CN109208041A - Additive is used in a kind of preparation of high-performance ultrathin dual light copper foil - Google Patents
Additive is used in a kind of preparation of high-performance ultrathin dual light copper foil Download PDFInfo
- Publication number
- CN109208041A CN109208041A CN201811086886.0A CN201811086886A CN109208041A CN 109208041 A CN109208041 A CN 109208041A CN 201811086886 A CN201811086886 A CN 201811086886A CN 109208041 A CN109208041 A CN 109208041A
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- copper foil
- parts
- additive
- copper
- dual light
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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
-
- 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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)
- Electrolytic Production Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention belongs to electrolytic copper foil processing technique fields, more particularly to a kind of high-performance ultrathin dual light copper foil prepares and uses additive, contains in every 10000 parts of electrolyte: 0.1-0.5 parts of 2- mercaptobenzoimidazoles, 0.8-1 portions of polyethyleneimine alkyl salt, 0.5-1 parts of sour copper wetting agents, 10-30 parts of collagen protein powders and 0.1-1 parts of cerium oxide.The lithium ion battery dual light copper foil prepared using additive of the invention, can by the curl control of copper foil in 4mm hereinafter, coating the problem of unevenness caused by thus, it is possible to improve when manufacture lithium ion battery due to copper foil curling；The internal stress of copper foil itself becomes smaller simultaneously, and folding can reach 9000 times or more, and folding resistance also greatly improves, and enhance the cohesive force with active material；And the copper foil of preparation has good mechanical flexibility, under alternating bending or distortion, electrode structure is without damage, chemical property without significant change.
Description
Technical field
The invention belongs to electrolytic copper foil processing technique fields more particularly to a kind of preparation of high-performance ultrathin dual light copper foil to use
Additive.
Background technique
When high-capacity dynamical battery core high magnification fast charging and discharging, with the variation of battery core internal temperature in the process, as
The lithium electrolytic copper foil of negative current collector with negative electrode material dilation also dilation repeatedly, for tensile strength, extensibility,
All kinds of performance indicators such as flexibility, oxygen-proof property, caking property will also increase.One of critical material as new energy battery,
The superiority and inferiority of lithium electrolytic copper foil quality directly influences battery process and performance, is the important neck of current global new energy battery competition
Domain.
The additives such as SPS, SP, polyethylene glycol are commonly used in the production of dual light copper foil, although substance of this kind has well
Surface flat, but be also easier to cause the increase of Copper thin film internal stress, so as to cause copper foil curling, it is easy when producing lithium battery
It causes to be unevenly coated, to influence battery performance, endanger larger；Besides in the production of takeup type type cell, it is desirable that copper
Foil has better folding resistance, so selected dual light copper foil must have higher performance indicator.
In dual light copper foil production process, the selection and control of additive are most crucial one of technology, actual production
In must be produced using compound additive, each component collocation mutually works, used after optimization, the copper foil prepared can be only achieved
Excellent performance.
Summary of the invention
The present invention in view of the deficiency of the prior art, provides a kind of preparation of high-performance ultrathin dual light copper foil with adding
Add agent.
The technical scheme to solve the above technical problems is that a kind of preparation of high-performance ultrathin dual light copper foil is with adding
Add agent, according to parts by weight, contains in every 10000 parts of electrolyte: 0.1-0.5 parts of 2- mercaptobenzoimidazoles, 0.8-1 parts of polyethylene
Imines alkyl salt, 0.5-1 parts of sour copper wetting agents, 10-30 parts of collagen protein powders and 0.1-1 parts of cerium oxide.
Further, the sour copper wetting agent is aliphatic amine polyoxyethylene ether, amine ethoxy compound, alkylamino radical phenol polyoxy
The mixing of one or both of vinethene or perfluoro alkyl sulfonic acid potassium.
Further, the molecular weight of the collagen protein powder is 3000-10000.
Further, the copper ion concentration in the electrolyte is 80-100g/L, sulfuric acid concentration 90-120g/L, Cl-It is dense
Degree is 10-40ppm, and electrolysis temperature is 45-62 DEG C, and current density is 50-60 A/dm2。
Further, the ultrathin double-face optical copper foil of preparation with a thickness of 6-8 μm, smooth surface and hair side are in mirror surface, hair side gloss
Degree is Gs (60 °) 150-200.
Further, (60 °) of the glossiness Gs glossiness for indicating to receive optic angle measurement with 60 ° of transmitting.
