CN108425122B - Method for removing scale on surface of titanium-based oxide coating anode for electrolytic copper foil - Google Patents
Method for removing scale on surface of titanium-based oxide coating anode for electrolytic copper foil Download PDFInfo
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- CN108425122B CN108425122B CN201810246280.2A CN201810246280A CN108425122B CN 108425122 B CN108425122 B CN 108425122B CN 201810246280 A CN201810246280 A CN 201810246280A CN 108425122 B CN108425122 B CN 108425122B
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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
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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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
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention provides a method for removing scale on the surface of an anode of a titanium-based oxide coating for electrolytic copper foil, which mainly comprises the following steps: (1) placing the titanium anode with scale in a mixed solution of carbonate and acetate, fully soaking under ultrasonic stirring to loosen a scale layer, and washing away the loosened scale with water; (2) placing the titanium anode treated in the step (1) in an acetic acid or nitric acid solution, fully soaking under ultrasonic stirring, and then washing with water; (3) and (3) placing the treated titanium anode in the step (2) in DTPA or DTPA pentasodium solution, fully soaking under ultrasonic stirring, and then washing with water. The method can effectively remove the scale on the surface of the titanium anode without damaging the oxide coating on the surface of the anode, thereby solving the problems of the voltage rise of an electrolytic bath and the uneven thickness of the produced copper foil caused by the scale on the surface of the titanium anode.
Description
Technical Field
The invention relates to a method for removing scale on the surface of an anode of a titanium-based oxide coating for an electrolytic copper foil.
Background
The titanium-based oxide coating anode has excellent electrocatalytic activity and electrochemical stability, and is widely applied to the electrolytic copper foil industry. In the production of copper foil, some impurity metal ions such as Mg, Ga, Pb and the like in the electrolyte can generate metal compounds in the electrolytic process, so that the surface of a titanium anode is gradually covered with a layer of compact scale, and the energy spectrum detection result shows that the main components of the scale are lead sulfate and lead oxide. Lead sulfate is non-conductive, which not only causes the increase of tank pressure and the increase of power consumption, but also causes the uneven distribution of anode current and the uneven thickness of the produced copper foil. At present, the common methods for removing the anode scale are as follows: mechanical removal methods, acid cooking methods, alkaline cooking methods and the like, which not only have low scale removal efficiency, but also can cause great damage to the anode.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a method for removing the scale on the surface of the anode of the titanium-based oxide coating for the electrolytic copper foil, which has simple process and high removal efficiency and can cause less damage to the anode.
The technical scheme of the invention is as follows: a method for removing scale on the surface of an anode of a titanium-based oxide coating for electrolytic copper foil comprises the following steps:
placing a titanium anode with scale in a mixed solution of soluble carbonate and soluble acetate, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring to loosen a scale layer, and washing away the loosened scale with water;
step (2) placing the titanium anode treated in the step (1) in an acetic acid or nitric acid solution, soaking for 30 ~ 60min under ultrasonic stirring at the temperature of 10-30 ℃, and then washing with water;
and (3) placing the treated titanium anode in the step (2) in DTPA or DTPA pentasodium solution, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring, and then washing with water.
Further, in the step (1), the concentration of the soluble carbonate is 30 ~ 100g/L, the concentration of the soluble acetate is 50 ~ 150g/L, and the ultrasonic frequency is 20 ~ 40 kHz.
Further, the soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
Further, the soluble acetate is one or more of sodium acetate, potassium acetate and ammonium acetate.
Further, in the step (2), the mass concentration of the acetic acid or nitric acid solution is 5 ~ 30%, and the ultrasonic frequency is 20 ~ 40 kHz.
Further, in the step (3), the mass concentration of the DTPA or DTPA pentasodium solution is 5 ~ 30%, the pH value of the solution is 7 ~ 12, and the ultrasonic frequency is 20 ~ 40 kHz.
The invention has the beneficial effects that: by adopting the technical scheme, the method has simple process, adopts the mixed solution of soluble carbonate and soluble acetate to carry out pretreatment under ultrasonic wave, adopts the solution of acetic acid or nitric acid to carry out secondary treatment, and finally adopts the solution of DTPA or DTPA pentasodium to carry out treatment, so that the scaling removal efficiency is greatly improved, the damage to the anode caused by scaling removal is greatly reduced, and the method is suitable for large-scale popularization.
