CN109943868B - Composite additive for preparing high-tensile-strength electrolytic copper foil - Google Patents
Composite additive for preparing high-tensile-strength electrolytic copper foil Download PDFInfo
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- CN109943868B CN109943868B CN201910318197.6A CN201910318197A CN109943868B CN 109943868 B CN109943868 B CN 109943868B CN 201910318197 A CN201910318197 A CN 201910318197A CN 109943868 B CN109943868 B CN 109943868B
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- copper foil
- tensile strength
- electrolytic copper
- additive
- modified cellulose
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011889 copper foil Substances 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 title claims abstract description 31
- 230000000996 additive effect Effects 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 239000001913 cellulose Substances 0.000 claims abstract description 13
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 10
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 6
- 235000010489 acacia gum Nutrition 0.000 claims description 6
- 239000001785 acacia senegal l. willd gum Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- 229940057995 liquid paraffin Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XDOJOKWCSKACQT-UHFFFAOYSA-M CCSSCCCOC([O-])=O.[K+] Chemical compound CCSSCCCOC([O-])=O.[K+] XDOJOKWCSKACQT-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a composite additive for preparing an electrolytic copper foil with high tensile strength, and belongs to the technical field of electrolytic copper foil production. The technical proposal is that each liter of additive solution contains: 20-30mg of modified cellulose, 1-4mg of titanium sulfate, 2-7mg of potassium ethyl dithio propyl carbonate sulfonate and 5-15mg of polypropylene glycol. The hydroxyethyl cellulose is modified to be used as an additive of the electrolytic copper foil, and the prepared copper foil has the advantages of high tensile strength, low double-sided roughness, high elongation and uniform thickness. The tensile strength at normal temperature is greater than or equal to 860MPa, and the tensile strength at 180 ℃ is greater than or equal to 300 MPa.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil production, and particularly relates to a composite additive for preparing electrolytic copper foil with high tensile strength.
Background
Compared with high-performance alkaline batteries, rechargeable nickel-insulated batteries and nickel-hydrogen batteries, lithium ion batteries have recently become the first choice of power sources for a plurality of portable electronic products due to the advantages of high specific energy, high working voltage, no memory effect, long cycle life, no pollution, small volume, light weight, self-discharge and the like. The copper foil is used as a key raw material for manufacturing the lithium ion battery, and the development of the production technology and the quality of the copper foil directly influence the manufacturing process, the performance, the production cost and the like of the lithium ion battery. Although the production level of copper foil in China is greatly improved from the end of the 90 s to the beginning of the 21 st century in the 20 th century, compared with developed countries, the production technology and manufacturing equipment still have great gaps, and high-performance electrolytic copper foil with zero appearance defect, low surface roughness, high strength, good ductility and the like is far from meeting the requirements of domestic users. The demand for high-performance electrolytic copper foil is increasing after more than ten years of research and development of new energy pure electric vehicles in China, as the endurance and the power performance of the electric vehicles are not completely solved, and the power and the capacity of power batteries of the electric vehicles directly restrict the endurance of the electric vehicles. The copper foil is used as a negative electrode material of the automobile power battery, if the tensile property of the copper foil is not high enough or the surface density is not uniform, the pole piece of the power battery is cracked, and the power and the capacity of the battery are greatly reduced; therefore, the tensile properties and surface uniformity of the copper foil require certain requirements. The electrolytic copper foil in the prior art has low tensile property and elongation, and the pole piece can not bear rapid charge and discharge and is easy to crack; the copper foil has a rough surface and a small contact area with the negative electrode active material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the composite additive for the production of the electrolytic copper foil, which can obviously improve the tensile strength of the electrolytic copper foil.
In order to solve the technical problems, the invention is realized by the following technical scheme: a composite additive for preparing high tensile strength electrolytic copper foil, each liter of additive solution comprises: 20-30mg of modified cellulose and 1-4mg of titanium sulfate; 2-7mg of potassium ethyl dithio-propyl carbonate sulfonate and 5-15mg of polypropylene glycol.
Further, each liter of additive solution contains: 25mg of modified cellulose, 3mg of titanium sulfate; 5mg of potassium ethyldithio-propyl carbonate sulfonate and 10mg of polypropylene glycol.
The preparation method of the modified cellulose comprises the following steps: weighing equal amount of Arabic gum and gelatin, respectively preparing into solution with certain concentration by using distilled water, stirring and mixing the two solutions uniformly, dissolving three fifths of hydroxyethyl cellulose of the total weight of the Arabic gum and the gelatin in the solution to obtain uniform single-phase sol, adding the sol into liquid paraffin, wherein the amount of the liquid paraffin is 18 times of the total amount of the colloid, shearing and mixing the mixed solution at high speed by using a high-shear mixing emulsifying machine at the temperature of 50-70 ℃ and at the rotating speed of 8000n/min to form W/O emulsion, filtering, washing a filter cake by using a small amount of water, draining, and drying at 70 ℃ to obtain the modified cellulose.
