CN115172060A - Method for preparing aluminum electrolytic capacitor anode foil based on electrophoretic deposition - Google Patents
Method for preparing aluminum electrolytic capacitor anode foil based on electrophoretic deposition Download PDFInfo
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 367
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 334
- 239000011888 foil Substances 0.000 title claims abstract description 332
- 238000000034 method Methods 0.000 title claims abstract description 117
- 238000001652 electrophoretic deposition Methods 0.000 title claims abstract description 85
- 239000003990 capacitor Substances 0.000 title claims abstract description 70
- 238000010438 heat treatment Methods 0.000 claims abstract description 130
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002002 slurry Substances 0.000 claims abstract description 74
- 238000005245 sintering Methods 0.000 claims abstract description 66
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 238000009835 boiling Methods 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 59
- 238000004140 cleaning Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 126
- 230000008569 process Effects 0.000 claims description 91
- 238000001291 vacuum drying Methods 0.000 claims description 91
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 70
- 239000008367 deionised water Substances 0.000 claims description 55
- 229910021641 deionized water Inorganic materials 0.000 claims description 55
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 51
- 238000000151 deposition Methods 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
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- 238000001962 electrophoresis Methods 0.000 claims description 36
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 25
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- 239000002270 dispersing agent Substances 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
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- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 229920000193 polymethacrylate Polymers 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
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- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- 239000000787 lecithin Substances 0.000 claims description 7
- 235000010445 lecithin Nutrition 0.000 claims description 7
- 229940067606 lecithin Drugs 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 16
- 230000003068 static effect Effects 0.000 description 16
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
- C25D13/16—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
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/14—Structural combinations or circuits for modifying, or compensating for, electric characteristics of electrolytic capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a method for preparing an aluminum electrolytic capacitor anode foil based on electrophoretic deposition, which comprises the following steps: 1. preparing slurry; 2. coating the slurry on an aluminum foil matrix and drying; 3. sintering treatment; 4. boiling in water; 5. cleaning and drying after electrophoretic deposition treatment; 6. heat treatment; 7. and cleaning and drying after the formation treatment to obtain the aluminum electrolytic capacitor anode foil. The invention forms a porous layer by coating the slurry on the surface of an aluminum foil substrate and sintering the coated substrate so thatThe obtained aluminum foil has higher specific surface area and larger pores, and Al with higher dielectric constant is formed on the surface of the aluminum foil by combining electrophoretic deposition and chemical conversion treatment 2 O 3 ‑BaTiO 3 The composite oxide film improves the specific capacity of the electrolytic capacitor anode foil, meets the use requirement of medium and high pressure environment, and simultaneously expands the average grain diameter of the raw material powder to 10-20 mu m, thereby greatly reducing the cost of the preparation raw material.
Description
Technical Field
The invention belongs to the technical field of aluminum electrolytic capacitors, and particularly relates to a method for preparing an aluminum electrolytic capacitor anode foil based on electrophoretic deposition.
Background
The aluminum electrolytic capacitor is a universal electrolytic capacitor which is made of aluminum materials and has good electrical property, wide application range and high reliability, and has wide application prospect in the fields of industrial control, household appliances, automobile electronics and the like. The key to determining the performance of the aluminum electrolytic capacitor is its specific capacity, which is mainly provided by the anode foil. With the rapid development of the electronic industry, the demand for large capacity and small volume of the aluminum electrolytic capacitor is increasing, which requires the anode foil to have higher specific capacity. However, the existing preparation method for improving the specific capacity of the anode foil by adopting corrosion hole forming and hole expanding to improve the specific surface area of the anode foil is difficult to break through, and waste acid is generated in the process of the method to cause environmental pollution.
