CN115172054B - Medium-high voltage anodic oxidation pretreatment method, aluminum foil and aluminum electrolytic capacitor - Google Patents
Medium-high voltage anodic oxidation pretreatment method, aluminum foil and aluminum electrolytic capacitor Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 108
- 230000003647 oxidation Effects 0.000 title claims abstract description 75
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 75
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 58
- 239000003990 capacitor Substances 0.000 title claims abstract description 12
- 238000002203 pretreatment Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000005260 corrosion Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 230000000295 complement effect Effects 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 7
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007743 anodising Methods 0.000 claims description 9
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229940067597 azelate Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 19
- 239000011259 mixed solution Substances 0.000 abstract description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 6
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 230000001502 supplementing effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000010407 anodic oxide Substances 0.000 description 8
- 230000008439 repair process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- IKFMRFYLIRAXAJ-UHFFFAOYSA-N azane;nonanedioic acid Chemical compound N.OC(=O)CCCCCCCC(O)=O IKFMRFYLIRAXAJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- 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
- H01G9/0029—Processes of manufacture
-
- 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
- H01G9/042—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
-
- 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
- H01G9/055—Etched foil electrodes
Abstract
The invention relates to the technical field of medium-high voltage anodic oxidation, in particular to a medium-high voltage anodic oxidation pretreatment method, an aluminum foil and an aluminum electrolytic capacitor, wherein the medium-high voltage corrosion foil is pretreated in pure water at 100 ℃; then soaking treatment is carried out in a mixed solution of alkali and corrosion inhibitor, the pH value of the mixed solution is 9-13, the treatment temperature is 50-80 ℃, the treatment time is 10-60 minutes, and the treated corrosion foil is sequentially subjected to anodic oxidation, annealing and complementary formation to obtain an anode aluminum foil, so that the energy consumption in the anodic oxidation process is saved by 6.6-8.1% on the premise that the capacity of the anode foil is not attenuated, and the pretreatment can reduce the energy consumption in the anodic oxidation process of the aluminum foil; the addition of the polyhydroxy organic corrosion inhibitor can avoid corrosion of the alkaline pretreatment process to the aluminum core, ensure the mechanical strength and capacitance of the anode foil, and compared with other acid or alkaline treatment processes, the performance of the anode foil is not reduced, and the problems of low quality and a lot of defects of a hydrated oxide film formed by the traditional water treatment process are overcome.
Description
Technical Field
The invention belongs to the field of anodic oxidation, and relates to a medium-high voltage anodic oxidation pretreatment method, an aluminum foil and an aluminum electrolytic capacitor.
Background
Anodic oxidation is an electrochemical process of forming a compact oxide film on the surface of a metal anode through the action of an externally applied electric field. This process is widely used in the manufacture of electrolytic capacitor anode foils. However, in the anodic oxidation process, the anodic resistance increases with the continuous growth of the oxide film, so that a large amount of joule heat or electric breakdown is generated, and the oxide film is further damaged or burned. In addition, the anodic oxidation process inevitably accompanies electrode polarization and oxygen evolution side reactions, causing additional energy consumption. The huge energy consumption cost has become the most important limitation in the field of electrolytic capacitors.
High-pressure anodic oxidation (generally > 200V) is different from general low-pressure anodic oxidation, and needs to convert metal simple substance into hydroxide or hydrated oxide through pretreatment process, and the metal simple substance is converted into a compact oxide film through the action of an external electric field in corresponding electrolyte. Compared with the direct anodic oxidation process, the pretreatment process can reduce the energy consumption of anodic oxidation and improve the quality of the oxide film. The current pretreatment process in industry is a water treatment process, but the grown hydrated oxide film has a large number of defects, so that the leakage current of the anode foil is increased, and the service life of the capacitor is reduced. And due to the defects, side reactions in the anodic oxidation process are increased, the oxidation time is prolonged, and the anodic oxidation efficiency is low. Therefore, improving the pretreatment process and improving the quality of the hydrated oxide film, thereby improving the anodic oxidation efficiency and reducing the corresponding energy consumption becomes a key problem for urgent breakthrough.
According to the research of the literature, the patent CN109859949A provides a pretreatment method for soaking an organic acid solution or a weak alkaline inorganic salt solution, so that the leakage current of the formed foil is effectively reduced. Patent CN112017865a provides a solution for hydration treatment of a formed foil, which contains sulfate, weak acid and weak acid salt, so as to improve the leakage performance of the formed foil, increase specific volume and prolong the service life of a capacitor. Patent CN111139508A provides a strong reducing agent in aqueous solution for a laminated foil pretreatment to increase the specific volume of the formed foil. However, the pretreatment solution provided by the above patent only considers improving the electrical properties of the anode foil, but ignores the energy consumption problem during the anodic oxidation. In addition, excessive acid or base treatment can corrode metallic aluminum, reduce the mechanical strength of the electrode foil, and affect the anode foil capacitance.