Taking the electrolyte with the copper content of 85g/L, the sulfuric acid content of 100g/L, the chloride ion content of 25ppm and the temperature of 50 ℃, and then adding the composite additive into the electrolyte to ensure that the flow of the electrolyte is 50m3H, current density 7000A/m2Under the parameters ofAnd performing electrodeposition.
In view of the limitations of hydroxyethyl cellulose in acid and alkali resistance, oxidation resistance, reducing agent, etc., hydroxyethyl cellulose cannot be used satisfactorily in many environments where it is oxidized, reduced, or contains additives such as antioxidants. The method comprises the steps of modifying hydroxyethyl cellulose by taking Arabic gum and gelatin as modifying materials, mixing the hydroxyethyl cellulose with solutions of the gelatin and the Arabic gum in the same amount, and preparing emulsion in liquid paraffin so as to slowly release the surface activity effects of the two substances.
The invention has the beneficial effects that: the hydroxyethyl cellulose is modified, and the hydroxyethyl cellulose is not reported as a raw material of an electrolytic copper foil additive, and particularly, the hydroxyethyl cellulose is modified to improve the tensile strength of the electrolytic copper foil. The copper foil prepared by the additive has the advantages of high tensile strength, low double-sided roughness, high elongation and uniform thickness. The tensile strength at normal temperature is greater than or equal to 860MPa, and the tensile strength at 180 ℃ is greater than or equal to 300 MPa.
To further verify that the tensile strength of the electrolytic copper foil prepared using the additive of the present invention is greater than that of the electrolytic copper foil prepared using the conventional additive, the inventors conducted the following tests at the present company.
Test groups: the electrolytic copper foil prepared by the additive of the invention is used for tensile strength test, namely the additive comprises the following components: 25mg of modified cellulose, 3mg of titanium sulfate; 5mg of potassium ethyldithio-propyl carbonate sulfonate and 10mg of polypropylene glycol.
Control group: the electrolytic copper foil prepared by adopting the conventional additive is used for tensile strength test, namely the additive comprises the following components: 25mg of cellulose, 3mg of titanium sulfate; 5mg of potassium ethyldithio-propyl carbonate sulfonate and 10mg of polypropylene glycol. The two groups of electrolytic copper foils have the same production process except that the components of the additives are different.
The tensile strength test adopts a universal testing machine, the copper foil of the sample to be tested is required to have no folds, and wavy edges, burrs and gaps can not appear when the sample is cut by a knife-carving method. When the normal temperature tensile strength is tested, the copper foil sample is directly clamped between an upper clamp and a lower clamp of a universal testing machine at normal temperature to test the tensile strength.
Tensile strength at 180 ℃: after the temperature of a high-temperature oven of the universal testing machine is increased to 180 ℃, opening the oven door of the oven to clamp the copper foil sample between an upper clamp and a lower clamp, keeping the sample vertical to the plane of the clamps, starting the clamps to clamp the sample, and closing the oven door; starting the universal testing machine to start the test: and starting timing after the temperature of the high-temperature oven rises to 180 ℃, and starting the universal testing machine to start testing after 5 minutes. The test proves that the tensile strength of the test group at normal temperature is 860MPa, and the tensile strength at 180 ℃ is more than or equal to 300 MPa. The tensile strength of the control group at normal temperature is 520MPa, and the tensile strength at 180 ℃ is more than or equal to 210 MPa.
Detailed Description
The first embodiment is as follows: the composite additive for preparing the electrolytic copper foil with high tensile strength contains the following components in each liter of additive solution: 20mg of modified cellulose, 4mg of titanium sulfate; 2mg of potassium ethyldithio-propyl carbonate sulfonate and 15mg of polypropylene glycol. Taking the electrolyte with the copper content of 85g/L, the sulfuric acid content of 100g/L, the chloride ion content of 25ppm and the temperature of 50 ℃, and then adding the composite additive into the electrolyte to ensure that the flow of the electrolyte is 50m3H, current density 7000A/m2Electrodeposition was carried out under the parameters of (1). The test shows that the tensile strength of the produced electrolytic copper foil at normal temperature is 810Mpa, and the tensile strength at 180 ℃ is more than or equal to 285 Mpa.
Example two: the composite additive for preparing the electrolytic copper foil with high tensile strength contains the following components in each liter of additive solution: 25mg of modified cellulose, 3mg of titanium sulfate, 5mg of potassium ethyldithio-propyl carbonate sulfonate and 10mg of polypropylene glycol. Taking the electrolyte with the copper content of 85g/L, the sulfuric acid content of 100g/L, the chloride ion content of 25ppm and the temperature of 50 ℃, and then adding the composite additive into the electrolyte to ensure that the flow of the electrolyte is 50m3H, current density 7000A/m2Electrodeposition was carried out under the parameters of (1). The test shows that the tensile strength of the produced electrolytic copper foil at normal temperature is 855Mpa, and the tensile strength at 180 ℃ is more than or equal to 310 Mpa.