In recent years, researchers have developed a method of sintering a porous layer on the surface of an aluminum foil substrate instead of etching an etched foil. Chinese patents CN 102714098B, CN 102804302A, CN 103688327A, CN 104409215A, CN 104919919552B, CN 110993347B, CN 110993348A and CN 111146005B all refer to sintering a porous aluminum or aluminum alloy powder layer on an aluminum foil substrate to increase the specific surface area of the aluminum foil, thereby improving the specific capacity of the aluminum foil. However, the above patent is high in demand for the raw material aluminum and aluminum alloy powder, and both are small-particle-size powders having an average particle size of 10 μm or less, which results in high cost of the powder raw material. Compared with aluminum and aluminum alloy powder with small particle size, the raw material powder with larger particle size is favorable for reducing the raw material cost, but the specific surface area of the powder with large particle size is smaller than that of the powder with small particle size, so that when the aluminum foil of a sintered product with the same thickness is manufactured, the specific capacity of the porous layer sintered by the raw material powder with large particle size is smaller than that of the porous layer sintered by the raw material powder with small particle size. Therefore, there is a need for a method that can utilize aluminum or aluminum alloy powder having a large particle size, which is less expensive to manufacture, and can provide a porous layer sintered on the surface of an aluminum foil substrate with a high specific capacity.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing an aluminum electrolytic capacitor anode foil based on electrophoretic deposition, aiming at the defects of the prior art. The method comprises the steps of coating raw material powder slurry on the surface of an aluminum foil substrate and sintering to form a porous layer, so that the aluminum foil has a higher specific surface area and larger pores, and depositing BaTiO on hydrated alumina on the surface of the aluminum foil in combination with electrophoretic deposition 3 Forming Al with dielectric constant ratio on the surface of the aluminum foil by chemical conversion treatment 2 O 3 Al with higher film dielectric constant 2 O 3 -BaTiO 3 The composite oxide film improves the specific capacity of the electrolytic capacitor anode foil, so that the average particle size of the raw material powder is enlarged to 10-20 mu m, and the cost of the preparation raw material is greatly reduced.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing an anode foil of an aluminum electrolytic capacitor based on electrophoretic deposition is characterized by comprising the following steps:
step one, mixing and stirring spherical aluminum powder or/and spherical aluminum alloy powder with a solvent, a binder and a dispersant uniformly to obtain slurry;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2);
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor.
The invention firstly prepares spherical aluminum powder or/and spherical aluminum alloy powder into slurry to be coated on the surface of an aluminum foil substrate, the slurry forms a porous layer on the surface of the aluminum foil substrate after drying and sintering, so that the aluminum foil has higher specific surface area and larger pores, the aluminum foil with hydrated alumina on the surface is obtained by boiling in water, and then BaTiO is deposited on the hydrated alumina on the surface of the aluminum foil through electrophoretic deposition 3 And the hydrated alumina is converted into alumina by heat treatment, and the alumina is mixed with BaTiO 3 Closely combined, and formed into Al with dielectric constant ratio on the surface of the aluminum foil after formation treatment 2 O 3 Al with higher film dielectric constant 2 O 3 -BaTiO 3 The aluminum electrolytic capacitor anode foil is obtained by compounding the oxide film, the specific capacity of the aluminum electrolytic capacitor anode foil is improved, and the aluminum electrolytic capacitor anode foil meeting the use requirements of medium and high voltage environments is obtained.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that in the first step, the average grain diameter of the spherical aluminum powder and the average grain diameter of the spherical aluminum alloy powder are both 10 micrometers-20 micrometers, and the mass purity of the spherical aluminum powder and the spherical aluminum alloy powder is not lower than 99.95%; the solvent is at least one of absolute ethyl alcohol, glycerol, terpineol and glycol, the binder is at least one of polymethacrylate, polyvinyl alcohol, ethyl cellulose and carboxymethyl cellulose, and the dispersant is at least one of lecithin, oleic acid, polyethylene glycol and triethanolamine. According to the invention, the particle size of the raw material powder is controlled to provide a higher specific surface area and larger pores for the porous layer formed after the surface of the aluminum foil substrate is sintered, and impurities are prevented from being introduced by controlling the quality and purity of the raw material powder, so that the performance of the porous layer is ensured; by controlling the type of the solvent, the dissolution of the binder and the dispersant in the solvent is promoted, so that the slurry is easy to dry and has no residue after sintering; by controlling the type of the binder, the viscosity of the slurry is suitable for coating, the aluminum foil matrix does not fall off powder after being coated and dried, and no residue is left after sintering; by controlling the type of the dispersing agent, the raw material powder is uniformly dispersed in the slurry, the slurry is not easy to layer, and no residue is left after sintering.