CN113161150A - Preparation method of anode foil composite film of aluminum electrolytic capacitor - Google Patents
Preparation method of anode foil composite film of aluminum electrolytic capacitor Download PDFInfo
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- CN113161150A CN113161150A CN202110435491.2A CN202110435491A CN113161150A CN 113161150 A CN113161150 A CN 113161150A CN 202110435491 A CN202110435491 A CN 202110435491A CN 113161150 A CN113161150 A CN 113161150A
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- gel
- composite film
- electrolytic capacitor
- anode foil
- aluminum electrolytic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
Abstract
A preparation method of an anode foil composite film of an aluminum electrolytic capacitor comprises the following steps of 1) gel preparation, namely, uniformly mixing butyl titanate and water according to a molar ratio of 1:8-1:12, and then adding a solvent for uniform mixing to obtain gel; the solvent comprises one or more of glacial acetic acid, ethanol, ethylene glycol monomethyl ether or isopropanol; 2) dipping the sintered aluminum foil in the gel obtained in the step 1) for 2-5min, and taking out to uniformly coat the gel; then drying at 80-120 ℃ for 10-20min, and sintering at 500-540 ℃ for 5-15 min; 3) and (4) formation. In the invention, butyl titanate is used as a raw material to prepare gel, the gel is uniformly coated on a sintered aluminum foil and then hydrolyzed to form a continuous and uniform gel film, and then the gel film is sintered at high temperature to form Al on the sintered aluminum foil2O3‑TiO2A composite film having a high dielectric constant characteristic and thus an improved specific volume of an anode foil.
Description
Technical Field
The invention relates to an anode foil of an aluminum electrolytic capacitor, in particular to a preparation method of a composite foil on the anode foil of the aluminum electrolytic capacitor by adopting a sintered aluminum foil.
Background
The anode foil adopted by the traditional aluminum electrolytic capacitor needs a large amount of strong acid for corrosion, which causes a plurality of environmental problems, and particularly has higher requirements on the optical foil material for high-voltage corrosion foil, and is easy to cause over-corrosion, thereby reducing the mechanical property of the aluminum foil. In order to improve these problems and further increase the capacitance, japanese companies have first proposed to prepare a powder sintered anode foil with a high specific surface by sintering aluminum powder on a plain foil in a layered manner. However, the method has a limit in increasing the specific surface area of the aluminum foil under a certain thickness condition, thereby increasing the capacitance. Therefore, on the basis of the sintered foil, Al can be replaced by a composite film with high dielectric constant2O3And the specific volume of the aluminum electrolytic capacitor can be greatly improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an anode foil composite film of an aluminum electrolytic capacitor.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing an anode foil composite film of an aluminum electrolytic capacitor comprises the following steps,
1) preparing gel, namely uniformly mixing butyl titanate and water according to the molar ratio of 1:8-1:12, and then adding a solvent with the molar ratio of 1:17-1:25 to the butyl titanate for uniformly mixing to obtain gel; the solvent comprises one or more of glacial acetic acid, ethanol, ethylene glycol monomethyl ether or isopropanol;
2) dipping the sintered aluminum foil in the gel obtained in the step 1) for 2-5min, and taking out to uniformly coat the gel; then drying at 80-120 ℃ for 10-20min, and sintering at 500-540 ℃ for 5-15 min;
3) and (4) formation.
Preferably, the preparation method of the anode foil composite film for the aluminum electrolytic capacitor repeats the step 2) for 1 to 5 times.
Preferably, the chelating agent with the molar ratio of 1:0.7-1:1.2 to the butyl titanate is added into the gel prepared in the step 1) and then is uniformly stirred; the chelating agent comprises one or more of acetylacetone, EDTA, sodium potassium tartrate or ammonium citrate.
In the above method for preparing the anode foil composite film for the aluminum electrolytic capacitor, preferably, the chelating agent is added, and then the stabilizing agent is added to adjust the pH value to 0.1-1, wherein the stabilizing agent comprises one or more of nitric acid, citric acid or adipic acid.
In the above method for preparing the anode foil composite film for the aluminum electrolytic capacitor, preferably, the thickness of the gel coated on the sintered aluminum foil in the step 2) is 200-600 nm.