The production technology of double photocell electrolytic copper foils is prepared, step is followed successively by molten copper electrolyte, electrolysis foil and prevents
Oxidation processes；Of the invention add is added in electrolysis foil step, the copper sulfate electrolyte obtained to molten copper electrolyte step
Add agent.
Wherein, anti-oxidation processing uses Chrome-free anti-oxidation processing method, specifically comprises the processes of: benzotriazole 3-10g/L,
Tannic acid 1-2g/L, 25-35 DEG C of temperature.
The beneficial effects of the present invention are:
The lithium ion battery dual light copper foil prepared using additive of the invention, can be existed the curl control of copper foil
4mm is hereinafter, coat uneven problem caused by thus, it is possible to improve when manufacturing lithium ion battery due to copper foil curling；Copper simultaneously
The internal stress of foil itself becomes smaller, and folding can reach 9000 times or more, and folding resistance also greatly improves, and enhances and active material
Cohesive force；And the copper foil of preparation has good mechanical flexibility, under alternating bending or distortion, electrode structure is without damage, electricity
Chemical property is without significant change.
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1
A kind of high-performance ultrathin dual light copper foil preparation additive contains in every 10000 parts of electrolyte according to parts by weight
Have: 0.15 part of 2- mercaptobenzoimidazole, 1 portion of polyethyleneimine alkyl salt, 0.5 part of sour copper wetting agent aliphatic amine polyoxyethylene ether,
10 parts of collagen protein powders and 0.2 part of cerium oxide.
It is electrolysed the process conditions of foil step are as follows: will be sent into foil machine in copper sulfate electrolyte, content of copper ion is
80g/L, sulfuric acid content 120g/L, chloride ion content 25ppm, 45-62 DEG C of electrolysis temperature, current density 50-60A/dm2,
Two-sided optical ultrathin copper foil produced is 8 μm.
The folding number and angularity of test gained copper foil, testing result are shown in Table 1.
Embodiment 2
A kind of high-performance ultrathin dual light copper foil preparation additive contains in every 10000 parts of electrolyte according to parts by weight
Have: 0.3 part of 2- mercaptobenzoimidazole, 0.8 portion of polyethyleneimine alkyl salt, 0.65 part of sour copper wetting agent amine ethoxy compound,
20 parts of collagen protein powders and 0.5 part of cerium oxide.
It is electrolysed the process conditions of foil step are as follows: will be sent into foil machine in copper sulfate electrolyte, content of copper ion is
85g/L, sulfuric acid content 112g/L, chloride ion content 17ppm, 45-62 DEG C of electrolysis temperature, current density 50-60A/dm2,
Two-sided optical ultrathin copper foil produced is 8 μm.
The folding number and angularity of test gained copper foil, testing result are shown in Table 1.
Embodiment 3
A kind of high-performance ultrathin dual light copper foil preparation additive contains in every 10000 parts of electrolyte according to parts by weight
Have: 0.5 part of 2- mercaptobenzoimidazole, 0.9 portion of polyethyleneimine alkyl salt, 0.1 part of sour copper wetting agent (alkylamino radical phenol polyethenoxy
Ether and perfluoro alkyl sulfonic acid potassium are mixed according to weight ratio 1:1), 30 parts of collagen protein powders and 0.1 part of cerium oxide.
It is electrolysed the process conditions of foil step are as follows: will be sent into foil machine in copper sulfate electrolyte, content of copper ion is
98g/L, sulfuric acid content 90g/L, chloride ion content 36ppm, 45-62 DEG C of electrolysis temperature, current density 50-60A/dm2, institute
The two-sided optical ultrathin copper foil of production is 8 μm.
The folding number and angularity of test gained copper foil, testing result are shown in Table 1.
Comparative example
A kind of copper foil preparation additive contains: 0.7 part of ethoxy in every 10000 parts of electrolyte according to parts by weight
Cellulose, 0.3 part of collagen protein powder and 0.3 part of SPS.
It is electrolysed the process conditions of foil step are as follows: will be sent into foil machine in copper sulfate electrolyte, content of copper ion 80-
100g/L, sulfuric acid content 90-120g/L, chloride ion content 10-40ppm, 45-62 DEG C of electrolysis temperature, current density 50-60A/
dm2, two-sided optical ultrathin copper foil produced is 8 μm.
The folding number and angularity of test gained copper foil, testing result are shown in Table 1.