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that in the second step, the thickness of the aluminum foil substrate is 20-60 micrometers, the two sides of the slurry are symmetrically coated on the upper surface and the lower surface of the aluminum foil substrate, the vacuum drying temperature is 80-150 ℃, and the thickness of the aluminum foil after vacuum drying after coating of the slurry is 120-180 micrometers. The invention ensures that the aluminum foil has certain mechanical strength by controlling the thickness of the aluminum foil substrate; usually, a scraper is adopted for coating so as to easily control the thickness of the slurry coated on the surface of the aluminum foil substrate, and the surface of the aluminum foil is smooth after the slurry is dried; by controlling the two sides of the slurry to be symmetrically coated, the thickness difference of the slurry coated on the two sides of the aluminum foil substrate is reduced, the surface of the aluminum foil is ensured to be kept flat after sintering, and the subsequent boiling treatment and the electrodeposition treatment are facilitated; the thickness of the aluminum foil substrate which is coated with the slurry and then is dried in vacuum is controlled, so that the slurry after sintering forms a porous layer with proper thickness on the surface of the aluminum foil substrate, the anode foil of the aluminum electrolytic capacitor is ensured to have higher specific capacity, the reduction of the specific capacity of the aluminum foil after water boiling treatment, electrodeposition treatment and formation treatment caused by too small thickness of the porous layer is avoided, and the aluminum foil after water boiling treatment, electrodeposition treatment and formation treatment caused by too large thickness of the porous layer is avoided to have higher hardness and be easy to break; according to the invention, by controlling the drying atmosphere and the drying temperature, impurities are prevented from being introduced, the volatilization of the solvent is promoted, and the powder layer formed after the slurry is dried is well combined with the aluminum foil substrate.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that the sintering process in the third step is as follows: heating from room temperature to 400-500 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 4-8 h, then heating to 600-650 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 6-12h, and then cooling along with a furnace; the atmosphere in the furnace in the sintering process is nitrogen, argon or vacuum. The invention adopts two-stage heating for sintering, the solvent, the binder and the dispersant which are remained in the powder layer on the surface of the aluminum foil substrate are removed at low temperature in the first stage, the aluminum or aluminum alloy powder on the surface of the aluminum foil substrate is sintered into the porous layer at high temperature in the second stage, and the porous layer and the aluminum foil substrate form the sintered aluminum foil with a sandwich structure.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that the water boiling treatment in the fourth step is carried out by using deionized water at 100 ℃, and the water boiling time is 10min to 20min. According to the invention, the deionized water is adopted for boiling to prevent impurities from being introduced, and the boiling time is controlled to form hydrated alumina with proper thickness on the surface of the aluminum foil, so that the subsequent electrophoretic deposition treatment and formation treatment are facilitated.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that BaTiO with the average grain diameter of 20nm-30nm is adopted in the electrophoretic deposition treatment process in the fifth step 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of the compound is 20 g/L-40 g/L, and the volume ratio of ethanol to acetylacetone is 0.8; the voltage of the electrophoretic deposition treatment is from 10V to 30V, and the deposition time is from 5min to 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃. The invention controls BaTiO in the electrophoretic solution 3 So that BaTiO 3 The powder is easy to enter a porous layer of the sintered aluminum foil and is easy to be evenly deposited on the surface of the hydrated alumina to form a film, and BaTiO is controlled 3 The volume ratio of the ethanol to the acetylacetone, so that the suspension has good stability, the voltage is in a safe voltage range by controlling the voltage of the electrophoretic deposition treatment, and the BaTiO in the suspension 3 The particles are not easy to settle, baTiO 3 The film deposition rate is controllable, and the time of electrodeposition is controlled in combination, so that BaTiO 3 The thickness of the film is controllable; and the introduction of impurities is avoided by adopting deionized water cleaning and vacuum drying.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that the temperature of the heat treatment in the sixth step is 480-520 ℃, and the time is 480-520 DEG C5min to 15min. The invention controls the temperature and time of heat treatment to convert hydrated alumina into alumina and react with BaTiO 3 The tight combination is beneficial to the formation of a compact composite oxide film by the subsequent formation treatment.
The method for preparing the anode foil of the aluminum electrolytic capacitor based on electrophoretic deposition is characterized in that boric acid solution with the mass concentration of 10-20% is adopted in the formation treatment in the seventh step, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃. According to the invention, the composite oxide film with the dielectric constant higher than that of the alumina film is obtained on the surface of the aluminum foil through the formation treatment of the process parameters, so that the specific capacity of the anode foil is improved; deionized water cleaning and vacuum drying are adopted, so that impurities are prevented from being introduced.
