CN110714205A - Electrolytic copper foil integrated machine anode plate descaling agent for lithium ion battery and preparation and use methods thereof - Google Patents
Electrolytic copper foil integrated machine anode plate descaling agent for lithium ion battery and preparation and use methods thereof Download PDFInfo
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- CN110714205A CN110714205A CN201910871991.3A CN201910871991A CN110714205A CN 110714205 A CN110714205 A CN 110714205A CN 201910871991 A CN201910871991 A CN 201910871991A CN 110714205 A CN110714205 A CN 110714205A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
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Abstract
The invention discloses an electrolytic copper foil integrated machine anode plate descaling agent for a lithium ion battery and a preparation method and a using method thereof, wherein the descaling agent comprises 50 ~ 300g/L of ammonium acetate, 10 ~ 50g/L of sodium carbonate, 0.5 ~ 5g/L of hydroxyethyl sodium sulfonate, 3 ~ 15g/L of sodium succinate, 0.2 ~ 5g/L of polyethylene imine alkyl salt, 0.3 ~ 6g/L of S-carboxyethyl isothiourea humate, 0.1 ~ 3g/L of hydroxypropyl sodium thiosulfate and 0.1 ~ 2g/L of 2-methyl-3-ethylmaleimide.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a metal surface cleaning scale remover, which is suitable for an iridium-coated tantalum coating insoluble titanium anode plate surface scale remover in the lithium electric copper foil industry and a preparation method and a use method thereof.
Background
The iridium-coated insoluble titanium anode plate of the lithium foil conjoined machine is one of particularly important parts in the lithium foil manufacturing industry, the scaling phenomenon of the anode plate of the lithium foil conjoined machine is a common fault in the whole industry, the scaling of the anode plate can cause uneven raw foil power lines, and further cause uneven surface density of a product, bubble formation, fish scale marks and other series of product quality problems, great influence is generated on the performance and safety of a downstream lithium ion battery, meanwhile, the scaling of the anode plate can also cause overhigh groove voltage of the lithium foil conjoined machine, the production power consumption is greatly increased, and the replacement of the anode plate is a consumable material with the maximum consumption in the lithium foil industry except additives.
The traditional anode plate descaling method comprises three methods: the first method is a mechanical scraping method, wherein scales on an anode plate are wiped off by using sand paper and polishing materials in a friction mode, and then the scales are washed by using pure water, so that the method is low in efficiency, high in labor intensity, not ideal in cleaning effect and seriously damaged by coating an iridium coating; the second and the third are acid bath method and alkali bath method, the two methods are to dismantle the anode plate completely, put into strong alkali and strong acid environment and heat and vibrate, the working environment of the method is bad, a large amount of acid and alkali waste can be caused, the iridium tantalum plating layer can be damaged, and the requirement of producing high-grade copper foil can not be met.
The existing lithium electro-copper foil enterprises have large raw foil current density, very complex additive decomposition products and various impurities, and are difficult to have an anode plate capable of solving the scaling of complex components.
Chinese patent publication No. CN109023399A discloses a regeneration treatment solution for titanium anode for electrolytic copper foil, a preparation method thereof, and a regeneration method for titanium anode, wherein the regeneration solution comprises alkali metal salt of acetic acid, ammonium acetate, and surfactant nonylphenol polyoxyethylene ether (NP-10). Wherein the concentration of alkali metal salt of acetic acid is 30-100g/L, the concentration of ammonium acetate is 50-150g/L, the concentration of surfactant nonylphenol polyoxyethylene ether (NP-10) is 0.01-0.5g/L, the regenerant still needs to completely remove the anode plate, the titanium anode is washed by deionized water and then placed in a regeneration treatment solution, and the titanium anode is soaked for 10-60 minutes under the condition of ultrasonic vibration at the temperature of 20-60 ℃. The regenerant cannot dissolve a complex additive decomposer system caused by ultrahigh current density, so that online treatment cannot be realized, and the regenerated liquid and the lithium battery foil are required to be separated by a combined machine.