Table 1
| Folding number | Angularity | |
| Embodiment 1 | 9652 | 3mm |
| Embodiment 2 | 9941 | 3mm |
| Embodiment 3 | 10067 | 2mm |
| Comparative example | 5581 | 7mm |
As can be seen from Table 1, using copper foil made from compound additive of the invention, folding number is significantly improved, warpage
Degree is substantially reduced.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of high-performance ultrathin dual light copper foil preparation additive, which is characterized in that according to parts by weight, every 10000 parts
Contain in electrolyte: 0.1-0.5 parts of 2- mercaptobenzoimidazoles, 0.8-1 portions of polyethyleneimine alkyl salt, 0.5-1 parts of sour copper wettings
Agent, 10-30 parts of collagen protein powders and 0.1-1 parts of cerium oxide.
2. additive according to claim 1, which is characterized in that the sour copper wetting agent is aliphatic amine polyoxyethylene
The mixing of one or both of ether, amine ethoxy compound, alkylamino radical phenol polyethenoxy ether or perfluoro alkyl sulfonic acid potassium.
3. additive according to claim 1, which is characterized in that the molecular weight of the collagen protein powder is 3000-
10000。
4. additive according to claim 1, which is characterized in that the copper ion concentration in the electrolyte is 80-100g/
L, sulfuric acid concentration 90-120g/L, Cl-Concentration is 10-40ppm, and temperature is 45-62 DEG C, current density 50-60A/dm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811086886.0A CN109208041B (en) | 2018-09-18 | 2018-09-18 | Additive for preparing high-performance ultrathin double-sided smooth copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Publication Number | Publication Date |
|---|---|
| CN109208041A true CN109208041A (en) | 2019-01-15 |
| CN109208041B CN109208041B (en) | 2020-06-02 |
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| CN201811086886.0A Active CN109208041B (en) | 2018-09-18 | 2018-09-18 | Additive for preparing high-performance ultrathin double-sided smooth copper foil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112981473A (en) * | 2021-02-05 | 2021-06-18 | 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 |
| CN116770374A (en) * | 2023-08-08 | 2023-09-19 | 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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| US4692221A (en) * | 1986-12-22 | 1987-09-08 | Olin Corporation | In-situ dendritic treatment of electrodeposited foil |
| CN1511976A (en) * | 2002-12-27 | 2004-07-14 | 财团法人工业技术研究院 | Method for producing anti-folding electrolytic copper foil |
| CN1726310A (en) * | 2002-12-16 | 2006-01-25 | 3M创新有限公司 | Plating solutions for electrochemical or chemical deposition of copper interconnects and methods therefor |
| CN101126168A (en) * | 2006-06-07 | 2008-02-20 | 古河电路铜箔株式会社 | Surface treatment electrolysis copper foil, method for manufacturing the same , and circuit board |
| CN102965698A (en) * | 2012-11-28 | 2013-03-13 | 山东金宝电子股份有限公司 | Production process of low-warpage electrolytic copper foil |
| CN104651884A (en) * | 2014-04-28 | 2015-05-27 | 雷磊 | Compound additive for electrolytic copper foil |
| CN106558703A (en) * | 2015-09-24 | 2017-04-05 | Ls美创有限公司 | Electrolytic copper foil, including its electrode and secondary cell and its manufacture method |
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| US4692221A (en) * | 1986-12-22 | 1987-09-08 | Olin Corporation | In-situ dendritic treatment of electrodeposited foil |
| CN1726310A (en) * | 2002-12-16 | 2006-01-25 | 3M创新有限公司 | Plating solutions for electrochemical or chemical deposition of copper interconnects and methods therefor |
| CN1511976A (en) * | 2002-12-27 | 2004-07-14 | 财团法人工业技术研究院 | Method for producing anti-folding electrolytic copper foil |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112981473A (en) * | 2021-02-05 | 2021-06-18 | 广东嘉元科技股份有限公司 | Electrolytic copper foil and preparation method thereof |
| 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 |
| CN116770374A (en) * | 2023-08-08 | 2023-09-19 | 广东盈华电子科技有限公司 | Production process and equipment of 10-12oz ultra-thick electrolytic copper foil |
| 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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| CN109208041B (en) | 2020-06-02 |
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Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Patentee after: Shandong Jinbao Electronics Co.,Ltd. Address before: 265400 No. 128, Wenquan Road, Zhaoyuan, Shandong, Yantai Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |