CN114411219A - High-acid-resistance low-pressure formed foil, preparation method and application thereof - Google Patents
High-acid-resistance low-pressure formed foil, preparation method and application thereof Download PDFInfo
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- CN114411219A CN114411219A CN202111664070.3A CN202111664070A CN114411219A CN 114411219 A CN114411219 A CN 114411219A CN 202111664070 A CN202111664070 A CN 202111664070A CN 114411219 A CN114411219 A CN 114411219A
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- 239000011888 foil Substances 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 125
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 125
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 65
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 30
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000010030 laminating Methods 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000003475 lamination Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 50
- 230000008439 repair process Effects 0.000 claims description 32
- 239000003990 capacitor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 26
- 239000001741 Ammonium adipate Substances 0.000 description 26
- 235000019293 ammonium adipate Nutrition 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000013589 supplement Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Abstract
The invention discloses a high-acid-resistance low-pressure formed foil and a preparation method and application thereof, wherein the preparation method comprises the following steps: the pretreatment sequentially comprises a first-stage pretreatment and a second-stage pretreatment; the first-stage pretreatment comprises the following specific steps: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, then performing first-stage laminating treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and performing high-temperature heat treatment to complete first-stage pretreatment; the second stage of pretreatment comprises the following specific steps: carrying out secondary lamination treatment on the aluminum foil subjected to the primary pretreatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the secondary pretreatment; also comprises multi-stage formation treatment and drying treatment. The high-acid-resistance low-pressure formed foil provided by the invention has the characteristics of high temperature resistance, long storage life, acid resistance and good corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of aluminum foil formation, and particularly relates to a high-acid-resistance low-pressure formed foil, a preparation method and application thereof.
Background
The manufacture of the aluminum foil by anodizing the low-voltage aluminum electrolytic capacitor needs to form a layer of compact oxide film on the surface of the aluminum foil as a working medium of the capacitor. The method usually employs a chemical conversion treatment method, in which a metal surface is chemically or electrochemically treated to obtain a coating film of a metal compound.
The inside of the aluminum electrolytic capacitor needs to be filled with electrolyte, and various acid additives exist in the electrolyte at present. The acid additives can corrode and damage the surface oxide film of the anode aluminum foil, and the service life of the aluminum electrolytic capacitor is influenced.
With the development of the electronic industry, electronic products are increasingly miniaturized, and thus various electronic components tend to develop in a microminiature direction. The volume of the aluminum electrolytic capacitor is mainly limited by the electrostatic capacity of the anode foil (i.e., formed foil). The higher the electrostatic capacity of the formed foil, the smaller the volume of the capacitor can be made. The capacitance of the formed foil is proportional to the dielectric constant and specific surface area of the oxide film and inversely proportional to the thickness of the oxide film.
The aluminum electrolytic capacitor is divided into a high-voltage aluminum electrolytic capacitor and a low-voltage aluminum electrolytic capacitor according to the use environment, and the high-voltage aluminum electrolytic capacitor and the low-voltage aluminum electrolytic capacitor have different microstructures of the oxide film of the formed foil and different manufacturing processes due to different electrical properties.
Currently, low-voltage aluminum electrolytic capacitors are anodized to form aluminum foil, and in the formation production process, in order to obtain an anode foil with high electrostatic capacity per unit area, the aluminum foil is generally formed by using a 15% ammonium adipate solution. Many reports are made about the high electrostatic capacity of the anode foil per unit area, but the formed oxide film has poor acid resistance, and cannot meet the requirements of various acid additives in the electrolyte for the aluminum electrolytic capacitor on the compactness and the corrosion resistance of the oxide film formed on the surface, and the produced aluminum electrolytic capacitor has the high temperature load at 85 ℃ and the storage life of only 1000 hours.