Compared with the prior art, the invention has the following advantages:
1. the invention makes spherical aluminum powder or/and spherical aluminum alloy powder into slurry to be coated on the surface of an aluminum foil substrate and to be sintered to form a porous layer, so that the aluminum foil has higher specific surface area and larger pores, and BaTiO is deposited on hydrated alumina on the surface of the aluminum foil by combining electrophoretic deposition 3 Forming Al with dielectric constant ratio on the surface of the aluminum foil through heat treatment and chemical treatment 2 O 3 Al having higher film dielectric constant 2 O 3 -BaTiO 3 The composite oxide film improves the specific capacity of the electrolytic capacitor anode foil and meets the use requirements of medium and high voltage environments.
2. The invention forms Al with dielectric constant ratio on the surface of the aluminum foil 2 O 3 Al having higher film dielectric constant 2 O 3 -BaTiO 3 The composite oxide film improves the specific capacity of the anode foil of the aluminum electrolytic capacitor, so that the average particle size of raw material powder, namely aluminum and aluminum alloy powder, is enlarged to 10-20 mu m, and the cost of the preparation raw material is greatly reduced.
3. The invention adopts nano BaTiO 3 The suspension prepared by mixing the powder, the ethanol and the acetylacetone and performing ultrasonic dispersion is used as an electrophoresis solution, and the electrophoresis solution has simple components and is easy to prepare.
4. The invention adopts electrophoretic deposition on the surface of the aluminum foilDeposition of BaTiO on hydrated alumina 3 The control of the electrophoretic deposition rate and the electrophoretic deposition thickness is realized by controlling the voltage and time of electrophoretic deposition, the operation is safe, and the process is simple.
5. The invention carries out heat treatment after electrophoretic deposition to convert hydrated alumina on the surface of the aluminum foil into Al 2 O 3 ，Al 2 O 3 With deposited BaTiO 3 Closely combined, improve Al 2 O 3 -BaTiO 3 Compactness of the composite oxide film.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, a solvent, namely absolute ethyl alcohol, ethylene glycol, a binder, namely ethyl cellulose, and a dispersant, namely polyethylene glycol, according to the mass ratio of 55; the average grain diameter of the spherical aluminum powder is 15 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil matrix is 30 micrometers, the slurry is symmetrically coated on the upper surface and the lower surface of the aluminum foil matrix in a double-sided mode by a scraper coating mode, the vacuum drying temperature is 80 ℃, and the thickness of the aluminum foil after vacuum drying after coating the slurry is 120 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at a heating rate of 2 ℃/min, preserving heat for 6 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 hours, and cooling along with the furnace; in the sintering process, the furnace atmosphere is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 10min;
step five, obtaining the product in the step fourThe aluminum foil with hydrated alumina on the surface is subjected to electrophoretic deposition treatment, and then is cleaned and dried in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (1); baTiO with the average grain diameter of 25nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (3) is 30g/L, and the volume ratio of ethanol to acetylacetone is 1; the voltage of the electrophoretic deposition treatment is 20V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 500 ℃, and the time is 10min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.83 mu F/cm 2 。
The solvent in this embodiment may be replaced with at least one of anhydrous ethanol, glycerol, terpineol, and ethylene glycol other than anhydrous ethanol and ethylene glycol, the binder may be replaced with at least one of polymethacrylate, polyvinyl alcohol, ethylcellulose, and carboxymethyl cellulose other than ethylcellulose, and the dispersant may be replaced with at least one of lecithin, oleic acid, polyethylene glycol, and triethanolamine other than polyethylene glycol.