Disclosure of Invention
The invention aims to solve the technical problems that the existing anode plate descaling agent has poor descaling effect or cannot be processed on line, and provides the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery and the preparation and use methods thereof.
The technical scheme is that the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises 50 ~ 300g/L of ammonium acetate, 10 ~ 50g/L of sodium carbonate, 0.5 ~ 5g/L of hydroxyethyl sodium sulfonate, 3 ~ 15g/L of sodium succinate, 0.2 ~ 5g/L of polyethylene imine alkyl salt, 0.3 ~ 6g/L of S-carboxyethyl isothiourea salt, 0.1 ~ 3g/L of hydroxypropyl sodium thiosulfate and 0.1 ~ 2g/L of 2-methyl-3-ethyl maleimide.
The preparation method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps of uniformly mixing 50 g/L50 ~ 300g/L ammonium acetate, 10 g/L10 ~ 50g/L sodium carbonate, 0.5 g/L0.5 ~ 5g/L hydroxyethyl sodium sulfonate, 3 g/L3 ~ 15g/L sodium succinate, 0.2 g/L0.2 ~ 5g/L polyethyleneimine alkyl salt, 0.3 g/L0.3 ~ 6g/L S-carboxyethyl isothiourea humate, 0.1 g/L0.1 ~ 3g/L hydroxypropyl sodium thiosulfate and 0.1 g/L0.1 ~ 2 g/L2-methyl-3-ethyl maleimide, and then adding water and uniformly stirring for 1 ~ 3 min.
The use method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps: the descaling agent is placed in a spray pot to continuously spray the surface of the anode plate for a plurality of times, each time lasts for a plurality of seconds, and then the anode plate is wiped to be scaled by using a rag.
The other using method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps: the descaling agent is placed in an open container, and the anode plate is dipped by a towel to wipe the scale formation of the anode plate.
The method has the beneficial effects that the ammonium acetate and the sodium carbonate can effectively remove the scale of lead sulfate, lead oxide and lead dioxide outside the iridium tantalum coating; sodium isethionate, sodium succinate (sodium succinate), polyethylene imine alkyl salt, S-carboxyethyl isothiourea humate and sodium hydroxypropyl thiosulfate can greatly improve the wetting and cleaning effect, can effectively dissolve a complex additive decomposition system caused by ultrahigh current density, and can realize online treatment; the ethylene imine alkyl salt and the 2-methyl-3-ethyl maleimide can not only increase the cleaning effect, but also have a certain fresh scent.
Drawings
FIG. 1 is a photograph of an electrolytic copper foil integrated machine anode plate for a lithium ion battery before cleaning;
FIG. 2 is a photograph of an anode plate of the electrolytic copper foil integrated machine for a lithium ion battery after cleaning.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments based on the embodiments in the present invention, without any inventive work, will be apparent to those skilled in the art from the following description.
As shown in fig. 1, the electrolytic copper foil integrated anode plate for lithium ion battery before cleaning.
As shown in fig. 2, the anode plate of the lithium ion battery with the electrolytic copper foil connector after cleaning.
Example 1:
an electrolytic copper foil integrated machine anode plate descaling agent for a lithium ion battery comprises the following components:
250g/L of ammonium acetate, 10g/L of sodium carbonate, 3g/L of hydroxyethyl sodium sulfonate, 5g/L of sodium succinate, 0.5g/L of polyethyleneimine alkyl salt, 0.5g/L of S-carboxyethyl isothiouronium salt, 2g/L of hydroxypropyl sodium thiosulfate and 2g/L of 2-methyl-3-ethylmaleimide.
