CN109267109B - Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof - Google Patents
Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof Download PDFInfo
- Publication number
- CN109267109B CN109267109B CN201711079427.5A CN201711079427A CN109267109B CN 109267109 B CN109267109 B CN 109267109B CN 201711079427 A CN201711079427 A CN 201711079427A CN 109267109 B CN109267109 B CN 109267109B
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- Prior art keywords
- copper foil
- additive
- ppm
- polypropylene glycol
- phytic acid
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
-
- 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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- 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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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an additive for manufacturing a double-sided photoelectron copper foil of a negative current collector of a lithium ion energy storage battery and a using method thereof, wherein the additive comprises polypropylene glycol, phytic acid, sodium propane sulfonate and hydroxymethyl cellulose, and the components are as follows in percentage by weight: 10-15: 2-10: 1.5-5: 120-150. The method solves the problems that the existing additive can not produce copper foil with high tensile strength (more than 55kg/mm 2) and high extensibility (more than 10%), so that the copper foil with the thickness less than 6 microns can not be normally used at a client, and the copper foil has fatal influence on the service life of a battery due to wrinkling, fragmentation and the like in the process of manufacturing a lithium battery cell due to low tensile strength and extensibility. The invention belongs to the field of manufacturing of negative copper foils of lithium batteries.
Description
Technical Field
The invention provides an additive for manufacturing a copper foil and a using method thereof, belonging to the technical field of copper foil manufacturing.
Background
At present, in the field of manufacturing of double-sided photoelectron copper foils of negative current collectors of lithium ion energy storage batteries, the thickness of copper foils produced by using the existing additives is more than 6 microns, the main reason is that the existing electrolytic copper foil additives of lithium ion batteries mainly use peptide cyanine dyes and sodium sulfonate, and due to the limitation of the copper foil additives, the existing technical means can not produce copper foils with high tensile strength (more than 55kg/mm 2) and high extensibility (more than 10%), so that the copper foils smaller than 6 microns can not be normally used at a client, and the low tensile strength and the low extensibility can cause the defects that the copper foils have fatal influences on the service life of the batteries, such as wrinkling, breaking and the like in the process of manufacturing lithium ion battery cells.
Disclosure of Invention
The invention aims to: the additive is used for solving the problems that the existing additive cannot produce copper foil with high tensile strength (more than 55kg/mm 2) and high extensibility (more than 10%), so that the copper foil smaller than 6 microns cannot be normally used at a client, and the copper foil has the fatal influence on the service life of a battery due to the fact that the copper foil is wrinkled, broken and the like in the process of manufacturing a lithium battery cell due to low tensile strength and extensibility.
In order to solve the problems, the additive is prepared by adopting the double-sided photoelectron copper foil of the negative current collector of the lithium ion energy storage battery, and comprises polypropylene glycol, phytic acid, sodium propane sulfonate and hydroxymethyl cellulose, wherein the components are sequentially in the following content ratio by weight: 10-15: 2-10: 1.5-5: 120-150.
The use method of the additive is as follows:
when in use, the additive is added into the copper sulfate electrolyte, so that the content of each component in the copper sulfate electrolyte is kept as follows: copper ion content: 90-110 g/L; sulfate radical content: 40-60 g/L; content of chloride ion: less than or equal to 3 ppm; phytic acid: 2-10 ppm; polypropylene glycol: 10-15 ppm; sodium propane sulfonate: 1.5-5 ppm; a hydroxymethyl cellulose; 120-150 ppm.
In the using method, 10-15g of polypropylene glycol and 1.5-5g of propane sodium sulfonate are dissolved in 500 ml of DI water, 2-10g of phytic acid and 150g of hydroxymethyl cellulose 120-sodium sulfonate are dissolved in another 500 ml of DI water, the two mixed solutions are respectively stirred and stood at room temperature, when the two mixed solutions are added into a copper sulfate electrolyte, the two mixed solutions are mixed and stirred uniformly, and then a metering device is used for dropwise adding the mixed solution into a CuSO4 solution according to 70 ml per minute.
Compared with the prior art, the additive and the method can produce the copper foil with high tensile strength and high extensibility, solve the fatal defects of easy breaking, crumpling and the like in the manufacturing process of the lithium battery cell, greatly reduce the thickness of the copper foil to 3-400 mu m, improve the battery capacity of unit volume, and increase the number of positive and negative electrode materials in the cell of unit volume as the copper foil is thinner, thereby achieving the purpose of improving the battery capacity.
Detailed Description
In order that the present invention may be more clearly and clearly described, the present invention will now be described in further detail.