Comparative example 1
This comparative example comprises the following steps:
step one, uniformly mixing and stirring spherical aluminum powder, solvent absolute ethyl alcohol, glycol, binder ethyl cellulose and dispersant polyethylene glycol according to the mass ratio of (55); the average grain diameter of the spherical aluminum powder is 15 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 30 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 80 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 120 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 2 ℃/min, preserving heat for 6 hours, then heating to 600 ℃ at the heating rate of 5 ℃/min, preserving heat for 10 hours, and then cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 10min;
fifthly, carrying out formation treatment on the aluminum foil with hydrated alumina on the surface obtained in the fourth step, and then cleaning and vacuum drying to obtain an aluminum electrolytic capacitor anode foil; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the comparative example reaches 0.52 mu F/cm 2 。
Comparing example 1 of the present invention with comparative example 1, it can be seen that the present invention deposits BaTiO on hydrated alumina on the surface of aluminum foil by electrophoretic deposition 3 Forming Al with dielectric constant ratio on the surface of the aluminum foil through heat treatment and chemical treatment 2 O 3 Al having higher film dielectric constant 2 O 3 -BaTiO 3 The composite oxide film improves the specific capacity of the anode foil of the electrolytic capacitor,
example 2
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, spherical 6061 aluminum alloy powder, a solvent ethylene glycol, terpineol, a binder polymethacrylate, ethyl cellulose and a dispersant polyethylene glycol according to a mass ratio of 40; the average grain diameter of the spherical aluminum powder and the spherical 6061 aluminum alloy powder is 10 mu m, and the mass purity is 99.95 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 30 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 100 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 130 micrometers;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 480 ℃ at the heating rate of 2 ℃/min and preserving heat for 5h, then heating to 640 ℃ at the heating rate of 5 ℃/min and preserving heat for 8h, and then cooling along with the furnace; the atmosphere in the furnace is vacuum in the sintering process;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 30nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 20g/L, and the volume ratio of ethanol to acetylacetone is 0.8; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.91 mu F/cm 2 。
Example 3
The embodiment comprises the following steps:
step one, mixing and stirring spherical aluminum powder, spherical 6061 aluminum alloy powder, solvent absolute ethyl alcohol, terpineol, binder polyvinyl alcohol, ethyl cellulose, dispersant oleic acid and polyethylene glycol uniformly according to the mass ratio of 20; the average grain diameter of the spherical aluminum powder and the spherical 6061 aluminum alloy powder is 20 mu m, and the mass purity is 99.95 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil matrix is 40 micrometers, the slurry is symmetrically coated on the upper surface and the lower surface of the aluminum foil matrix in a double-sided mode by a scraper coating mode, the vacuum drying temperature is 90 ℃, and the thickness of the aluminum foil after vacuum drying after coating the slurry is 150 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 5 ℃/min and preserving heat for 6h, then heating to 650 ℃ at the heating rate of 10 ℃/min and preserving heat for 6h, and then cooling along with the furnace; the furnace atmosphere in the sintering process is nitrogen;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 20min;
step five, the aluminum foil with hydrated alumina on the surface obtained in the step four is subjected to electrophoretic deposition treatment, and thenThen cleaning and vacuum drying are carried out to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (A) is 25g/L, and the volume ratio of ethanol to acetylacetone is 1.1; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment; the temperature of the heat treatment is 510 ℃, and the time is 8min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts a boric acid solution with the mass concentration of 20%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.03 mu F/cm 2 。
Example 4
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, terpineol as a solvent, glycerol, carboxymethyl cellulose as a binder, ethyl cellulose, lecithin as a dispersant and polyethylene glycol according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 20 mu m, and the mass purity is 99.95%;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 40 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 150 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 180 micrometers;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 5 hours, heating to 640 ℃ at a heating rate of 5 ℃/min, preserving heat for 10 hours, and cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 20min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (A) is 40g/L, and the volume ratio of ethanol to acetylacetone is 1.2; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 5min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 480 ℃, and the time is 15min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.24F/cm 2 。
Example 5
The embodiment comprises the following steps:
step one, mixing and stirring spherical 6061 aluminum alloy powder, solvent anhydrous ethanol, glycol, glycerol, binder polymethacrylate, ethyl cellulose, dispersant lecithin and polyethylene glycol uniformly according to a mass ratio of 60; the average grain diameter of the spherical 6061 aluminum alloy powder is 20 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 50 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 120 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 170 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 6h, then heating to 620 ℃ at the heating rate of 10 ℃/min, preserving heat for 12h, and then cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (1); baTiO with the average grain diameter of 25nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (A) is 25g/L, and the volume ratio of ethanol to acetylacetone is 1; the voltage of the electrophoretic deposition treatment is 20V, and the deposition time is 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 500 ℃, and the time is 10min;