The preparation method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps of uniformly mixing 250g/L of ammonium acetate, 10g/L of sodium carbonate, 3g/L of hydroxyethyl sodium sulfonate, 5g/L of sodium succinate, 0.5g/L of polyethyleneimine alkyl salt, 0.5g/L of S-carboxyethyl isothiourea humate, 2g/L of hydroxypropyl sodium thiosulfate and 2g/L of 2-methyl-3-ethyl maleimide, and then adding water and uniformly stirring for 1 ~ 3 min.
The anode plate scaling thickness is 0.5mm, the scale remover is sprayed by a spray can for 20 times continuously, each time lasts for 10 seconds, and then the anode plate is wiped by a rag to scale, so that the scale removal rate is over 90 percent.
Example 2:
an electrolytic copper foil integrated machine anode plate descaling agent for a lithium ion battery comprises the following components:
300g/L of ammonium acetate, 50g/L of sodium carbonate, 5g/L of hydroxyethyl sodium sulfonate, 3g/L of sodium succinate, 0.2g/L of polyethyleneimine alkyl salt, 0.3g/L of S-carboxyethyl isothiouronium salt, 3g/L of hydroxypropyl sodium thiosulfate and 1g/L of 2-methyl-3-ethylmaleimide.
The preparation method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps of uniformly mixing 300g/L of ammonium acetate, 50g/L of sodium carbonate, 5g/L of hydroxyethyl sodium sulfonate, 3g/L of sodium succinate, 0.2g/L of polyethyleneimine alkyl salt, 0.3g/L of S-carboxyethyl isothiourea humate, 3g/L of hydroxypropyl sodium thiosulfate and 1g/L of 2-methyl-3-ethyl maleimide, and then adding water and uniformly stirring for 1 ~ 3 min.
The anode plate scaling thickness is 0.3mm, a descaling agent is prepared by using a beaker, the anode plate is wiped by using a towel for descaling, and the descaling rate is more than 98% after half an hour.
Example 3:
an electrolytic copper foil integrated machine anode plate descaling agent for a lithium ion battery comprises the following components:
50g/L of ammonium acetate, 15g/L of sodium carbonate, 0.5g/L of hydroxyethyl sodium sulfonate, 15g/L of sodium succinate, 5g/L of polyethyleneimine alkyl salt, 6g/L of S-carboxyethyl isothiourea humate, 0.1g/L of hydroxypropyl sodium thiosulfate and 0.1g/L of 2-methyl-3-ethylmaleimide.
The preparation method of the electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery comprises the following steps of uniformly mixing 50g/L of ammonium acetate, 15g/L of sodium carbonate, 0.5g/L of hydroxyethyl sodium sulfonate, 15g/L of sodium succinate, 5g/L of polyethyleneimine alkyl salt, 6g/L of S-carboxyethyl isothiourea humate, 0.1g/L of hydroxypropyl sodium thiosulfate and 0.1g/L of 2-methyl-3-ethyl maleimide, and then adding water and uniformly stirring for 1 ~ 3 min.
The anode plate scaling thickness is 0.2mm, a descaling agent is prepared by using a beaker, the anode plate is wiped by using a towel for descaling, and the descaling rate is over 95 percent after half an hour.
The polyethyleneimine alkyl salt is a cationic surfactant, mainly is a nitrogenous organic amine derivative, and can be combined with hydrogen in acid molecules by hydrogen bonds to make amino carry positive charges because nitrogen atoms in molecules of the polyethyleneimine alkyl salt contain lone-pair electrons. Therefore, they have good surface activity in acidic media;
s-carboxyethyl isothiouronium salt is easy to adsorb on the titanium surface, from the view of electronic arrangement, 3P electrons of sulfur atoms and 3d orbitals of titanium atoms are easy to form S-Ti feedback delta bonds, the strong electronegativity of S can attract surrounding electrons, the electronegativity of nearby points is changed, the adsorption energy of acetate on the titanium surface is reduced, the acetate is easy to adsorb, and the cleaning effect is improved.