Example (b):
the embodiment provides an additive for manufacturing a double-sided photoelectron copper foil of a negative current collector of a lithium ion energy storage battery, which comprises phytic acid, polypropylene glycol, sodium propane sulfonate and hydroxymethyl cellulose, wherein the components are as follows in percentage by weight: 6: 12.5: 3.25: 135.
the use method of the additive is as follows:
dissolving 12.5g of polypropylene glycol and 3.25g of sodium propane sulfonate into 500 ml of DI water, dissolving 6g of phytic acid and 135g of hydroxymethyl cellulose into another 500 ml of DI water, stirring and standing the two mixed solutions at room temperature respectively, when adding the mixed solutions into a copper sulfate electrolyte, firstly mixing and uniformly stirring the two mixed solutions, and dropwise adding the mixed solutions into a CuSO4 solution by using a metering device according to 70 ml per minute so that the content of each component in the copper sulfate electrolyte is always kept: copper ion content: 90-110 g/L; sulfate radical content: 40-60 g/L; content of chloride ion: less than or equal to 3 ppm; phytic acid: 2-10 ppm; polypropylene glycol: 10-15 ppm; sodium propane sulfonate: 1.5-5 ppm; a hydroxymethyl cellulose; and (4) 150ppm, the additives are dripped when the copper foil is started for debugging and production, and the additives are stopped when the copper foil is stopped, wherein 60 liters of additives are needed when one ton of double-lithium-ion battery copper foil is produced.
The copper foil produced by the method. The physical properties were determined as follows:
(1) surface density: 27-3600g/m2；
(2) Thickness: 3-400 mu m;
(3) normal temperature tensile strength: 55-90kg/mm2；
(4) The normal temperature elongation is more than 10 percent;
the produced copper foil has high tensile strength and high extensibility, solves the fatal defects of no breaking, no crumpling and the like of a lithium battery cell in the manufacturing process, and can improve the battery capacity per unit volume (the thinner the copper foil is, the more the positive and negative electrode materials in the cell per unit volume are increased, thereby achieving the purpose of improving the battery capacity).
Claims (2)
1. The additive is prepared from a double-sided photoelectron copper foil of a negative current collector of a lithium ion energy storage battery, and is characterized in that: the high-performance polypropylene glycol and phytic acid composite material comprises polypropylene glycol, phytic acid, sodium propane sulfonate and hydroxymethyl cellulose, and the components are as follows in percentage by weight: 10-15: 2-10: 1.5-5: 120-150;
the specific use method is as follows: when in use, the additive is added into the copper sulfate electrolyte, so that the content of each component in the copper sulfate electrolyte is kept as follows: copper ion content: 90-110 g/L; sulfate radical content: 40-60 g/L; content of chloride ion: less than or equal to 3 ppm; phytic acid: 2-10 ppm; polypropylene glycol: 10-15 ppm; sodium propane sulfonate: 1.5-5 ppm; a hydroxymethyl cellulose; 120-150 ppm.
2. The additive of claim 1, wherein: 10-15g of polypropylene glycol and 1.5-5g of propane sodium sulfonate are dissolved in 500 ml of DI water, 2-10g of phytic acid and 150g of hydroxymethyl cellulose 120-one are dissolved in another 500 ml of DI water, the two mixed solutions are respectively stirred and stood at room temperature, when the two mixed solutions are added into a copper sulfate electrolyte, the two mixed solutions are mixed and stirred uniformly, and then a metering device is used for dropwise adding the mixed solution into a CuSO4 solution according to 70 ml per minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711079427.5A CN109267109B (en) | 2017-11-06 | 2017-11-06 | Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711079427.5A CN109267109B (en) | 2017-11-06 | 2017-11-06 | Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109267109A CN109267109A (en) | 2019-01-25 |
| CN109267109B true CN109267109B (en) | 2021-04-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711079427.5A Active CN109267109B (en) | 2017-11-06 | 2017-11-06 | Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof |
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| CN (1) | CN109267109B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943868B (en) * | 2019-04-19 | 2020-10-23 | 山东金盛源电子材料有限公司 | Composite additive for preparing high-tensile-strength electrolytic copper foil |
| 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 |
| CN111785975A (en) * | 2020-07-31 | 2020-10-16 | 蜂巢能源科技有限公司 | Current collector, preparation method and application thereof, cathode and lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN103834972A (en) * | 2014-02-10 | 2014-06-04 | 东莞华威铜箔科技有限公司 | Additive for 4-micrometre carrier-free electrolytic copper foil, preparation method and application thereof |
| CN106086945A (en) * | 2016-06-22 | 2016-11-09 | 安徽铜冠铜箔有限公司 | The preparation method of a kind of ultra-thin type double face photoelectron Copper Foil and prepared Copper Foil |
| CN106480479A (en) * | 2016-10-12 | 2017-03-08 | 东莞华威铜箔科技有限公司 | The preparation method of flexible additive for electrolytic copper foil, product and its application |
-
2017
- 2017-11-06 CN CN201711079427.5A patent/CN109267109B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277597A (en) * | 2011-08-12 | 2011-12-14 | 合肥铜冠国轩铜材有限公司 | Preparation of double-sided photoelectrolytic copper foil for special lithium battery |
| CN103834972A (en) * | 2014-02-10 | 2014-06-04 | 东莞华威铜箔科技有限公司 | Additive for 4-micrometre carrier-free electrolytic copper foil, preparation method and application thereof |
| CN106086945A (en) * | 2016-06-22 | 2016-11-09 | 安徽铜冠铜箔有限公司 | The preparation method of a kind of ultra-thin type double face photoelectron Copper Foil and prepared Copper Foil |
| CN106480479A (en) * | 2016-10-12 | 2017-03-08 | 东莞华威铜箔科技有限公司 | The preparation method of flexible additive for electrolytic copper foil, product and its application |
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| CN109267109A (en) | 2019-01-25 |
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