CN114411219B - High acid-resistant low-pressure formed foil, preparation method and application thereof - Google Patents
High acid-resistant low-pressure formed foil, preparation method and application thereof Download PDFInfo
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- CN114411219B CN114411219B CN202111664070.3A CN202111664070A CN114411219B CN 114411219 B CN114411219 B CN 114411219B CN 202111664070 A CN202111664070 A CN 202111664070A CN 114411219 B CN114411219 B CN 114411219B
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- 239000011888 foil Substances 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002253 acid Substances 0.000 title claims abstract description 34
- 238000011282 treatment Methods 0.000 claims abstract description 137
- 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 106
- 239000000243 solution Substances 0.000 claims abstract description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 32
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 28
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 230000008439 repair process Effects 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- 239000003990 capacitor Substances 0.000 claims description 19
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 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 20
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- 230000001502 supplementing effect Effects 0.000 description 6
- 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
- 230000002378 acidificating effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 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
Classifications
-
- 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 application discloses a high acid resistance low pressure formed foil, a preparation method and application thereof, wherein the preparation method comprises the following steps of: the pretreatment comprises a first-stage pretreatment and a second-stage pretreatment in sequence; the specific steps of the first-stage pretreatment are as follows: placing aluminum foil into a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, then performing first-stage compound tablet treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and then performing high-temperature heat treatment to complete first-stage pretreatment; the specific steps of the second-stage pretreatment are as follows: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the second-stage pretreatment; the method also comprises a multistage formation treatment and a drying treatment. The high acid resistance low pressure formed foil provided by the application has the characteristics of high temperature resistance, long storage life, acid resistance and good corrosion resistance.
Description
Technical Field
The application belongs to the technical field of aluminum foil formation, and particularly relates to a high acid resistance low-pressure formation foil, a preparation method and application thereof.
Background
The low-voltage aluminum electrolytic capacitor is anodized to be manufactured into aluminum foil, and a compact oxide film is required to be formed on the surface of the aluminum foil to be used as a working medium of the capacitor. The method is usually a chemical treatment method, wherein the chemical treatment is a chemical or electrochemical treatment of the metal surface to obtain a coating of the metal compound.
The inside of the aluminum electrolytic capacitor needs to be filled with electrolyte, and various acidic additives exist in the electrolyte at present. These acidic additives can cause corrosion damage to the surface oxide film of the anode aluminum foil, affecting the service life of the aluminum electrolytic capacitor.
With the development of the electronic industry, electronic products are becoming smaller and smaller, so various electronic components tend to be miniaturized. The volume of an aluminum electrolytic capacitor is mainly limited by the electrostatic capacity of the anode foil (i.e., the formation foil). The higher the electrostatic capacity of the formed foil, the smaller the volume of the capacitor can be made. The capacitance of the formation 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.
Aluminum electrolytic capacitors are classified into high-voltage aluminum electrolytic capacitors and low-voltage aluminum electrolytic capacitors according to the use environment, and the high-voltage aluminum electrolytic capacitors and the low-voltage aluminum electrolytic capacitors differ in the electric properties, and the microstructure of the oxide film formed into a foil and the manufacturing process.
In the current low-voltage aluminum electrolytic capacitor, aluminum foil is anodized, and in the process of formation, 15% ammonium adipate is generally dissolved to obtain an anode foil with high electrostatic capacity per unit area. There are many reports about the research of the high electrostatic capacity of the single-unit area anode foil, but the acid resistance of the formed oxide film is poor, the requirements of various acid additives in the electrolyte for the aluminum electrolytic capacitor on the compactness and corrosion resistance of the oxide film formed on the surface cannot be met, and the high-temperature load and the storage life of the produced aluminum electrolytic capacitor at 85 ℃ are 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 is difficult to meet the requirement of high acid resistance.
Disclosure of Invention
In order to overcome the defects in the prior art, the application 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 products.