Therefore, there is a need for development of a pretreatment process that can reduce the energy consumption of anodic oxidation without losing the capacitance of the electrode foil and without decreasing the mechanical strength.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a pretreatment method for energy conservation of medium-high voltage anodic oxidation with alkali-corrosion inhibitor. The problem of corrosion of excessive acid or alkali to the electrode foil in the existing pretreatment process is solved, so that the pretreatment process which can realize anodic oxidation energy conservation and can not lose the capacity of the finished electrode foil is designed.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme: a medium-high voltage anodic oxidation pretreatment method comprises the following steps:
step 1: treating the medium-high pressure corrosion foil with the thickness of 90-150 mu m in boiling water for 10 minutes to obtain an aluminum foil with a composite hydrated oxide film with a loose layer and a compact layer on the surface;
step 2: soaking the aluminum foil obtained in the step 1 in a solution containing alkali and an organic corrosion inhibitor, wherein the pH of the solution is 9-13, the treatment temperature is 50-80 ℃, and the treatment time is 10-60 minutes;
step 3: and (3) sequentially carrying out anodic oxidation, annealing and complementary formation on the treated corrosion foil to obtain the anode aluminum foil.
The alkali is one or more of potassium hydroxide, sodium carbonate, triethylamine, ethylenediamine, hexamethylenetetramine and ammonia water; the organic corrosion inhibitor is one or more of ethylene glycol, glycerol, 1, 4-butanediol, pentaerythritol, glucose, polyethylene glycol and polyvinyl alcohol; wherein the solubility of the organic corrosion inhibitor is 0.5-5 wt%.
Wherein the anodic oxidation electrolyte is one or more of boric acid 1-20wt%, azelaic acid 1-20wt%, ammonium pentaborate 0.01-2wt% and ammonium azelate 0.01-2wt%.
Wherein the anodic oxidation has a formation voltage of 200-800V and a formation current of 10-100 mA cm -2 The constant-fluidization time is determined by the formation voltage and the formation current, and the constant-fluidization time is 5-10 minutes.
The annealing temperature is 400-600 ℃, and the annealing time is 1-5 minutes.
Wherein the complementary process current is the same as the formation current, and the complementary time is 1-5 minutes.
The anode foil obtained by the pretreatment method is treated by adopting the pretreatment process for two times, and the oxide film is obtained by anodic oxidation of the hydrated oxide film, so that the anode foil has higher breakdown field intensity, lower energy consumption in the anodic oxidation process and higher anodic oxidation efficiency.
The invention relates to an aluminum electrolytic capacitor, which comprises an anode foil, electrolyte and a cathode foil, and has higher withstand voltage and smaller leakage current.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention discloses a pretreatment method for energy saving of medium-high voltage anodic oxidation with alkali-corrosion inhibitor, which comprises the steps of firstly pretreating aluminum foil in boiling water, then soaking in a solution containing alkali and corrosion inhibitor at a set temperature to obtain an electrode foil, and carrying out anodic oxidation, annealing and complementary formation to obtain the anode foil with low leakage current. The method has the beneficial effects that:
1. the problems of low quality and more defects of a hydrated oxide film formed by the traditional water treatment process are solved, and a thicker hydrated oxide film is formed under a milder condition, so that the time of an anodic oxidation process is reduced, the occurrence of side reactions is reduced, and the effects of energy conservation and consumption reduction of anodic oxidation are realized;
2. the secondary pretreatment process can enable excessive aluminum hydroxide in the hydrated oxide film to react with organic/inorganic alkali, so that the compactness of the hydrated oxide film is improved, defects in the hydrated oxide film are correspondingly reduced, the withstand voltage of the finally obtained anode foil is increased, and the oxide film is more compact;
3. the addition of the organic/inorganic alkali can promote the chemical reaction of water and the aluminum core, increase the thickness of the compact layer of the hydrated oxide film, and facilitate the anodic oxidation process of converting the hydrated oxide film into the anodic oxide film, thereby reducing the anodic oxidation time, reducing the energy consumption and improving the anodic oxidation efficiency;
4. the addition of the organic corrosion inhibitor can form a protective layer on the surface of the aluminum core, avoid excessive corrosion of the alkali pretreatment process to the aluminum core, ensure the mechanical strength and capacitance of the anode foil, and can not obviously reduce the performance of the electrode foil compared with other acid or alkali treatment processes.
In addition, the method can be used for large-scale industrialized production, thereby greatly reducing the energy consumption and the corresponding cost of the medium-high voltage anodic oxidation process, promoting the green energy-saving development of the field of electrolytic capacitors, and improving the industrial competitiveness of the electrolytic capacitors.
Drawings
FIG. 1 is a graph comparing the alkali-corrosion inhibitor pretreatment.
Fig. 2 is a cross-sectional SEM image of the hydrated oxide film after water treatment.
Fig. 3 is a cross-sectional SEM picture of the alkali-corrosion inhibitor pretreated and anodized.
Fig. 4 is a cross-sectional SEM image of water treated and anodized.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present invention, all embodiments and preferred methods of implementation mentioned herein may be combined with each other to form new solutions, unless otherwise specified.
In the present invention, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, unless otherwise specified.
In the present invention, each reaction or operation step may be performed sequentially or sequentially unless otherwise indicated. Preferably, the reaction processes herein are performed sequentially.
Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any method or material similar or equivalent to those described may be used in the present invention.
Comparative examples 1 to 6
1) Pretreatment: using the same thickness of the medium-high pressure etched foil as in the examples, boiling in pure water at 100 ℃ for 10 minutes;
2) Anodic oxidation: anodic oxidation treatment is carried out on the pretreated aluminum foil in the electrolyte at the temperature of 85 ℃ as in the embodiment, the current density, constant current boosting reach the preset voltage and constant voltage time, and the constant current boosting reaches the preset voltage and constant voltage time, and the constant current boosting is consistent with the corresponding embodiment;
3) And (3) heat treatment: washing the aluminum foil after formation with water, wherein the heat treatment temperature and time are consistent with those of the corresponding embodiment;
4) And (3) supplementing: and (3) carrying out anodic oxidation complementary formation treatment on the aluminum foil subjected to heat treatment in the electrolyte at the temperature of 85 ℃ in the same way as that in the embodiment, wherein the current density, constant current boosting reach preset voltage and constant voltage time, and the constant current boosting reaches the preset voltage and constant voltage time, so that the anode foil is obtained in accordance with the corresponding embodiment.
Example 1
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 90 μm, and boiling in pure water at 100deg.C for 10 min;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution containing 0.5wt% of ethylene glycol and KOH for 10 minutes at 50 ℃ with the solution pH of 9.0;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 20wt% azelaic acid and 2wt% ammonium azelate at 85 ℃ to obtain a current density of 10mA cm -2 Constant current is boosted to 200V, and constant voltage is kept for 5 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 1 minute in an air atmosphere at 600 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in an aqueous solution of 20wt% azelaic acid and 2wt% azelaic acid ammonium at 85 ℃ with current density of 10mA cm -2 Constant current was boosted to 200V and kept at constant voltage for 1 minute to obtain an anode foil.
Example 2
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 90 μm, and boiling in pure water at 100deg.C for 10 min;
2) And (3) carrying out secondary pretreatment: the pretreated aluminum foil contains 1.0wt% of glycerol and Na 2 CO 3 In the mixed solution, the solution ph=10.0, soaking at 60 ℃ for 20 minutes;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 1wt% azelaic acid and 0.01wt% ammonium azelate at 85 ℃ to obtain a current density of 10mA cm -2 Constant current is boosted to 400V, constant voltageHolding for 5 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 1 minute in an air atmosphere at 600 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in an aqueous solution of 1wt% azelaic acid and 0.01wt% azelaic acid ammonium at 85 ℃, and the current density is 10mA cm -2 Constant current was boosted to 400V and constant voltage was maintained for 1 minute to obtain an anode foil.
Example 3
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 120 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution containing 2.0wt% of pentaerythritol and triethylamine for 30 minutes at the temperature of 65 ℃ with the pH of the solution being 11.0;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 20wt% boric acid and 0.01wt% ammonium pentaborate at 85 ℃ to obtain a current density of 50mA.cm -2 Constant current is boosted to 540V, and constant voltage is kept for 5 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 2 minutes in an air atmosphere at 500 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in an aqueous solution of 20 weight percent boric acid and 0.01 weight percent ammonium pentaborate at 85 ℃ with the current density of 50mA cm -2 Constant current was boosted to 540V and kept at constant pressure for 2 minutes to obtain an anode foil.