step seven, the surface after heat treatment in the step six is treatedDeposition of BaTiO 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.08 mu F/cm 2 。
Example 6
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, solvent absolute ethyl alcohol, glycerol, binder polymethacrylate, polyvinyl alcohol, dispersant lecithin and oleic acid according to a mass ratio of 65; the average grain diameter of the spherical aluminum powder is 10 mu m, and the mass purity is 99.95%;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 60 micrometers, the slurry is symmetrically coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode, the vacuum drying temperature is 110 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 160 micrometers;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 7h, then heating to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 11h, and then cooling along with the furnace; the atmosphere in the furnace is nitrogen in the sintering process;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 10min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (1); the electrophoretic deposition process adopts a flat surfaceBaTiO with average particle size of 20nm 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (A) is 20g/L, and the volume ratio of ethanol to acetylacetone is 1; the voltage of the electrophoretic deposition treatment is 25V, and the deposition time is 10min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.87 mu F/cm 2 。
Example 7
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, a solvent of ethylene glycol, glycerol, a binder of polymethacrylate, polyvinyl alcohol and a dispersant of triethanolamine according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 15 mu m, and the mass purity is 99.95%;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 50 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 130 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 150 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 5h, then heating to 630 ℃ at the heating rate of 10 ℃/min, preserving heat for 9h, and then cooling along with the furnace; in the sintering process, the furnace atmosphere is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 25nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 30g/L, and the volume ratio of ethanol to acetylacetone is 1.1; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 480 ℃, and the time is 8min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.93 mu F/cm 2 。
Example 8
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, a solvent, namely ethylene glycol, glycerol, a binder, namely carboxymethyl cellulose, and a dispersant, namely polyethylene glycol, according to the mass ratio of 55; the average grain diameter of the spherical aluminum powder is 15 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 30 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 120 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 140 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 480 ℃ at the heating rate of 5 ℃/min and preserving heat for 6h, then heating to 640 ℃ at the heating rate of 10 ℃/min and preserving heat for 7h, and then cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
fifthly, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the fourth step, then cleaning and vacuum drying to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (3) is 40g/L, and the volume ratio of ethanol to acetylacetone is 0.9; the voltage of the electrophoretic deposition treatment is 25V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the vacuum drying temperature is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; the above-mentionedDeionized water is adopted in the cleaning process, and the temperature of the vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.98 mu F/cm 2 。
Example 9
The embodiment comprises the following steps:
uniformly mixing and stirring spherical 6061 aluminum alloy powder, a solvent of ethylene glycol, terpineol, glycerol, a binder of ethyl cellulose, a dispersant of triethanolamine and polyethylene glycol according to a mass ratio of 55; the average grain diameter of the spherical 6061 aluminum alloy powder is 20 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 60 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 140 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 180 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 500 ℃ at the heating rate of 2 ℃/min, preserving heat for 4h, then heating to 650 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, and then cooling along with the furnace; the atmosphere in the furnace is vacuum in the sintering process;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 20min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 Is 30g/L, ethanol and acetylThe volume ratio of acetone is 1; the voltage of the electrophoretic deposition treatment is 25V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the vacuum drying temperature is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 500 ℃, and the time is 10min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.18 mu F/cm 2 。
Example 10
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, solvent absolute ethyl alcohol, ethylene glycol, binder polyvinyl alcohol, ethyl cellulose, dispersant triethanolamine and oleic acid according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 10 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 30 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 100 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 130 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 5 hours, then heating to 640 ℃ at the heating rate of 10 ℃/min, preserving heat for 6 hours, and then cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