Hydroxypropyl sodium thiosulfate: s2O3 2- +Pb(Ac)2+ H2O=PbS + 2HAc+SO42-The sodium thiosulfate radical reacts with lead ions to form lead sulfide suspension.
The complex additive decomposer mainly comprises amino acid, micromolecular polypeptide, a small amount of ethanolamine, 1, 3-propane sultone, polyethyleneimine alkyl salt, S-carboxyethyl isothiouronium salt and additive decomposition products which are similar and compatible, so that online cleaning is realized.
Claims (4)
1. The electrolytic copper foil integrated machine anode plate descaling agent for the lithium ion battery is characterized by comprising 50 ~ 300g/L of ammonium acetate, 10 ~ 50g/L of sodium carbonate, 0.5 ~ 5g/L of hydroxyethyl sodium sulfonate, 3 ~ 15g/L of sodium succinate, 0.2 ~ 5g/L of polyethylene imine alkyl salt, 0.3 ~ 6g/L of S-carboxyethyl isothiourea humate, 0.1 ~ 3g/L of hydroxypropyl sodium thiosulfate and 0.1 ~ 2g/L of 2-methyl-3-ethylmaleimide.
2. The preparation method of the descaling agent for the anode plate of the electrolytic copper foil integrated machine for the lithium ion battery according to claim 1 is characterized by comprising the following steps of uniformly mixing 50 g/L50 ~ 300g/L of ammonium acetate, 10 g/L10 ~ 50g/L of sodium carbonate, 0.5 g/L0.5 ~ 5g/L of sodium isethionate, 3 g/L3 ~ 15g/L of sodium succinate, 0.2 g/L0.2 ~ 5g/L of polyethyleneimine alkyl salt, 0.3 g/L0.3 ~ 6g/L of S-carboxyethyl isothiourea humate, 0.1 g/L0.1 ~ 3g/L of hydroxypropyl sodium thiosulfate and 0.1 g/L0.1 ~ 2g/L of 2-methyl-3-ethylmaleimide, and then adding water and uniformly stirring for 1 ~ 3 min.
3. The use method of the electrolytic copper foil integrated machine anode plate descaling agent for lithium ion batteries according to claim 1 is characterized in that: it comprises the following steps: the descaling agent is placed in a spray pot to continuously spray the surface of the anode plate for a plurality of times, each time lasts for a plurality of seconds, and then the anode plate is wiped to be scaled by using a rag.
4. The use method of the electrolytic copper foil integrated machine anode plate descaling agent for lithium ion batteries according to claim 1 is characterized in that: it comprises the following steps: the descaling agent is placed in an open container, and the anode plate is dipped by a towel to wipe the scale formation of the anode plate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111349961A (en) * | 2020-04-29 | 2020-06-30 | 宝鸡市昌立特种金属有限公司 | Method for cleaning waste titanium anode plate for foil forming machine and removing and recycling precious metal |
| CN112011799A (en) * | 2020-08-18 | 2020-12-01 | 九江德福科技股份有限公司 | Additive for cleaning titanium anode plate of electrolytic cell and cleaning method |
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Application publication date: 20200121 Assignee: Guangxi Huachuang New Material Copper Foil Co.,Ltd. Assignor: Anhui Huachuang New Material Co.,Ltd. Contract record no.: X2023980038902 Denomination of invention: Electrolytic copper foil joint machine anode plate descaling agent for lithium-ion batteries and its preparation and use method Granted publication date: 20220201 License type: Common License Record date: 20230804 Application publication date: 20200121 Assignee: Guangxi Shidai Chuanneng New Material Technology Co.,Ltd. Assignor: Anhui Huachuang New Material Co.,Ltd. Contract record no.: X2023980038903 Denomination of invention: Electrolytic copper foil joint machine anode plate descaling agent for lithium-ion batteries and its preparation and use method Granted publication date: 20220201 License type: Common License Record date: 20230804 |
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