CN109208041B - Additive for preparing high-performance ultrathin double-sided smooth copper foil - Google Patents
Additive for preparing high-performance ultrathin double-sided smooth copper foil Download PDFInfo
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- CN109208041B CN109208041B CN201811086886.0A CN201811086886A CN109208041B CN 109208041 B CN109208041 B CN 109208041B CN 201811086886 A CN201811086886 A CN 201811086886A CN 109208041 B CN109208041 B CN 109208041B
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- 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
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- 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
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- 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
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- Electrochemistry (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention belongs to the technical field of electrolytic copper foil processing, and particularly relates to an additive for preparing a high-performance ultrathin double-sided smooth copper foil, wherein each 10000 parts of electrolyte comprises the following components in parts by weight: 0.1-0.5 part of 2-mercapto benzimidazole, 0.8-1 part of polyethyleneimine alkyl salt, 0.5-1 part of copper acid wetting agent, 10-30 parts of collagen powder and 0.1-1 part of cerium oxide. The double-sided smooth copper foil of the lithium ion battery prepared by the additive can control the curling of the copper foil to be less than 4mm, so that the problem of uneven coating caused by the curling of the copper foil during the manufacturing of the lithium ion battery can be solved; meanwhile, the internal stress of the copper foil is reduced, the folding resistance can reach more than 9000 times, the folding resistance is greatly improved, and the bonding force with an active substance is enhanced; the prepared copper foil has good mechanical flexibility, and the electrode structure of the copper foil is not damaged and the electrochemical performance of the copper foil is not obviously changed under repeated bending or twisting.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil processing, and particularly relates to an additive for preparing a high-performance ultrathin double-sided smooth copper foil.
Background
When a high-capacity power battery cell is charged and discharged rapidly at a high rate, along with the change of the internal temperature of the battery cell in the process, the lithium electrolytic copper foil serving as a negative current collector also expands and contracts repeatedly along with the expansion and contraction of a negative material, and various performance indexes such as tensile strength, extensibility, flexibility, oxidation resistance, cohesiveness and the like are improved. As one of key materials of the new energy battery, the quality of the lithium electrolytic copper foil directly influences the battery process and performance, and the lithium electrolytic copper foil is an important field of global new energy battery competition at present.
Additives such as SPS, SP, polyethylene glycol and the like are commonly used in the production of the double-sided polished copper foil, although the additives have good leveling property, the increase of the internal stress of a copper film is easily caused, so that the copper foil is curled, the coating is easily uneven when a lithium battery is produced, the performance of the battery is affected, and the harm is large; in addition, in the production of winding type batteries, the copper foil is required to have better folding endurance, so the selected double-sided smooth copper foil has to have higher performance index.
In the production process of the double-sided polished copper foil, the selection and control of the additive are one of the most core technologies, the composite additive is required to be used for production in actual production, all components are matched and interact with each other, and the prepared copper foil can achieve excellent performance after optimized use.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an additive for preparing a high-performance ultrathin double-sided smooth copper foil.
The technical scheme for solving the technical problems is as follows: an additive for preparing a high-performance ultrathin double-sided smooth copper foil comprises the following components in parts by weight in 10000 parts of electrolyte: 0.1-0.5 part of 2-mercapto benzimidazole, 0.8-1 part of polyethyleneimine alkyl salt, 0.5-1 part of copper acid wetting agent, 10-30 parts of collagen powder and 0.1-1 part of cerium oxide.
Further, the acid copper wetting agent is one or a mixture of two of fatty amine polyoxyethylene ether, amine ethoxy compound, alkylamino phenol polyoxyethylene ether or perfluoroalkyl potassium sulfonate.
Further, the molecular weight of the collagen powder is 3000-10000.
Further, copper ions in the electrolyteConcentration of 80-100g/L, sulfuric acid concentration of 90-120g/L, Cl-The concentration is 10-40ppm, the electrolysis temperature is 45-62 ℃, and the current density is 50-60A/dm2。
Further, the thickness of the prepared ultrathin double-sided smooth copper foil is 6-8 μm, the smooth surface and the rough surface are both mirror surfaces, and the glossiness of the rough surface is Gs (60 degrees) 150-200.
Further, the glossiness Gs (60 °) indicates the glossiness measured at an emission-reception light angle of 60 °.
The production process of the electrolytic copper foil for the double-light battery comprises the steps of preparing electrolyte by dissolving copper, electrolyzing raw foil and carrying out anti-oxidation treatment in sequence; in the step of electrolytic foil generation, the additive of the invention is added to the copper sulfate electrolyte obtained in the step of dissolving copper to prepare the electrolyte.
The anti-oxidation treatment adopts a chromium-free anti-oxidation treatment method, and the specific process comprises the following steps: 3-10g/L of benzotriazole, 1-2g/L of tannic acid and 25-35 ℃ of temperature.
The invention has the beneficial effects that:
the double-sided smooth copper foil of the lithium ion battery prepared by the additive can control the curling of the copper foil to be less than 4mm, so that the problem of uneven coating caused by the curling of the copper foil during the manufacturing of the lithium ion battery can be solved; meanwhile, the internal stress of the copper foil is reduced, the folding resistance can reach more than 9000 times, the folding resistance is greatly improved, and the bonding force with an active substance is enhanced; the prepared copper foil has good mechanical flexibility, and the electrode structure of the copper foil is not damaged and the electrochemical performance of the copper foil is not obviously changed under repeated bending or twisting.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
An additive for preparing a high-performance ultrathin double-sided smooth copper foil comprises the following components in parts by weight in 10000 parts of electrolyte: 0.15 part of 2-mercapto benzimidazole, 1 part of polyethyleneimine alkyl salt, 0.5 part of copper acid wetting agent fatty amine polyoxyethylene ether, 10 parts of collagen powder and 0.2 part of cerium oxide.
The process conditions of the step of electrolyzing the green foil are as follows: sending copper sulfate electrolyte into foil forming machine, wherein the copper ion content is 80g/L, the sulfuric acid content is 120g/L, the chlorine ion content is 25ppm, the electrolysis temperature is 45-62 ℃, and the current density is 50-60A/dm2The produced double-sided optical ultrathin copper foil is 8 mu m.
The obtained copper foil was tested for the folding times and warping degree, and the test results are shown in table 1.
Example 2
An additive for preparing a high-performance ultrathin double-sided smooth copper foil comprises the following components in parts by weight in 10000 parts of electrolyte: 0.3 part of 2-mercapto benzimidazole, 0.8 part of polyethyleneimine alkyl salt, 0.65 part of copper acid wetting agent amine ethoxy compound, 20 parts of collagen powder and 0.5 part of cerium oxide.
The process conditions of the step of electrolyzing the green foil are as follows: sending the copper sulfate electrolyte into a foil forming machine, wherein the copper ion content is 85g/L, the sulfuric acid content is 112g/L, the chlorine ion content is 17ppm, the electrolysis temperature is 45-62 ℃, and the current density is 50-60A/dm2The produced double-sided optical ultrathin copper foil is 8 mu m.
The obtained copper foil was tested for the folding times and warping degree, and the test results are shown in table 1.
Example 3
An additive for preparing a high-performance ultrathin double-sided smooth copper foil comprises the following components in parts by weight in 10000 parts of electrolyte: 0.5 part of 2-mercapto benzimidazole, 0.9 part of polyethyleneimine alkyl salt, 0.1 part of copper acid wetting agent (mixing alkylamino phenol polyoxyethylene ether and perfluoroalkyl potassium sulfonate according to a weight ratio of 1: 1), 30 parts of collagen powder and 0.1 part of cerium oxide.
The process conditions of the step of electrolyzing the green foil are as follows: sending the copper sulfate electrolyte into a foil forming machine, wherein the copper ion content is 98g/L, the sulfuric acid content is 90g/L, the chlorine ion content is 36ppm, the electrolysis temperature is 45-62 ℃, and the current density is 50-60A/dm2The produced double-sided optical ultrathin copper foil is 8 mu m.
The obtained copper foil was tested for the folding times and warping degree, and the test results are shown in table 1.
Comparative example
An additive for preparing copper foil comprises the following components in parts by weight in 10000 parts of electrolyte: 0.7 part of hydroxyethyl cellulose, 0.3 part of collagen powder and 0.3 part of SPS.