fifthly, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the fourth step, then cleaning and vacuum drying to obtain BaTiO deposited on the surface 3 The aluminum foil of (1); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 25g/L, and the volume ratio of ethanol to acetylacetone is 1.2; the voltage of the electrophoretic deposition treatment is 10V, and the deposition time is 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.88 mu F/cm 2 。
Example 11
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, a solvent of ethylene glycol, glycerol, a binder of polymethacrylate, polyvinyl alcohol and a dispersant of triethanolamine according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 15 mu m, and the mass purity is 99.95%;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 20 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 120 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 120 micrometers;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 400 ℃ at a heating rate of 2 ℃/min, preserving heat for 8 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 12 hours, and cooling along with the furnace; the atmosphere in the furnace is nitrogen in the sintering process;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 10min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 30nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 20g/L, and the volume ratio of ethanol to acetylacetone is 1; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment; the temperature of the heat treatment is 500 ℃, and the time is 10min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static state of the anode foil of the aluminum electrolytic capacitor prepared in the embodimentThe specific capacity reaches 0.86 mu F/cm 2 。
Example 12
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, solvent absolute ethyl alcohol, ethylene glycol, glycerol, binder polyvinyl alcohol, ethyl cellulose, dispersant triethanolamine and oleic acid according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 10 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 30 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 110 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 130 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 6 hours, then heating to 630 ℃ at the heating rate of 10 ℃/min, preserving heat for 9 hours, and then cooling along with the furnace; in the sintering process, the furnace atmosphere is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (A) is 30g/L, and the volume ratio of ethanol to acetylacetone is 1.1; the voltage of the electrophoretic deposition treatment is 30V, and the deposition time is 5min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.91 mu F/cm 2 。
Example 13
The embodiment comprises the following steps:
step one, uniformly mixing and stirring spherical aluminum powder, a solvent of ethylene glycol, glycerol, a binder of carboxymethyl cellulose and a dispersant of polyethylene glycol according to the mass ratio of (55); the average grain diameter of the spherical aluminum powder is 20 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of an aluminum foil matrix, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 20 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 130 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 140 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 480 ℃ at the heating rate of 2 ℃/min, preserving heat for 6 hours, heating to 640 ℃ at the heating rate of 5 ℃/min, preserving heat for 8 hours, and cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 15min;
step five, obtaining the product in the step fourThe aluminum foil with hydrated alumina on the surface is subjected to electrophoretic deposition treatment, and then is cleaned and dried in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (1); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (3) is 40g/L, and the volume ratio of ethanol to acetylacetone is 0.9; the voltage of the electrophoretic deposition treatment is 10V, and the deposition time is 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 480 ℃, and the time is 8min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 0.97 mu F/cm 2 。
Example 14
The embodiment comprises the following steps:
step one, mixing and stirring spherical 6061 aluminum alloy powder, solvent absolute ethyl alcohol, glycol, glycerol, binder polyvinyl alcohol, ethyl cellulose, dispersant triethanolamine and oleic acid uniformly according to the mass ratio of (60); the average grain diameter of the spherical aluminum alloy powder is 20 mu m, and the mass purity is 99.95%;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 40 mu m, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 120 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 180 mu m;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, then heating to 650 ℃ at the heating rate of 10 ℃/min, preserving heat for 6h, and then cooling along with the furnace; the atmosphere in the furnace is vacuum in the sintering process;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 20min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 25nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and then performing ultrasonic dispersion to prepare a suspension serving as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 30g/L, and the volume ratio of ethanol to acetylacetone is 1; the voltage of the electrophoretic deposition treatment is 20V, and the deposition time is 10min; deionized water is adopted in the cleaning process, and the vacuum drying temperature is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment; the temperature of the heat treatment is 520 ℃, and the time is 5min;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.09 mu F/cm 2 。
Example 15
The embodiment comprises the following steps:
uniformly mixing and stirring spherical aluminum powder, terpineol as a solvent, glycerol, carboxymethyl cellulose as a binder, ethyl cellulose, lecithin as a dispersant and polyethylene glycol according to a mass ratio of 60; the average grain diameter of the spherical aluminum powder is 20 mu m, and the mass purity is 99.99 percent;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying; the thickness of the aluminum foil substrate is 50 micrometers, the slurry is coated on the upper surface and the lower surface of the aluminum foil substrate in a scraper coating mode in a double-sided symmetrical mode, the vacuum drying temperature is 140 ℃, and the thickness of the aluminum foil after being coated with the slurry and being dried in vacuum is 170 micrometers;