On the basis of not changing other parameters or designs, the acid resistance of the formed foil oxide film is improved, and the service life of the aluminum electrolytic capacitor can be prolonged. However, the formed foil prepared by the conventional technical method at present is difficult to meet the requirement of high acid resistance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the high-acid-resistance low-pressure formed foil, the preparation method and the application thereof, which are beneficial to improving the acid resistance of the formed foil, and improving the stability and the service life of the product.
The method is realized by the following technical scheme:
a preparation method of high-acid-resistance low-pressure formed foil is used for carrying out formation treatment on aluminum foil and comprises the following steps:
s1, preprocessing: the pretreatment sequentially comprises a first-stage pretreatment and a second-stage pretreatment;
the first-stage pretreatment comprises the following specific steps: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, then performing first-stage laminating treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and performing high-temperature heat treatment to complete first-stage pretreatment;
the second stage of pretreatment comprises the following specific steps: carrying out secondary lamination treatment on the aluminum foil subjected to the primary pretreatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the secondary pretreatment;
s2, multilevel formation treatment: carrying out multi-stage formation treatment on the aluminum foil subjected to the second-stage pretreatment;
s3, drying: and drying the aluminum foil subjected to the multistage formation treatment to obtain the high-acid-resistance low-pressure-resistance formed foil.
Specifically, in the first-stage pretreatment, in the step of treating the aluminum foil by placing the aluminum foil in a phosphoric acid solution with the mass concentration of 0.5-15%, the temperature of the phosphoric acid solution is controlled to be 60 +/-5 ℃, and the voltage is controlled to be 2 +/-0.5V; in the first-stage multi-tablet treatment in the ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, the control temperature of the ammonium dihydrogen phosphate aqueous solution is 82 +/-5 ℃, and the control voltage is 2 +/-0.5V.
In the second-stage pretreatment, in the second-stage tabletting treatment of the aluminum foil after the first-stage pretreatment in 0.02-2% ammonium dihydrogen phosphate aqueous solution, the temperature of the ammonium dihydrogen phosphate aqueous solution is controlled to be 85 +/-5 ℃, and the voltage is controlled to be 2 +/-0.5V.
Specifically, the multistage formation treatment is a four-stage formation treatment, and sequentially comprises a first stage formation treatment, a second stage formation treatment, a third stage formation treatment and a fourth stage formation treatment; wherein, the formation liquids of the first-stage formation treatment, the second-stage formation treatment, the third-stage formation treatment and the fourth-stage formation treatment are hexamethylenediamine solutions, and the temperature is controlled to be 82 +/-5 ℃.
Preferably, an in-liquid electricity feeding treatment is arranged between the second-stage formation treatment and the third-stage formation treatment, the control temperature of the in-liquid electricity feeding treatment is 30 +/-3 ℃, and the applied voltage is 1 +/-0.1V.
Preferably, a phosphoric acid treatment is provided at the rear end of the fourth formation treatment, and the control temperature of the phosphoric acid treatment is 60 ± 6 ℃.
Preferably, a primary repair treatment and a final repair treatment are further provided, wherein the formation liquid of the primary repair treatment is a hexamethylenediamine solution, and the temperature is controlled to be 82 +/-5 ℃; the formation liquid for final repair treatment is ammonium dihydrogen phosphate aqueous solution, and the temperature is controlled to be 85 +/-5 ℃.
Preferably, a heat treatment is arranged between the primary repair treatment and the final repair treatment, and the temperature of the heat treatment is 460 +/-40 ℃.
The invention also provides the high-acid-resistance low-pressure formed foil prepared by the method.
The invention also provides application of the high-acid-resistance low-voltage formed foil in a high-acid-resistance low-voltage aluminum electrolytic capacitor.