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, pretreatment: the pretreatment comprises a first-stage pretreatment and a second-stage pretreatment in sequence;
the specific steps of the first-stage pretreatment are as follows: placing aluminum foil into a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, then performing first-stage compound tablet treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and then performing high-temperature heat treatment to complete first-stage pretreatment;
the specific steps of the second-stage pretreatment are as follows: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the second-stage pretreatment;
s2, multistage formation treatment: carrying out multistage 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-resistant low-pressure formation foil.
Specifically, in the first-stage pretreatment, the aluminum foil is placed in a phosphoric acid solution with the mass concentration of 0.5-15% for treatment, 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 compound treatment in 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, the aluminum foil subjected to the first-stage pretreatment is subjected to second-stage compound treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, wherein 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 multi-stage formation process is a four-stage formation process, and sequentially comprises a first-stage formation process, a second-stage formation process, a third-stage formation process and a fourth-stage formation process; wherein the formation liquid of the first, second, third and fourth stage formation treatments is hexamethylenediamine solution, and the temperature is controlled to be 82+/-5 ℃.
Preferably, an in-liquid power feeding process is provided between the second and third chemical conversion processes, the control temperature of the in-liquid power feeding process is 30±3 ℃, and the applied voltage is 1±0.1V.
Preferably, a phosphoric acid treatment is arranged at the rear end of the fourth-stage formation treatment, and the control temperature of the phosphoric acid treatment is 60+/-6 ℃.
Preferably, the method is also provided with primary repair treatment and final repair treatment, wherein the formation liquid of the primary repair treatment is hexamethylenediamine solution, and the temperature is controlled to be 82+/-5 ℃; the formation liquid of the final repair treatment is ammonium dihydrogen phosphate aqueous solution, and the temperature is controlled to be 85+/-5 ℃.
Preferably, a heat treatment is provided between the primary repair treatment and the final repair treatment, and the temperature of the heat treatment is 460±40 ℃.
The application also provides the high acid resistance low pressure formed foil prepared by the method.
The application also provides application of the high acid-resistant low-voltage formation foil in a high acid-resistant low-voltage aluminum electrolytic capacitor.
Compared with the prior art, the application has the advantages and effects that:
1. according to the technical scheme, at the front end of the formation process, the aluminum foil is subjected to twice pre-formation treatment, an aluminum orthophosphate structure with excellent performance is formed on the outer surface of the aluminum foil, defects and cracks generated on the surface of an oxide film during high-temperature transformation can be repaired into the oxide film, and the acid resistance of the anode foil oxide film is solved on the basis of high electrostatic capacity of the unit area of the anode foil, so that the high-temperature load at 85 ℃ and the storage life of the produced aluminum electrolytic capacitor are ensured to be 5000 hours;
2. according to the technical scheme, the two repair treatments are adopted, and the 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 supplementing, so that the defects in the oxide film can be better repaired;
3. according to the technical scheme, after the final repairing treatment, water washing and heat treatment are not needed, the product can be obtained by directly drying treatment, the energy for heat treatment again is saved, the rest of ammonium dihydrogen phosphate in the final repairing treatment can be used for protecting the chemical film by phosphate ions after the drying treatment, and the surface of the chemical film forms cured phosphate, so that the performance of the chemical foil is effectively improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the pretreatment process in example 1 of the present application;
FIG. 2 is a schematic system diagram of the preparation method of example 1 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
Referring to fig. 2, fig. 2 is a schematic system diagram of the preparation method of example 1, and fig. 1 is a schematic pretreatment process in which PA is phosphoric acid, PM is monoammonium phosphate, AD is ammonium adipate, and SF is in-liquid power supply.