Detailed Description
The following further description of specific embodiments of the present invention is provided in connection with the exemplary embodiments, and is not intended to limit the invention to the exemplary embodiments described.
The invention relates to a method for removing scale on the surface of an anode of a titanium-based oxide coating for electrolytic copper foil, which comprises the following steps:
placing a titanium anode with scale in a mixed solution of soluble carbonate and soluble acetate, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring to loosen a scale layer, and washing away the loosened scale with water;
step (2) placing the titanium anode treated in the step (1) in an acetic acid or nitric acid solution, soaking for 30 ~ 60min under ultrasonic stirring at the temperature of 10-30 ℃, and then washing with water;
and (3) placing the treated titanium anode in the step (2) in DTPA or DTPA pentasodium solution, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring, and then washing with water.
In the step (1), the concentration of the soluble carbonate is 30 ~ 100g/L, the concentration of the soluble acetate is 50 ~ 150g/L, and the ultrasonic frequency is 20 ~ 40 kHz.
The soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
The soluble acetate is one or more of sodium acetate, potassium acetate and ammonium acetate.
In the step (2), the mass concentration of the acetic acid or nitric acid solution is 5 ~ 30%, and the ultrasonic frequency is 20 ~ 40 kHz.
In the step (3), the mass concentration of the DTPA or DTPA pentasodium solution is 5 ~ 30%, the pH value of the solution is 7 ~ 12, and the ultrasonic frequency is 20 ~ 40 kHz.
Example 1
Placing the titanium anode with scale in a solution of 30g/L sodium carbonate and 50g/L sodium acetate, soaking for 30min at 15 ℃, and then washing loose scale with water; placing the titanium anode treated in the step (1) in a nitric acid solution with the mass concentration of 5%, soaking for 30min at 15 ℃, and then washing with water; and (3) placing the titanium anode treated in the step (2) into an EDTA solution with the mass concentration of 10%, soaking the titanium anode in the EDTA solution at the pH value of 7 for 45min at the temperature of 15 ℃, and washing the titanium anode with water, wherein the scale is basically and completely removed.
Example 2
Placing the titanium anode with scale in a solution of 50g/L potassium carbonate and 80g/L sodium acetate, soaking for 45min at 20 ℃, and then washing loose scale with water; placing the titanium anode treated in the step (1) in an acetic acid solution with the mass concentration of 25%, soaking for 45min at 20 ℃, and then washing with water; and (3) placing the titanium anode treated in the step (2) into a pentasodium EDTA solution with the mass concentration of 20%, soaking the titanium anode in the solution at the pH value of 8 for 30min at the temperature of 20 ℃, and washing the titanium anode with water, wherein the scale is basically and completely removed.
Example 3
Placing the titanium anode with scale in a solution of 80g/L potassium carbonate and 120g/L potassium acetate, soaking for 45min at 25 ℃, and then washing loose scale with water; placing the titanium anode treated in the step (1) in a nitric acid solution with the mass concentration of 10%, soaking for 30min at 25 ℃, and then washing with water; and (3) placing the titanium anode treated in the step (2) into an EDTA solution with the mass concentration of 15%, wherein the pH value of the solution is 10, soaking for 30min at 20 ℃, and then washing with water, wherein the scale is basically and completely removed.
Claims (6)
1. A method for removing scale on the surface of an anode of a titanium-based oxide coating for electrolytic copper foil is characterized by comprising the following steps:
placing a titanium anode with scale in a mixed solution of soluble carbonate and soluble acetate, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring to loosen a scale layer, and washing away the loosened scale with water;
step (2) placing the titanium anode treated in the step (1) in an acetic acid or nitric acid solution, soaking for 30 ~ 60min under ultrasonic stirring at the temperature of 10-30 ℃, and then washing with water;
and (3) placing the treated titanium anode in the step (2) in DTPA or DTPA pentasodium solution, soaking for 30 ~ 60min at the temperature of 10-30 ℃ under ultrasonic stirring, and then washing with water.
2. The method of claim 1, wherein the concentration of the soluble carbonate in step (1) is 30 ~ 100g/L, the concentration of the soluble acetate in step (1) is 50 ~ 150g/L, and the ultrasonic frequency is 20 ~ 40 kHz.
3. The method according to claim 2, wherein the soluble carbonate is one or more of sodium carbonate, potassium carbonate and ammonium carbonate.
4. The method according to claim 2, wherein the soluble acetate is one or more of sodium acetate, potassium acetate and ammonium acetate.
5. The method as claimed in claim 1, wherein the mass concentration of the acetic acid or nitric acid solution in the step (2) is 5 ~ 30%, and the ultrasonic frequency is 20 ~ 40 kHz.
6. The method according to claim 1, wherein the mass concentration of the solution of DTPA or DTPA pentasodium in the step (3) is 5 ~ 30%, the pH value of the solution is 7 ~ 12, and the ultrasonic frequency is 20 ~ 40 kHz.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810246280.2A CN108425122B (en) | 2018-03-23 | 2018-03-23 | Method for removing scale on surface of titanium-based oxide coating anode for electrolytic copper foil |
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| CN201810246280.2A CN108425122B (en) | 2018-03-23 | 2018-03-23 | Method for removing scale on surface of titanium-based oxide coating anode for electrolytic copper foil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109023399B (en) * | 2018-08-28 | 2020-08-14 | 常州大学 | Regeneration treatment liquid of titanium anode for electrolytic copper foil, preparation method thereof and regeneration method of titanium anode |
| CN109112605B (en) * | 2018-08-28 | 2020-04-14 | 常州大学 | Regeneration treatment liquid and regeneration method of titanium-based iridium-tantalum oxide coating anode for electrolytic copper foil |
| CN110004468B (en) * | 2019-04-20 | 2021-03-23 | 山东金盛源电子材料有限公司 | Composite additive for preparing low-brittleness electrolytic copper foil |
| CN110714205B (en) * | 2019-09-16 | 2022-02-01 | 铜陵市华创新材料有限公司 | Electrolytic copper foil integrated machine anode plate descaling agent for lithium ion battery and preparation and use methods thereof |
| 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 |
| CN116254536A (en) * | 2023-02-17 | 2023-06-13 | 九江斯坦德能源工业有限公司 | Cleaning agent and cleaning method for titanium anode plate of foil producing machine |
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| KR100848286B1 (en) * | 2007-01-09 | 2008-07-25 | 한국동서발전(주) | Scale Preventer and Scale Preventing Method for Wastewater Disposal Facility in Flue Gas Desulfurization System Using Sodium Hypochlorite |
| CN104120460B (en) * | 2014-07-02 | 2016-09-21 | 广州鸿葳科技股份有限公司 | A kind of method removing electrolytic copper foil Ni-Ti anode surface scale |
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Address after: 335400 No. 15 metallurgical Avenue, Yingtan, Jiangxi, Guixi Patentee after: JIANGXI COPPER CORPORATION Ltd. Address before: 330096 No. 7666, Dong Dong Avenue, Jiangxi, Nanchang Patentee before: JIANGXI COPPER CORPORATION Ltd. |
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Effective date of registration: 20210225 Address after: 330000 No. 1129, Gaoxin Avenue, Nanchang hi tech Industrial Development Zone, Nanchang City, Jiangxi Province Patentee after: JIANGXI COPPER YATES FOIL Inc. Address before: No.15 metallurgical Avenue, Guixi City, Yingtan City, Jiangxi Province, 335400 Patentee before: JIANGXI COPPER Corp.,Ltd. |
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Address after: 330000 No. 1129, Gaoxin Avenue, Nanchang hi tech Industrial Development Zone, Nanchang City, Jiangxi Province Patentee after: Jiangxi Jiangxi Jiangxi Copper Foil Technology Co.,Ltd. Address before: 330000 No. 1129, Gaoxin Avenue, Nanchang hi tech Industrial Development Zone, Nanchang City, Jiangxi Province Patentee before: JIANGXI COPPER YATES FOIL Inc. |