Example three: the composite additive for preparing the electrolytic copper foil with high tensile strength is one liter of additiveThe solution contains: 30mg of modified cellulose, 1mg of titanium sulfate; 7mg of potassium ethyldithio-propyl carbonate sulfonate and 5mg of polypropylene glycol. Taking the electrolyte with the copper content of 85g/L, the sulfuric acid content of 100g/L, the chloride ion content of 25ppm and the temperature of 50 ℃, and then adding the composite additive into the electrolyte to ensure that the flow of the electrolyte is 50m3H, current density 7000A/m2Electrodeposition was carried out under the parameters of (1). The test shows that the tensile strength of the produced electrolytic copper foil at normal temperature is 790Mpa, and the tensile strength at 180 ℃ is more than or equal to 260 Mpa.
Claims (1)
1. A composite additive for preparing high tensile strength electrolytic copper foil, each liter of additive solution comprises: 20-30mg of modified cellulose, 1-4mg of titanium sulfate, 2-7mg of potassium ethyl dithio propyl carbonate sulfonate and 5-15mg of polypropylene glycol, and is characterized in that the preparation method of the modified cellulose comprises the following steps: weighing equal amount of Arabic gum and gelatin, respectively preparing into solution with certain concentration by using distilled water, stirring and mixing the two solutions uniformly, dissolving three fifths of hydroxyethyl cellulose of the total weight of the Arabic gum and the gelatin in the solution to obtain uniform single-phase sol, adding the sol into liquid paraffin, wherein the amount of the liquid paraffin is 18 times of the total amount of the colloid, shearing and mixing the mixed solution at high speed by using a high-shear mixing emulsifying machine at the temperature of 50-70 ℃ and at the rotating speed of 8000n/min to form W/O emulsion, filtering, washing a filter cake by using a small amount of water, draining, and drying at 70 ℃ to obtain the modified cellulose.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910318197.6A CN109943868B (en) | 2019-04-19 | 2019-04-19 | Composite additive for preparing high-tensile-strength electrolytic copper foil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910318197.6A CN109943868B (en) | 2019-04-19 | 2019-04-19 | Composite additive for preparing high-tensile-strength electrolytic copper foil |
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| Publication Number | Publication Date |
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| CN109943868A CN109943868A (en) | 2019-06-28 |
| CN109943868B true CN109943868B (en) | 2020-10-23 |
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| CN110699715A (en) * | 2019-10-21 | 2020-01-17 | 湖北中科铜箔科技有限公司 | Composite additive composition for preparing electrolytic copper foil and preparation method thereof |
| CN113046797A (en) * | 2021-03-10 | 2021-06-29 | 四川恒创博联科技有限责任公司 | Electrolytic copper foil additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702361B (en) * | 2012-05-19 | 2014-03-19 | 吉林大学 | Esterification modification method of microcrystalline cellulose |
| CN103866354B (en) * | 2014-03-07 | 2016-06-01 | 东莞华威铜箔科技有限公司 | Flexible PCB electrolytic copper foil additive, preparation method and application thereof |
| KR102218889B1 (en) * | 2016-06-14 | 2021-02-22 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper foil, lithium ion secondary cell negative electrode, lithium ion secondary cell, and printed wiring board |
| CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔（连州）铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
| CN109267109B (en) * | 2017-11-06 | 2021-04-06 | 贵州中鼎高精铜箔制造有限公司 | Additive for manufacturing double-sided photoelectron copper foil of negative current collector of lithium ion energy storage battery and using method thereof |
| CN108677223A (en) * | 2018-06-21 | 2018-10-19 | 广东嘉元科技股份有限公司 | A kind of manufacturing method of the super book electrolytic copper foil of new energy resource power battery |
| CN109183081B (en) * | 2018-08-24 | 2020-03-31 | 邵武永太高新材料有限公司 | Additive for electrolytic copper foil and preparation method of double-sided photoelectrolytic copper foil |
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Denomination of invention: Composite additive for preparing electrolytic copper foil with high tensile strength Effective date of registration: 20211018 Granted publication date: 20201023 Pledgee: Shandong Shengmu Tourism Development Co.,Ltd. Pledgor: SHANDONG JINSHENGYUAN ELECTRONIC MATERIAL Co.,Ltd. Registration number: Y2021980010790 |
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Granted publication date: 20201023 Pledgee: Shandong Shengmu Tourism Development Co.,Ltd. Pledgor: SHANDONG JINSHENGYUAN ELECTRONIC MATERIAL CO.,LTD. Registration number: Y2021980010790 |