First-stage pretreatment: placing the aluminum foil into 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 tablet treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature is 82 ℃, and the applied voltage is 2V; then carrying out high-temperature heat treatment, wherein the temperature of the high-temperature heat treatment is 460 ℃, and completing the first-stage pretreatment;
second stage pretreatment: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature of the second-stage compound treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first stage formation treatment (F1): placing the aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for primary formation treatment for 10 minutes, wherein the current is 1500A, and the voltage is 2V to obtain primary formation aluminum foil;
second stage formation treatment (F2): placing the primary formed aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for secondary formation treatment, wherein the time is 10 minutes, the current is 1200A, and the voltage is applied to the aluminum foil to obtain the secondary formed aluminum foil;
and (3) in-liquid power supply treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, carrying out current supplementing treatment on the secondary aluminum foil in a liquid power supply tank;
third stage formation treatment (F3): placing the secondary formation aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20% for three-level formation treatment, wherein the time is 30 minutes, the current is 600A, and the voltage is applied to the solution to obtain the three-level formation aluminum foil;
fourth stage formation process (F4): placing the tertiary aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for tertiary formation treatment for 30 minutes, wherein the current is 500A, and the voltage is 5V to obtain a quaternary aluminum foil;
phosphoric acid treatment (P treatment): placing the four-stage formed aluminum foil into phosphoric acid preparation solution with the temperature of 60 ℃ and the concentration of 5 percent for P treatment for 5 minutes to obtain P-treated formed aluminum foil;
primary repair treatment: placing the P-treated aluminum foil into an ammonium adipate solution with the temperature of 82 ℃ and the concentration of 3 percent for 10 minutes and the voltage of 4V to obtain a primary repaired aluminum foil;
and (3) final repairing: placing the primary repair formation aluminum foil into ammonium dihydrogen phosphate preparation solution with the temperature of 85 ℃ and the concentration of 3 percent for final repair treatment for 10 minutes and with the voltage of 4V to obtain final repair formation aluminum foil;
and (3) drying: and (3) drying the final-stage repaired formed aluminum foil at 170 ℃ to obtain the high acid-resistant low-pressure formed foil.
Example 2
First-stage pretreatment: placing the aluminum foil into 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 tablet treatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02 percent, wherein the temperature is 82 ℃, and the applied voltage is 2V; then carrying out high-temperature heat treatment, wherein the temperature of the high-temperature heat treatment is 460 ℃, and completing the first-stage pretreatment;
second stage pretreatment: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02%, wherein the temperature of the second-stage compound treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first stage formation treatment (F1): placing the aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for primary formation treatment for 10 minutes, wherein the current is 1500A, and the voltage is 2V to obtain primary formation aluminum foil;
second stage formation treatment (F2): placing the primary formed aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for secondary formation treatment, wherein the time is 10 minutes, the current is 1200A, and the voltage is applied to the aluminum foil to obtain the secondary formed aluminum foil;
and (3) in-liquid power supply treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, carrying out current supplementing treatment on the secondary aluminum foil in a liquid power supply tank;
third stage formation treatment (F3): placing the secondary formation aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20% for three-level formation treatment, wherein the time is 30 minutes, the current is 600A, and the voltage is applied to the solution to obtain the three-level formation aluminum foil;
fourth stage formation process (F4): placing the tertiary aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for tertiary formation treatment for 30 minutes, wherein the current is 500A, and the voltage is 5V to obtain a quaternary aluminum foil;
phosphoric acid treatment (P treatment): placing the four-stage formed aluminum foil into phosphoric acid preparation solution with the temperature of 60 ℃ and the concentration of 5 percent for P treatment for 5 minutes to obtain P-treated formed aluminum foil;
primary repair treatment: placing the P-treated aluminum foil into an ammonium adipate solution with the temperature of 82 ℃ and the concentration of 3 percent for 10 minutes and the voltage of 4V to obtain a primary repaired aluminum foil;
and (3) final repairing: placing the primary repair formation aluminum foil into ammonium dihydrogen phosphate preparation solution with the temperature of 85 ℃ and the concentration of 3 percent for final repair treatment for 10 minutes and with the voltage of 4V to obtain final repair formation aluminum foil;
and (3) drying: and (3) drying the final-stage repaired formed aluminum foil at 170 ℃ to obtain the high acid-resistant low-pressure formed foil.