Compared with the prior art, the invention has the advantages that: in the invention, butyl titanate is used as a raw material to prepare gel, the gel is uniformly coated on a sintered aluminum foil and then hydrolyzed to form a continuous and uniform gel film, and then the gel film is sintered at high temperature to form Al on the sintered aluminum foil2O3-TiO2A composite film having a high dielectric constant characteristic and thus an improved specific volume of an anode foil.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Example 1
A preparation method of an anode foil composite film of an aluminum electrolytic capacitor comprises the following steps;
1) preparing a sintered aluminum foil, wherein the principle of the sintered aluminum is that aluminum powder is actually placed on a substrate aluminum foil to be sintered, and the sintered aluminum foil is close to the melting point of aluminum, namely 660 ℃; the aluminum powder is not completely melted, so that the aluminum powder is adhered to the aluminum foil, and a porous structure is formed on the surface of the aluminum foil. In the present invention, the base aluminum foil is a plain foil, that is, an aluminum foil having no oxide film formed on the surface thereof.
In the embodiment, aluminum powder, NMP and PVDF are put into a container according to the mass ratio of 50:30:1, and are stirred and mixed uniformly in vacuum; NMP as solvent and PVDF as binder. Then coating and sintering the aluminum powder slurry: coating the uniformly mixed slurry on an aluminum foil, curing and sintering to obtain a sintered foil; the temperature during sintering can be between 640 ℃ and 659 ℃, and the time is controlled within 5 min.
The method for manufacturing the sintered aluminum foil of the present example can also be manufactured by the method of the following patent. The patent numbers are: 2008801287834, the patent names: an electrode material for an aluminum electrolytic capacitor and a method of manufacturing the electrode material.
2) Preparing gel, namely uniformly mixing butyl titanate and water according to the molar ratio of 1:10, wherein the chemical formula of the butyl titanate is as follows: butyl titanate; then adding a solvent, and uniformly mixing, wherein the molar ratio of the solvent to the butyl titanate is 1:20, so as to obtain the gel. In this example, the solvent is glacial acetic acid and has the chemical formula C2H4O2(ii) a Adding a chelating agent, and uniformly stirring, wherein the molar ratio of the chelating agent to the butyl titanate is 1: 1; adding chelating agent and stabilizer to regulate pH value to 0.5. In this example, the chelating agent is acetylacetone and has the chemical formula C5H8O2The stabilizer is adipic acid with a chemical formula of C2H4O2. In this example, Ti (OC)4H9)4：C5H8O2:C2H4O2Where the ratio is a molar ratio, 1:1: 20.
Butyl titanate is extremely easy to hydrolyze, and acetylacetone is added into the solution as a chelating agent to control the hydrolysis rate of the butyl titanate. The enol group of acetylacetone is easier to generate chelating reaction with butyl titanate than OH-generated by water, so that hydrolysis of butyl titanate is prevented, and hydrolysis reaction of alkoxy in butyl titanate substituted by OH-in water is slowed down. Hydrolysis of the butyl titanate will further condense, slowly forming a sol, and will remain stable for a longer period of time. In addition to controlling the hydrolysis rate of butyl titanate, acetylacetone can also control the gelation time of the sol and the size of the colloidal particles.
By adding a certain amount of inorganic acid into the sol system, hydrolysis can be inhibited, colloidal ions are positively charged, and agglomeration of colloidal groups is prevented. Adding a proper amount of water into the sol system can promote the hydrolysis of the butyl titanate to form a continuous and uniform film. However, too much water can cause TiO2The gel time of the sol is greatly reduced, which reduces TiO2The surface area and pore volume of the film sometimes also hydrolyze rapidly to form precipitates. If the water content in the sol is too low, a discontinuous film is formed.
3) Dipping the sintered aluminum foil in the gel obtained in the step 1) for 2-5min, and taking out to uniformly coat the gel; the thickness of the gel coated on the sintered aluminum foil is 300 nm; then drying at 80-120 ℃ for 10-20min, and sintering at 500-540 ℃ for 5-15 min;
the high-temperature heat treatment is the key for ensuring the generation of the valve metal composite aluminum oxide film, and the titanium-containing material can not be completely decomposed into TiO at the low temperature2The holes of the surface film layer are increased when the temperature is too high, and the electrolyte reacts with the direct aluminum foil to cause the TiO composite film2The content is reduced. The above process may be repeated 1-5 times in order to obtain a film of suitable thickness.
4) And (4) formation.
The compound prepared in this example has Al2O3-TiO2The specific volume of the aluminum foil of the composite film under 520V can reach 1.077 mu F/cm2(ii) a Only Al is used than the prior2O3The height of the aluminum foil is 16-23%.
In this example, in order to obtain more dense Al2O3-TiO2The composite film can be electrodeposited with the aluminum foil obtained in step 3). The electrodeposition step is as follows, with Ti (SO)4)2As a starting material, with H2O2Preparing peroxide of titanium at a molar ratio of 1: 1-1: 3, adding a solvent such as a mixed solution of methanol (or ethanol) and water (volume ratio of 1: 5-1: 10) or a dimethylformamide solution, and adjusting Ti (SO)4)2The concentration of the solution is 0.005-0.02 mol/L.
The hydrogen peroxide ions generated by hydrogen peroxide ionization have the function of inhibiting the hydrolysis of titanium ions, and the cathodic electrodeposition rate in an aqueous solution system is reduced along with the increase of the hydrogen peroxide concentration.
The methanol has the function of adsorbing free water in the solution, and the function reduces the amount of adsorbed water in the deposited film, thereby being capable of well reducing the cracking and porosity of the film during drying. Meanwhile, the addition of methanol or ethanol into water reduces the dielectric constant of a solution system, reduces the solubility of sediments and improves the cathode electrodeposition rate; the reduction of the dielectric constant of the solution system also reduces the thickness of an electric double layer near an electrode, and promotes the coagulation of particles.
Water is an important substance for realizing cathodic electrodeposition, and in the electrodeposition process, water obtains electrons near a cathode to generate OH-The pH value near the cathode is increased to hydrolyze the peroxide complex of titanium and condense the peroxide complex to form a thin film on the surface of the cathode.
The current density is 1-3mA/cm2. Although the deposition speed of the high-current density film is high, a large amount of gas is generated at the cathode, so that the porosity of the deposited film is increased, and the performance of the film is damaged; the low current density is advantageous for producing films with good continuity and adhesion. And (4) electrodepositing for 10-50 s. Short deposition time and insufficient deposition time can generate concentration polarization at the cathode, so that excessive electrons are obtained by water, a large number of bubbles are released, and the deposited film is not tightly combined with an aluminum matrix.
In fact, in this embodiment, Al can be formed on the base aluminum foil directly by electrodeposition2O3-TiO2Composite films, i.e. directly using the matrix aluminium foil on Ti (SO) without the need for gel sintering4)2Carrying out electrodeposition in the solution; after electrodeposition, the mixture is cleaned and dried, and is subjected to high-temperature heat treatment at 350-500 ℃ for 2-10min in a tubular furnace. However, this method requires much electric energy and is not suitable for mass production, and Al is formed on the substrate aluminum foil by electrodeposition directly2O3-TiO2When the film is formed, Ti (SO)4)2The concentration of the solution can be 0.03-0.06 mol/L; the current density can be 2-6mA/cm2(ii) a The time may be 40-120 s.
Claims (5)
1. A preparation method of an anode foil composite film of an aluminum electrolytic capacitor is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
1) preparing gel, namely uniformly mixing butyl titanate and water according to the molar ratio of 1:8-1:12, and then adding a solvent with the molar ratio of 1:17-1:25 to the butyl titanate for uniformly mixing to obtain gel; the solvent comprises one or more of glacial acetic acid, ethanol, ethylene glycol monomethyl ether or isopropanol;
2) dipping the sintered aluminum foil in the gel obtained in the step 1) for 2-5min, and taking out to uniformly coat the gel; then drying at 80-120 ℃ for 10-20min, and sintering at 500-540 ℃ for 5-15 min;
3) and (4) formation.
2. The method for preparing the anode foil composite film for the aluminum electrolytic capacitor according to claim 1, wherein: repeating the step 2) for 1-5 times.
3. The method for preparing the anode foil composite film for the aluminum electrolytic capacitor according to claim 1, wherein: adding a chelating agent into the gel prepared in the step 1) in a molar ratio of 1:0.7-1:1.2 with butyl titanate, and uniformly stirring; the chelating agent comprises one or more of acetylacetone, EDTA, sodium potassium tartrate or ammonium citrate.
4. The method for preparing the anode foil composite film for the aluminum electrolytic capacitor according to claim 3, wherein: adding a chelating agent, and then adding a stabilizing agent to adjust the pH value to 0.1-1, wherein the stabilizing agent comprises one or more of nitric acid, citric acid or adipic acid.
5. The method for preparing the anode foil composite film for the aluminum electrolytic capacitor according to claim 1, wherein: the thickness of the gel coated on the sintered aluminum foil in the step 2) is 200nm-600 nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113718310A (en) * | 2021-08-09 | 2021-11-30 | 中南大学 | Preparation method of high-dielectric-constant composite anodic oxide film |
| CN113871205A (en) * | 2021-09-27 | 2021-12-31 | 江苏和煊电子科技股份有限公司 | Preparation method of anode foil of aluminum electrolytic capacitor |
| CN114843108A (en) * | 2022-05-18 | 2022-08-02 | 武汉理工大学 | Electrode foil and preparation method and application thereof |
| CN115116752A (en) * | 2022-07-05 | 2022-09-27 | 新疆众和股份有限公司 | Electrode foil with composite oxide film, preparation method thereof and aluminum electrolytic capacitor |
| CN115172061A (en) * | 2022-08-02 | 2022-10-11 | 南通海星电子股份有限公司 | Preparation method of high-dielectric composite powder sintered foil |
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| CN101191224A (en) * | 2006-11-24 | 2008-06-04 | 横店集团东磁有限公司 | Manufacturing method of anode foil for aluminum electrolytic capacitor |
| CN101609748A (en) * | 2008-06-16 | 2009-12-23 | 吴昊 | Modified liquid of anode aluminum foil of electrolytic capacitor and preparation method thereof and purposes |
| CN102360954A (en) * | 2011-09-19 | 2012-02-22 | 常州大学 | Method capable of improving specific volume of anode foil of aluminum electrolytic capacitor |
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2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1766168A (en) * | 2005-10-10 | 2006-05-03 | 西安交通大学 | Titanium oxide/aluminum oxide high dielectric constant composite anode film preparation method |
| CN101191224A (en) * | 2006-11-24 | 2008-06-04 | 横店集团东磁有限公司 | Manufacturing method of anode foil for aluminum electrolytic capacitor |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113718310A (en) * | 2021-08-09 | 2021-11-30 | 中南大学 | Preparation method of high-dielectric-constant composite anodic oxide film |
| CN113871205A (en) * | 2021-09-27 | 2021-12-31 | 江苏和煊电子科技股份有限公司 | Preparation method of anode foil of aluminum electrolytic capacitor |
| CN113871205B (en) * | 2021-09-27 | 2023-01-31 | 江苏和煊电子科技股份有限公司 | Preparation method of anode foil of aluminum electrolytic capacitor |
| CN114843108A (en) * | 2022-05-18 | 2022-08-02 | 武汉理工大学 | Electrode foil and preparation method and application thereof |
| CN114843108B (en) * | 2022-05-18 | 2023-11-14 | 武汉理工大学 | Electrode foil and preparation method and application thereof |
| CN115116752A (en) * | 2022-07-05 | 2022-09-27 | 新疆众和股份有限公司 | Electrode foil with composite oxide film, preparation method thereof and aluminum electrolytic capacitor |
| CN115116752B (en) * | 2022-07-05 | 2023-10-13 | 新疆众和股份有限公司 | Electrode foil with composite oxide film, preparation method thereof and aluminum electrolytic capacitor |
| CN115172061A (en) * | 2022-08-02 | 2022-10-11 | 南通海星电子股份有限公司 | Preparation method of high-dielectric composite powder sintered foil |
| CN115172061B (en) * | 2022-08-02 | 2024-01-30 | 南通海星电子股份有限公司 | Preparation method of high-dielectric composite powder sintered foil |
| WO2024027122A1 (en) * | 2022-08-02 | 2024-02-08 | 南通海星电子股份有限公司 | Preparation method for high-dielectric composite powder sintered foil |
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Application publication date: 20210723 |