step three, sintering the aluminum foil subjected to vacuum drying in the step two to obtain a sintered aluminum foil; the sintering process comprises the following steps: heating from room temperature to 450 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, heating to 640 ℃ at a heating rate of 5 ℃/min, preserving heat for 6h, and cooling along with the furnace; the furnace atmosphere in the sintering process is argon;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface; the water boiling treatment is carried out by using deionized water at 100 ℃, and the water boiling time is 20min;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2); baTiO with the average grain diameter of 20nm is adopted in the electrophoretic deposition treatment process 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of (2) is 25g/L, and the volume ratio of ethanol to acetylacetone is 1.2; the voltage of the electrophoretic deposition treatment is 25V, and the deposition time is 15min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃;
step six, depositing BaTiO on the surface obtained in the step five 3 Carrying out heat treatment on the aluminum foil; the temperature of the heat treatment is 500 ℃, and the time is 10min;
step seven, step sixDepositing BaTiO on the surface after heat treatment 3 The aluminum foil is subjected to formation treatment, and then is cleaned and vacuum-dried to obtain the anode foil of the aluminum electrolytic capacitor; the formation treatment adopts boric acid solution with the mass concentration of 15%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
Through detection, the static specific capacity of the anode foil of the aluminum electrolytic capacitor prepared by the embodiment reaches 1.01 mu F/cm 2 。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. A method for preparing an aluminum electrolytic capacitor anode foil based on electrophoretic deposition is characterized by comprising the following steps:
step one, mixing and stirring spherical aluminum powder or/and spherical aluminum alloy powder with a solvent, a binder and a dispersant uniformly to obtain slurry;
coating the slurry obtained in the step one on the upper surface and the lower surface of the aluminum foil substrate, and then carrying out vacuum drying;
thirdly, sintering the aluminum foil dried in the vacuum in the second step to obtain a sintered aluminum foil;
step four, carrying out water boiling treatment on the sintered aluminum foil obtained in the step three to obtain an aluminum foil with hydrated alumina on the surface;
step five, carrying out electrophoretic deposition treatment on the aluminum foil with the hydrated alumina on the surface obtained in the step four, then cleaning and drying in vacuum to obtain BaTiO deposited on the surface 3 The aluminum foil of (2);
step six, depositing BaTiO on the surface obtained in the step five 3 The aluminum foil is subjected to heat treatment;
step seven, depositing BaTiO on the surface after heat treatment in the step six 3 The aluminum foil is subjected to formation treatment, and then is cleaned and dried in vacuum to obtain the aluminum capacitorAnd (4) electrolyzing the capacitor anode foil.
2. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the average particle diameter of the spherical aluminum powder and the spherical aluminum alloy powder in the first step is 10 μm to 20 μm, and the mass purity is not lower than 99.95%; the solvent is at least one of absolute ethyl alcohol, glycerol, terpineol and glycol, the binder is at least one of polymethacrylate, polyvinyl alcohol, ethyl cellulose and carboxymethyl cellulose, and the dispersant is at least one of lecithin, oleic acid, polyethylene glycol and triethanolamine.
3. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the thickness of the aluminum foil substrate in the second step is 20 μm to 60 μm, the slurry is symmetrically coated on the upper surface and the lower surface of the aluminum foil substrate on both sides, the vacuum drying temperature is 80 ℃ to 150 ℃, and the thickness of the aluminum foil after the slurry is coated and vacuum dried is 120 μm to 180 μm.
4. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the sintering process in step three is as follows: heating from room temperature to 400-500 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 4-8 h, heating to 600-650 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 6-12h, and cooling along with a furnace; the atmosphere in the furnace in the sintering process is nitrogen, argon or vacuum.
5. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the boiling treatment in the fourth step is performed with deionized water at 100 ℃ for 10min to 20min.
6. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1,the method is characterized in that BaTiO with the average grain diameter of 20nm to 30nm is adopted in the electrophoretic deposition treatment process in the fifth step 3 Mixing powder, ethanol and acetylacetone, and performing ultrasonic dispersion to prepare a suspension as an electrophoresis solution, wherein BaTiO in the electrophoresis solution 3 The concentration of the compound is 20 g/L-40 g/L, and the volume ratio of ethanol to acetylacetone is 0.8; the voltage of the electrophoretic deposition treatment is from 10V to 30V, and the deposition time is from 5min to 20min; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
7. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the temperature of the heat treatment in the sixth step is 480 ℃ to 520 ℃ and the time is 5min to 15min.
8. The method for preparing the anode foil of the aluminum electrolytic capacitor based on the electrophoretic deposition as claimed in claim 1, wherein the formation treatment in the seventh step is performed by using a boric acid solution with a mass concentration of 10% -20%, and the formation voltage is 520V; deionized water is adopted in the cleaning process, and the temperature of vacuum drying is 100 ℃.
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