Example 4
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 120 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution containing 3.0wt% of glucose and ethylenediamine at the solution pH of 11.5 for 40 minutes at the temperature of 70 ℃;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 20wt% boric acid at 85 ℃ to obtain a current density of 50mA cm -2 Constant current is boosted to 630V, and constant voltage is kept for 10 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 2 minutes in an air atmosphere at 500 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in an aqueous solution of 20wt% boric acid at 85 ℃ with current density of 50mA cm -2 Constant current was boosted to 630V and kept at constant voltage for 2 minutes to obtain an anode foil.
Example 5
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 150 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution containing 4.0wt% of polyethylene glycol and hexamethylenetetramine at the solution pH of 12.0 and the temperature of 75 ℃ for 50 minutes;
3) Anodic oxidation: anodizing the pretreated aluminum foil in 5wt% boric acid water solution at 85 ℃ with current density of 70mA cm -2 Constant current is boosted to 720V, and constant voltage is kept for 10 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 5 minutes in an air atmosphere at 400 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in 5wt% boric acid water solution at 85 ℃ with current density of 70mA cm -2 Constant current was boosted to 720V and constant voltage was maintained for 5 minutes to obtain an anode foil.
Example 6
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 150 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution containing 5.0wt% of polyvinyl alcohol and ammonia water for 60 minutes at the temperature of 80 ℃ with the pH value of the solution being 13.0;
3) Anodic oxidation: anodizing the pretreated aluminum foil in 1wt% boric acid water solution at 85 ℃ to obtain a current density of 100mA cm -2 Constant current is boosted to 800V, and constant voltage is kept for 10 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 5 minutes in an air atmosphere at 400 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is treated with 1 weight percent boric acid waterAnodic oxidation complementary formation treatment is carried out in the solution at 85 ℃ and the current density is 100mA cm -2 Constant current was boosted to 800V and kept at constant voltage for 5 minutes to obtain an anode foil.
Example 7
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 120 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: immersing the pretreated aluminum foil in a mixed solution of triethylamine and ammonia water containing 2.0wt% of polyethylene glycol and having the same mass fraction for 60 minutes at the temperature of 80 ℃ with the pH value of the solution being 13.0;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 10wt% boric acid and 1wt% ammonium pentaborate at 85 ℃ to obtain a current density of 50mA.cm -2 Constant current is boosted to 400V, and constant voltage is kept for 10 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 5 minutes in an air atmosphere at 500 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is subjected to anodic oxidation repair treatment in an aqueous solution of 10wt% boric acid and 1wt% ammonium pentaborate at 85 ℃, and the current density is 50mA cm -2 Constant current was boosted to 400V and constant voltage was maintained for 5 minutes to obtain an anode foil.
Example 8
1) Pretreatment: adopting medium-high pressure corrosion foil with thickness of 120 μm, and boiling in pure water at 100 ℃ for 10 minutes;
2) And (3) carrying out secondary pretreatment: the pretreated aluminum foil contains 2.0wt% glucose, KOH and Na with equal mass fractions 2 CO 3 In the mixed solution, the solution ph=13.0, soaking at 80 ℃ for 60 minutes;
3) Anodic oxidation: anodizing the pretreated aluminum foil in an aqueous solution of 10wt% boric acid and 2wt% ammonium pentaborate at 85 ℃ to obtain a current density of 50mA.cm -2 Constant current is boosted to 400V, and constant voltage is kept for 10 minutes;
4) And (3) heat treatment: washing the aluminum foil after formation, and performing heat treatment for 5 minutes in an air atmosphere at 500 ℃;
5) And (3) supplementing: the aluminum foil after heat treatment is treated with 10 weight percent boric acid and 2 weight percent pentaboric acidAnodic oxidation repair treatment is carried out in an aqueous solution of ammonium at 85 ℃ to obtain a current density of 50 mA.cm -2 Constant current was boosted to 400V and constant voltage was maintained for 5 minutes to obtain an anode foil.
The anode foils obtained in the comparative examples and examples were subjected to an electrical property test and an anodic oxidation energy consumption test, the electrical property test being carried out in 15% wt ammonium pentaborate solution at 120hz,300mv according to industry standards. Withstand voltage test current of 0.4 mA.cm -2 Constant pressure time is 3min. The energy consumption test is obtained by recording the voltage, current and time of the anodic oxidation process through an oscilloscope and calculating through integration E= square UIt.
The results of the capacitance and energy consumption tests are shown in Table 1.
Table 1 electrical properties and energy consumption of anode foils obtained in examples and comparative examples
As can be seen from Table 1, the anode foil capacity of the example based on the method of the invention is basically consistent with that of the comparative example, the pressure resistance is higher, and the energy consumption of the anodic oxidation is saved by 6.6% -8.1%, which indicates that the anodic oxidation process of the aluminum foil obtained by the pretreatment of the invention is more energy-saving.