Compared with the prior art, the invention has the advantages and effects that:
1. according to the technical scheme, the aluminum foil is subjected to two times of pre-formation treatment at the front end of the formation process, an aluminum orthophosphate structure with excellent performance is formed on the outer surface of the aluminum foil, and the oxide film can be repaired by defects and cracks generated on the surface of the oxide film during high-temperature transformation, so that the acid resistance of the oxide film of the anode foil is solved on the basis of high electrostatic capacity of the unit area of the anode foil, and the 85-DEG C high-temperature load and the storage life of the produced aluminum electrolytic capacitor are guaranteed to reach 5000 hours;
2. according to the technical scheme, two times of repair treatment are adopted, and heat treatment is added between the primary repair treatment and the final repair treatment, so that the repair film layer of the primary repair treatment can be cured, and then the final repair treatment is carried out for supplement, so that the defects in the oxide film can be better repaired;
3. according to the technical scheme, after the final repair treatment, the product can be obtained by directly drying without water washing and heat treatment, so that energy for heat treatment again is saved, the balance of ammonium dihydrogen phosphate in the final repair treatment can be protected by phosphate ions to form a film after the drying treatment, and the surface of the film can form solidified phosphate, so that the performance of the formed foil is effectively improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic view of a pretreatment process in example 1 of the present invention;
FIG. 2 is a schematic system diagram of the preparation process of example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 2, fig. 2 is a system diagram of the preparation method of example 1, and fig. 1 is a schematic diagram of a pretreatment process therein, wherein PA is phosphoric acid, PM is ammonium dihydrogen phosphate, AD is ammonium adipate, and SF is in-liquid power supply.
First-stage pretreatment: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 10% for treatment, wherein the temperature is 60 ℃, and the applied voltage is 2V; then, carrying out first-stage compound sheet treatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature is 82 ℃, and the applied voltage is 2V; then high-temperature heat treatment is carried out, the temperature of the high-temperature treatment is 460 ℃, and the first-stage pretreatment is completed;
second-stage pretreatment: carrying out second-stage laminating treatment on the aluminum foil subjected to the first-stage pretreatment in a 1% ammonium dihydrogen phosphate aqueous solution, wherein the temperature of the second-stage laminating treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first-stage formation treatment (F1): putting the aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for first-stage formation treatment for 10 minutes at 1500A and 2V of applied voltage to obtain a first-stage formed aluminum foil;
second-stage formation treatment (F2): putting the first-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for second-stage formed treatment, wherein the time is 10 minutes, the current is 1200A, and the applied voltage is 2V, so as to obtain a second-stage formed aluminum foil;
in-liquid electrification treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, the secondary formed aluminum foil is subjected to current supplement treatment in a liquid feed cell;
third-stage formation treatment (F3): putting the second-level formed aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation liquid with the temperature of 82 ℃ and the concentration of 20% for third-level formed treatment, wherein the time is 30 minutes, the current is 600A, and the applied voltage is 4V, so that a third-level formed aluminum foil is obtained;
fourth formation treatment (F4): putting the three-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for three-stage formed treatment for 30 minutes at 500A of current and 5V of applied voltage to obtain a four-stage formed aluminum foil;
phosphoric acid treatment (P treatment): putting the four-stage formed aluminum foil into phosphoric acid preparation liquid with the temperature of 60 ℃ and the concentration of 5% for P treatment for 5 minutes to obtain a P-treated formed aluminum foil;
primary repair treatment: the P is processed into the aluminum foil and is put into 3 percent ammonium adipate solution at the temperature of 82 ℃ for 10 minutes at the voltage of 4V, and a primary repaired formed aluminum foil is obtained;
final repair treatment: putting the primary repaired formed aluminum foil into 3% ammonium dihydrogen phosphate preparation solution at the temperature of 85 ℃ for final repair treatment for 10 minutes at the voltage of 4V to obtain a final repaired formed aluminum foil;
and (3) drying treatment: and drying the final-stage repaired formed aluminum foil at the drying temperature of 170 ℃ to obtain the high-acid-resistance low-pressure formed foil.
Example 2
First-stage pretreatment: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 0.5% for treatment, wherein the temperature is 60 ℃, and the applied voltage is 2V; then, carrying out first-stage compound sheet treatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02%, wherein the temperature is 82 ℃, and the applied voltage is 2V; then high-temperature heat treatment is carried out, the temperature of the high-temperature treatment is 460 ℃, and the first-stage pretreatment is completed;
second-stage pretreatment: carrying out second-stage laminating treatment on the aluminum foil subjected to the first-stage pretreatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02%, wherein the temperature of the second-stage laminating treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first-stage formation treatment (F1): putting the aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for first-stage formation treatment for 10 minutes at 1500A and 2V of applied voltage to obtain a first-stage formed aluminum foil;
second-stage formation treatment (F2): putting the first-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for second-stage formed treatment, wherein the time is 10 minutes, the current is 1200A, and the applied voltage is 2V, so as to obtain a second-stage formed aluminum foil;
in-liquid electrification treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, the secondary formed aluminum foil is subjected to current supplement treatment in a liquid feed cell;
third-stage formation treatment (F3): putting the second-level formed aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation liquid with the temperature of 82 ℃ and the concentration of 20% for third-level formed treatment, wherein the time is 30 minutes, the current is 600A, and the applied voltage is 4V, so that a third-level formed aluminum foil is obtained;
fourth formation treatment (F4): putting the three-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for three-stage formed treatment for 30 minutes at 500A of current and 5V of applied voltage to obtain a four-stage formed aluminum foil;
phosphoric acid treatment (P treatment): putting the four-stage formed aluminum foil into phosphoric acid preparation liquid with the temperature of 60 ℃ and the concentration of 5% for P treatment for 5 minutes to obtain a P-treated formed aluminum foil;
primary repair treatment: the P is processed into the aluminum foil and is put into 3 percent ammonium adipate solution at the temperature of 82 ℃ for 10 minutes at the voltage of 4V, and a primary repaired formed aluminum foil is obtained;
final repair treatment: putting the primary repaired formed aluminum foil into 3% ammonium dihydrogen phosphate preparation solution at the temperature of 85 ℃ for final repair treatment for 10 minutes at the voltage of 4V to obtain a final repaired formed aluminum foil;
and (3) drying treatment: and drying the final-stage repaired formed aluminum foil at the drying temperature of 170 ℃ to obtain the high-acid-resistance low-pressure formed foil.
Example 3
First-stage pretreatment: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 15% for treatment, wherein the temperature is 60 ℃, and the applied voltage is 2V; then, carrying out first-stage compound sheet treatment in 2 mass percent ammonium dihydrogen phosphate aqueous solution at the temperature of 82 ℃ and the applied voltage of 2V; then high-temperature heat treatment is carried out, the temperature of the high-temperature treatment is 460 ℃, and the first-stage pretreatment is completed;
second-stage pretreatment: carrying out second-stage laminating treatment on the aluminum foil subjected to the first-stage pretreatment in 2% ammonium dihydrogen phosphate aqueous solution, wherein the temperature of the second-stage laminating treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first-stage formation treatment (F1): putting the aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for first-stage formation treatment for 10 minutes at 1500A and 2V of applied voltage to obtain a first-stage formed aluminum foil;
second-stage formation treatment (F2): putting the first-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for second-stage formed treatment, wherein the time is 10 minutes, the current is 1200A, and the applied voltage is 2V, so as to obtain a second-stage formed aluminum foil;
in-liquid electrification treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, the secondary formed aluminum foil is subjected to current supplement treatment in a liquid feed cell;
third-stage formation treatment (F3): putting the second-level formed aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation liquid with the temperature of 82 ℃ and the concentration of 20% for third-level formed treatment, wherein the time is 30 minutes, the current is 600A, and the applied voltage is 4V, so that a third-level formed aluminum foil is obtained;
fourth formation treatment (F4): putting the three-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for three-stage formed treatment for 30 minutes at 500A of current and 5V of applied voltage to obtain a four-stage formed aluminum foil;
phosphoric acid treatment (P treatment): putting the four-stage formed aluminum foil into phosphoric acid preparation liquid with the temperature of 60 ℃ and the concentration of 5% for P treatment for 5 minutes to obtain a P-treated formed aluminum foil;
primary repair treatment: the P is processed into the aluminum foil and is put into 3 percent ammonium adipate solution at the temperature of 82 ℃ for 10 minutes at the voltage of 4V, and a primary repaired formed aluminum foil is obtained;
final repair treatment: putting the primary repaired formed aluminum foil into 3% ammonium dihydrogen phosphate preparation solution at the temperature of 85 ℃ for final repair treatment for 10 minutes at the voltage of 4V to obtain a final repaired formed aluminum foil;
and (3) drying treatment: and drying the final-stage repaired formed aluminum foil at the drying temperature of 170 ℃ to obtain the high-acid-resistance low-pressure formed foil.
Example 4
First-stage pretreatment: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 10% for treatment, wherein the temperature is 60 ℃, and the applied voltage is 2V; then, carrying out first-stage compound sheet treatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature is 82 ℃, and the applied voltage is 2V; then high-temperature heat treatment is carried out, the temperature of the high-temperature treatment is 460 ℃, and the first-stage pretreatment is completed;
second-stage pretreatment: carrying out second-stage laminating treatment on the aluminum foil subjected to the first-stage pretreatment in a 1% ammonium dihydrogen phosphate aqueous solution, wherein the temperature of the second-stage laminating treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first-stage formation treatment (F1): putting the aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for first-stage formation treatment for 10 minutes at 1500A and 2V of applied voltage to obtain a first-stage formed aluminum foil;
second-stage formation treatment (F2): putting the first-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for second-stage formed treatment, wherein the time is 10 minutes, the current is 1200A, and the applied voltage is 2V, so as to obtain a second-stage formed aluminum foil;
in-liquid electrification treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, the secondary formed aluminum foil is subjected to current supplement treatment in a liquid feed cell;
third-stage formation treatment (F3): putting the second-level formed aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation liquid with the temperature of 82 ℃ and the concentration of 20% for third-level formed treatment, wherein the time is 30 minutes, the current is 600A, and the applied voltage is 4V, so that a third-level formed aluminum foil is obtained;
fourth formation treatment (F4): putting the three-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for three-stage formed treatment for 30 minutes at 500A of current and 5V of applied voltage to obtain a four-stage formed aluminum foil;
and (3) drying treatment: and drying the four-stage formed aluminum foil at the drying temperature of 170 ℃ to obtain the high-acid-resistance low-pressure formed foil.
Comparative example 1
First-stage formation treatment (F1): putting the aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for first-stage formation treatment for 10 minutes at 1500A and 2V of applied voltage to obtain a first-stage formed aluminum foil;
second-stage formation treatment (F2): putting the first-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for second-stage formed treatment, wherein the time is 10 minutes, the current is 1200A, and the applied voltage is 2V, so as to obtain a second-stage formed aluminum foil;
in-liquid electrification treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, the secondary formed aluminum foil is subjected to current supplement treatment in a liquid feed cell;
third-stage formation treatment (F3): putting the second-level formed aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation liquid with the temperature of 82 ℃ and the concentration of 20% for third-level formed treatment, wherein the time is 30 minutes, the current is 600A, and the applied voltage is 4V, so that a third-level formed aluminum foil is obtained;
fourth formation treatment (F4): putting the three-stage formed aluminum foil into 20% ammonium adipate preparation liquid at 82 ℃ for three-stage formed treatment for 30 minutes at 500A of current and 5V of applied voltage to obtain a four-stage formed aluminum foil;
phosphoric acid treatment (P treatment): putting the four-stage formed aluminum foil into phosphoric acid preparation liquid with the temperature of 60 ℃ and the concentration of 5% for P treatment for 5 minutes to obtain a P-treated formed aluminum foil;
primary repair treatment: the P is processed into the aluminum foil and is put into 3 percent ammonium adipate solution at the temperature of 82 ℃ for 10 minutes at the voltage of 4V, and a primary repaired formed aluminum foil is obtained;
final repair treatment: putting the primary repaired formed aluminum foil into 3% ammonium dihydrogen phosphate preparation solution at the temperature of 85 ℃ for final repair treatment for 10 minutes at the voltage of 4V to obtain a final repaired formed aluminum foil;
and (3) drying treatment: and drying the final-stage repaired formed aluminum foil at the drying temperature of 170 ℃ to obtain the low-pressure formed foil.
Experimental example 1 high temperature standing test
The formed foils of the examples and comparative examples were subjected to a high temperature standing test at 105. + -. 3 ℃. The performance parameters of the formed foil before high-temperature standing (0 hour) and the performance parameters of the formed foil after 1000 hours of high-temperature standing are recorded. Tables 1 and 2 show the results of the tests, where cap is the electrostatic capacity, Δ% is the value of change in electrostatic capacity, and Δ% (electrostatic capacity measured after 1000 hours at high temperature — electrostatic capacity measured after 0 hours at high temperature)/electrostatic capacity measured after 0 hours at high temperature × 100%.
TABLE 1 high temperature standing test results (0 hr)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 206.6 | 207.8 | 198.5 | 202.2 | 197.2 |
| Δ％ | 0 | 0 | 0 | 0 | 0 |
TABLE 2 high temperature standing test results (1000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 201.4 | 201.9 | 192.9 | 197.0 | 190.1 |
| Δ％ | -2.52 | -2.83 | -2.82 | -2.57 | -3.6 |
As can be seen from tables 1 and 2, the change value of the electrostatic capacity of comparative example 1 after being placed at high temperature for 1000 hours is significantly higher than that of examples 1 to 4, and it can be shown that the high-acid-resistance low-voltage formed foil provided by the invention has high-temperature stability and long service life.
Experimental example 2 high-temperature load life test
The formed foils of the examples and comparative examples were subjected to a high temperature load life test, and the performance parameters of the formed foils after being subjected to high temperature load life tests for 0 hour, 1000 hours, 2000 hours, 5000 hours and 10000 hours at temperatures of 105 ± 3 ℃ were recorded, and the results are shown in the following table, where cap is electrostatic capacity, Δ% is a change in electrostatic capacity, and Δ% (electrostatic capacity measured after x hours of the high temperature load life test — electrostatic capacity measured at 0 hour of the high temperature load life test)/electrostatic capacity measured at 0 hour of the high temperature load life test × 100%; wherein x is 0, 1000, 2000, 5000 or 10000.
TABLE 3 high temperature load Life test (0 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 206.4 | 207.7 | 198.4 | 202.1 | 197.0 |
| Δ％ | 0 | 0 | 0 | 0 | 0 |
TABLE 4 high temperature load Life test (1000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 204.6 | 205.9 | 196.8 | 200.3 | 194.8 |
| Δ％ | -0.87 | -0.87 | -0.81 | -0.89 | -1.12 |
TABLE 5 high temperature load Life test (2000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 203.8 | 204.4 | 195.2 | 198.5 | 191.2 |
| Δ％ | -1.25 | -1.59 | -1.61 | -1.78 | -2.94 |
TABLE 6 high temperature load Life test (5000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 200.2 | 200.7 | 191.4 | 194.4 | 183.5 |
| Δ％ | -3.00 | -3.37 | -3.53 | -3.81 | -6.85 |
TABLE 7 high temperature load Life test (10000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm2) | 195.9 | 197.0 | 188.4 | 191.0 | 174.1 |
| Δ％ | -5.08 | -5.15 | -5.04 | -5.49 | -11.62 |
The data show that the high-temperature resistance of the low-voltage formed foil can be effectively improved by carrying out the pre-formation treatment twice at the front end of the formation process, the storage life is also prolonged, and the performance after the high-temperature load test of 10000 hours at high temperature can still be suitable for the aluminum electrolytic capacitor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of high-acid-resistance low-pressure formed foil is used for carrying out formation treatment on aluminum foil and comprises the following steps:
s1, preprocessing: the pretreatment sequentially comprises a first-stage pretreatment and a second-stage pretreatment;
the first-stage pretreatment comprises the following specific steps: placing the aluminum foil in a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, then performing first-stage laminating treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and performing high-temperature heat treatment to complete first-stage pretreatment;
the second stage of pretreatment comprises the following specific steps: carrying out secondary lamination treatment on the aluminum foil subjected to the primary pretreatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the secondary pretreatment;
s2, multilevel formation treatment: carrying out multi-stage formation treatment on the aluminum foil subjected to the second-stage pretreatment;
s3, drying: and drying the aluminum foil subjected to the multistage formation treatment to obtain the high-acid-resistance low-pressure-resistance formed foil.
2. The method for preparing high acid resistance low pressure formed foil according to claim 1, wherein in the first stage pretreatment, the aluminum foil is treated by placing the aluminum foil in a phosphoric acid solution with a mass concentration of 0.5-15%, the temperature of the phosphoric acid solution is controlled to be 60 ± 5 ℃, and the voltage is controlled to be 2 ± 0.5V; in the first-stage multi-tablet treatment in the ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, the control temperature of the ammonium dihydrogen phosphate aqueous solution is 82 +/-5 ℃, and the control voltage is 2 +/-0.5V.
3. The method for preparing high acid resistance low pressure formed foil according to claim 1, wherein in the second stage pretreatment, the aluminum foil after the first stage pretreatment is subjected to second stage re-sheeting treatment in 0.02-2% by mass of ammonium dihydrogen phosphate aqueous solution, the temperature of the ammonium dihydrogen phosphate aqueous solution is controlled to be 85 ± 5 ℃, and the voltage is controlled to be 2 ± 0.5V.
4. The method for preparing high acid resistance low pressure chemical foil according to claim 1, wherein the multi-stage chemical conversion treatment is a four-stage chemical conversion treatment, which comprises a first stage chemical conversion treatment, a second stage chemical conversion treatment, a third stage chemical conversion treatment and a fourth stage chemical conversion treatment in sequence; wherein, the formation liquids of the first-stage formation treatment, the second-stage formation treatment, the third-stage formation treatment and the fourth-stage formation treatment are hexamethylenediamine solutions, and the temperature is controlled to be 82 +/-5 ℃.
5. The method for preparing high acid resistance low pressure formed foil according to claim 4, wherein an in-liquid feeding treatment is provided between the second-stage formation treatment and the third-stage formation treatment, the temperature of the in-liquid feeding treatment is controlled to be 30 ± 3 ℃, and the applied voltage is 1 ± 0.1V.
6. The method for producing a high acid resistance low pressure formed foil according to claim 5, wherein a phosphoric acid treatment is provided at a rear end of the fourth formation treatment, and a control temperature of the phosphoric acid treatment is 60 ± 6 ℃.
7. The method for preparing high acid resistance low pressure formed foil according to claim 1, wherein a primary repair treatment and a final repair treatment are further provided, wherein a forming liquid of the primary repair treatment is a hexamethylenediamine solution, and the temperature is controlled to be 82 ± 5 ℃; the formation liquid for final repair treatment is ammonium dihydrogen phosphate aqueous solution, and the temperature is controlled to be 85 +/-5 ℃.
8. The method for preparing high acid resistance low pressure formed foil according to claim 7, wherein a heat treatment is provided between the primary repair treatment and the final repair treatment, the temperature of the heat treatment being 460 ± 40 ℃.
9. A high acid resistant low pressure formed foil, characterized in that it is produced according to the production method of any one of claims 1 to 8.
10. Use of a high acid resistance low voltage formed foil according to claim 9 in a high acid resistance low voltage aluminum electrolytic capacitor.
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