225.3 | 314.8 |
| Example 2 | 99.96 | 251.7 | 305.2 |
| Example 3 | 99.91 | 214.6 | 331.4 |
| Comparative example 1 | 99.92 | 223.5 | 310.5 |
| Comparative example 2 | 99.89 | 221.5 | 332.8 |
| Comparative example 3 | 99.97 | 198.5 | 318.2 |
| Comparative example 4 | 99.92 | 226.1 | 312.5 |
| Comparative example 5 | 99.93 | 220.5 | 319.7 |
Effect verification
1) Tensile Properties
Tensile properties of the electrolytic copper foils prepared in examples 1 to 3 and comparative examples 1 to 6 and tensile properties after heating at 350 ℃ for 1 hour in an inert gas atmosphere were measured by using a tensile tester, and the obtained tensile strengths are shown in table 2.
2) Folding endurance
At room temperature, the electrolytic copper foils prepared in examples 1 to 3 and comparative examples 1 to 6 and the folding test thereof were heated at 350 ℃ for 1 hour in an inert gas atmosphere, and first, a polyimide film having a thickness of 100 μm was used as a barrier layer having a bending radius of 0.2mm, and each group of samples was placed on the barrier layer to obtain a folded body of the sample and the barrier layer; then, this fold is bent so that the barrier is on the inside and the sample on the outside, i.e.: forming 4 layers after bending, wherein the two layers inside are the polyimide film interlayer, and the upper and lower outer layers are samples; then, a rubber roller (weight: 2kg, rubber hardness: 80Hs) was used to apply a load to the upper layer, and an optical microscope was used to observe whether or not the sample had cracks; if no cracks were present, the panels were opened again and the above procedure was repeated until cracks were observed and the number of folds was recorded as shown in table 2.
TABLE 2
As can be seen from tables 1 and 2, the electrolytic copper foil of the present invention has a Cl content of more than 200. mu.g/g and the copper foil has both excellent tensile properties and folding endurance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (5)
1. An electrolytic copper foil is characterized in that the copper content is more than or equal to 99.9 wt%, the chlorine element content is 210-260 mug/g, and the rare earth element content is 300-340 mug/g;
the preparation method of the electrolytic copper foil comprises the following steps: adding an additive into a sulfuric acid-copper sulfate solution to be used as an electrolyte for electrolysis, and washing and drying the obtained raw foil to obtain the electrolytic copper foil; the additive comprises graphene oxide, guar gum, soluble salt of rare earth elements, hydroxypropyl methyl cellulose, polyethylene glycol, polyethyleneimine and chlorine-containing compounds;
the molecular weight of the polyethylene glycol is 4000-6000; the molecular weight of the polyethyleneimine is 6000-8000;
in the electrolyte, Cu2+The concentration of the sulfuric acid is 50-100 g/L, and the concentration of the sulfuric acid is 120-200 g/L;
in the electrolyte, the concentration of graphene oxide is 3-6 mg/L, the concentration of guar gum is 10-15 mg/L, the concentration of rare earth elements is 40-60 mg/L, the concentration of hydroxypropyl methyl cellulose is 5-10 mg/L, the concentration of polyethylene glycol is 5-10 mg/L, the concentration of polyethyleneimine is 30-40 mg/L, and Cl is-Has a concentration of 20 to 30mg/L。
2. The electrolytic copper foil according to claim 1, wherein the copper content is not less than 99.9 wt%, the chlorine element content is 220 to 240 μ g/g, and the rare earth element content is 310 to 320 μ g/g.
3. The electrolytic copper foil according to claim 1, wherein the rare earth element is one of lanthanum, cerium, samarium and yttrium; the chlorine-containing compound is one or more of sodium chloride, potassium chloride, ammonium chloride, hydrogen chloride, magnesium chloride and calcium chloride.
4. The electrolytic copper foil according to claim 1, wherein the electrolyte temperature is 50 to 60 ℃ and the average current density on the cathode electrode surface is 50 to 65A/dm2。
5. The electrolytic copper foil according to claim 1, wherein the washing is carried out by washing with water, followed by dilute hydrochloric acid washing and then washing with water.
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