The process conditions of the step of electrolyzing the green foil are as follows: sending copper sulfate electrolyte into foil forming machine, wherein the copper ion content is 80-100g/L, the sulfuric acid content is 90-120g/L, the chlorine ion content is 10-40ppm, the electrolysis temperature is 45-62 ℃, and the current density is 50-60A/dm2The produced double-sided optical ultrathin copper foil is 8 mu m.
The obtained copper foil was tested for the folding times and warping degree, and the test results are shown in table 1.
TABLE 1
| Number of times of folding | Degree of warp | |
| Example 1 | 9652 | 3mm |
| Example 2 | 9941 | 3mm |
| Example 3 | 10067 | 2mm |
| Comparative example | 5581 | 7mm |
As can be seen from Table 1, the copper foil prepared by the composite additive provided by the invention has the advantages that the folding times are obviously improved, and the warping degree is obviously reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. The additive for preparing the high-performance ultrathin double-sided smooth copper foil is characterized by comprising the following components in parts by weight in 10000 parts of electrolyte: 0.1-0.5 part of 2-mercapto benzimidazole, 0.8-1 part of polyethyleneimine alkyl salt, 0.5-1 part of copper acid wetting agent, 10-30 parts of collagen powder and 0.1-1 part of cerium oxide.
2. The additive of claim 1, wherein the copper acid wetting agent is one or a mixture of two of fatty amine polyoxyethylene ether, amine ethoxy compound, alkylamino phenol polyoxyethylene ether and potassium perfluoroalkyl sulfonate.
3. The additive as claimed in claim 1, wherein the molecular weight of the collagen powder is 3000-10000.
4. The additive according to claim 1, wherein the concentration of copper ions in the electrolyte is 80-100g/L, the concentration of sulfuric acid is 90-120g/L, and Cl is present in the electrolyte-The concentration is 10-40ppm, the temperature is 45-62 ℃, and the current density is 50-60A/dm2。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811086886.0A CN109208041B (en) | 2018-09-18 | 2018-09-18 | Additive for preparing high-performance ultrathin double-sided smooth copper foil |
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| CN201811086886.0A CN109208041B (en) | 2018-09-18 | 2018-09-18 | Additive for preparing high-performance ultrathin double-sided smooth copper foil |
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| CN109208041A CN109208041A (en) | 2019-01-15 |
| CN109208041B true CN109208041B (en) | 2020-06-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110592568A (en) * | 2019-09-16 | 2019-12-20 | 铜陵市华创新材料有限公司 | Environment-friendly anti-oxidation liquid for negative current collector and preparation and use methods thereof |
| CN111455414A (en) * | 2020-03-09 | 2020-07-28 | 深圳市惟华电子科技有限公司 | Additive for producing gradual change type electrolytic copper foil |
| CN112981473B (en) * | 2021-02-05 | 2021-11-23 | 广东嘉元科技股份有限公司 | Electrolytic copper foil and preparation method thereof |
| CN114836744A (en) * | 2022-04-28 | 2022-08-02 | 浙江大学 | Chromium-free passivation solution for copper foil and preparation method thereof |
| CN116770374B (en) * | 2023-08-08 | 2024-02-06 | 广东盈华电子科技有限公司 | Production process and equipment of 10-12oz ultra-thick electrolytic copper foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4692221A (en) * | 1986-12-22 | 1987-09-08 | Olin Corporation | In-situ dendritic treatment of electrodeposited foil |
| US7147767B2 (en) * | 2002-12-16 | 2006-12-12 | 3M Innovative Properties Company | Plating solutions for electrochemical or chemical deposition of copper interconnects and methods therefor |
| CN1250775C (en) * | 2002-12-27 | 2006-04-12 | 财团法人工业技术研究院 | Method for producing anti-folding electrolytic copper foil |
| TWI414638B (en) * | 2006-06-07 | 2013-11-11 | Furukawa Electric Co Ltd | A method for manufacturing a surface-treated electrolytic copper foil, and a circuit board |
| CN102965698B (en) * | 2012-11-28 | 2015-09-09 | 山东金宝电子股份有限公司 | Low warpage electrolytic copper foil production technique |
| CN104651884A (en) * | 2014-04-28 | 2015-05-27 | 雷磊 | Compound additive for electrolytic copper foil |
| KR102473557B1 (en) * | 2015-09-24 | 2022-12-01 | 에스케이넥실리스 주식회사 | Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same |
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