Based on the pretreatment effect, the pH of the solution should be greater than 9, and since the alkaline solution will corrode the aluminum foil, the pH of the solution will not exceed 13, the treatment temperature will not exceed 80 ℃ and the treatment time will not exceed 60 minutes, otherwise the transitional corrosion will cause a reduction in the capacity of the final anode foil.
Fig. 1 is a SEM image of a cross section of a hydrated oxide film after water treatment after alkali-corrosion inhibitor pretreatment, and fig. 2 shows that the pretreated aluminum foil has a three-layer structure, namely an outermost loose layer of aluminum hydroxide, an inner dense layer of hydrated alumina film and an inner aluminum core, respectively. Through practical measurement, the thickness of the hydrated oxide film obtained after the alkali-corrosion inhibitor pretreatment reaches 122nm, and the thickness of the hydrated oxide film after the water treatment is only 108nm, which indicates that the addition of organic/inorganic alkali can promote the chemical reaction of water and an aluminum core, increase the thickness of a compact layer of the hydrated oxide film and facilitate the transformation of the hydrated oxide film into an anodic oxide film, thereby reducing the anodic oxidation time, reducing the energy consumption and improving the anodic oxidation efficiency.
Fig. 3 is a cross-sectional SEM picture after anodic oxidation after alkali-corrosion inhibitor pretreatment, and fig. 4 is a cross-sectional SEM picture after anodic oxidation after water treatment, as can be seen from fig. 3 and 4, the dense layer and part of the loose layer of the hydrated oxide film after anodic oxidation are converted into an anodic oxide film. The aluminum foil still has a three-layer structure, namely the residual aluminum hydroxide of the outermost layer, the anodic oxide film of the inner layer and the aluminum core inside. Through practical measurement, the thickness of the anodic oxide film obtained after the alkali-corrosion inhibitor pretreatment reaches 397nm, and the thickness of the anodic oxide film obtained after the water treatment reaches 422nm, which shows that under the condition of similar pressure resistance, the breakdown field strength of the anodic oxide film obtained after the alkali-corrosion inhibitor pretreatment is higher, and the thickness of a compact layer of the hydrated oxide film is increased, so that the hydrated oxide film is favorably converted into the anodic oxide film, thereby reducing the anodic oxidation energy consumption and improving the anodic oxidation efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. The medium-high voltage anodic oxidation pretreatment method is characterized by comprising the following steps of:
step 1: treating the medium-high pressure corrosion foil with the thickness of 90-150 mu m in boiling water for 10 minutes to obtain an aluminum foil with a composite hydrated oxide film with a loose layer and a compact layer on the surface;
step 2: soaking the aluminum foil obtained in the step 1 in a solution containing alkali and an organic corrosion inhibitor, wherein the pH of the solution is 9-13, the treatment temperature is 50-80 ℃, and the treatment time is 10-60 minutes;
step 3: sequentially performing anodic oxidation, annealing and complementary formation on the treated corrosion foil to obtain an anode aluminum foil; wherein the anodic oxidation has a formation voltage of 200-800V and a formation current of 10-100 mA cm -2 The constant fluidization time is determined by the formation voltage and the formation current, and the constant fluidization time is 5-10 minutes; wherein the complementary process current is the same as the formation current, and the complementary time is 1-5 minutes.
2. The method for pre-treatment of medium-high pressure anodic oxidation according to claim 1, wherein the alkali is one or more of potassium hydroxide, sodium carbonate, triethylamine, ethylenediamine, hexamethylenetetramine and ammonia water; the organic corrosion inhibitor is one or more of ethylene glycol, glycerol, 1, 4-butanediol, pentaerythritol, glucose, polyethylene glycol and polyvinyl alcohol; wherein the solubility of the organic corrosion inhibitor is 0.5-5 wt%.
3. The medium-high voltage anodic oxidation pretreatment method according to claim 1, wherein the anodic oxidation electrolyte is one or more of 1wt% to 20wt% boric acid, 1wt% to 20wt% azelaic acid, 0.01wt% to 2wt% ammonium pentaborate, and 0.01wt% to 2wt% ammonium azelate.
4. The medium-high pressure anodizing treatment method according to claim 1, wherein the annealing temperature is 400-600 ℃ and the annealing time is 1-5 minutes.
5. Anode foil obtainable by a pretreatment process according to any of claims 1 to 4, characterized in that the oxide film is converted from a hydrated oxide film by two pretreatment processes.
6. An aluminum electrolytic capacitor, characterized in that the anode foil of claim 5 is used as the anode foil.
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