Example 3
First-stage pretreatment: placing the aluminum foil into 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 tablet treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 2 percent, wherein the temperature is 82 ℃, and the applied voltage is 2V; then carrying out high-temperature heat treatment, wherein the temperature of the high-temperature heat treatment is 460 ℃, and completing the first-stage pretreatment;
second stage pretreatment: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 2%, wherein the temperature of the second-stage compound treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first stage formation treatment (F1): placing the aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for primary formation treatment for 10 minutes, wherein the current is 1500A, and the voltage is 2V to obtain primary formation aluminum foil;
second stage formation treatment (F2): placing the primary formed aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for secondary formation treatment, wherein the time is 10 minutes, the current is 1200A, and the voltage is applied to the aluminum foil to obtain the secondary formed aluminum foil;
and (3) in-liquid power supply treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, carrying out current supplementing treatment on the secondary aluminum foil in a liquid power supply tank;
third stage formation treatment (F3): placing the secondary formation aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20% for three-level formation treatment, wherein the time is 30 minutes, the current is 600A, and the voltage is applied to the solution to obtain the three-level formation aluminum foil;
fourth stage formation process (F4): placing the tertiary aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for tertiary formation treatment for 30 minutes, wherein the current is 500A, and the voltage is 5V to obtain a quaternary aluminum foil;
phosphoric acid treatment (P treatment): placing the four-stage formed aluminum foil into phosphoric acid preparation solution with the temperature of 60 ℃ and the concentration of 5 percent for P treatment for 5 minutes to obtain P-treated formed aluminum foil;
primary repair treatment: placing the P-treated aluminum foil into an ammonium adipate solution with the temperature of 82 ℃ and the concentration of 3 percent for 10 minutes and the voltage of 4V to obtain a primary repaired aluminum foil;
and (3) final repairing: placing the primary repair formation aluminum foil into ammonium dihydrogen phosphate preparation solution with the temperature of 85 ℃ and the concentration of 3 percent for final repair treatment for 10 minutes and with the voltage of 4V to obtain final repair formation aluminum foil;
and (3) drying: and (3) drying the final-stage repaired formed aluminum foil at 170 ℃ to obtain the high acid-resistant low-pressure formed foil.
Example 4
First-stage pretreatment: placing the aluminum foil into 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 tablet treatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature is 82 ℃, and the applied voltage is 2V; then carrying out high-temperature heat treatment, wherein the temperature of the high-temperature heat treatment is 460 ℃, and completing the first-stage pretreatment;
second stage pretreatment: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 1%, wherein the temperature of the second-stage compound treatment is 85 ℃, and the applied voltage is 2V; after cleaning and drying, finishing the second-stage pretreatment;
first stage formation treatment (F1): placing the aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for primary formation treatment for 10 minutes, wherein the current is 1500A, and the voltage is 2V to obtain primary formation aluminum foil;
second stage formation treatment (F2): placing the primary formed aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for secondary formation treatment, wherein the time is 10 minutes, the current is 1200A, and the voltage is applied to the aluminum foil to obtain the secondary formed aluminum foil;
and (3) in-liquid power supply treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, carrying out current supplementing treatment on the secondary aluminum foil in a liquid power supply tank;
third stage formation treatment (F3): placing the secondary formation aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20% for three-level formation treatment, wherein the time is 30 minutes, the current is 600A, and the voltage is applied to the solution to obtain the three-level formation aluminum foil;
fourth stage formation process (F4): placing the tertiary aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for tertiary formation treatment for 30 minutes, wherein the current is 500A, and the voltage is 5V to obtain a quaternary aluminum foil;
and (3) drying: and drying the four-stage formed aluminum foil at 170 ℃ to obtain the high acid-resistant low-pressure formed foil.
Comparative example 1
First stage formation treatment (F1): placing the aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for primary formation treatment for 10 minutes, wherein the current is 1500A, and the voltage is 2V to obtain primary formation aluminum foil;
second stage formation treatment (F2): placing the primary formed aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for secondary formation treatment, wherein the time is 10 minutes, the current is 1200A, and the voltage is applied to the aluminum foil to obtain the secondary formed aluminum foil;
and (3) in-liquid power supply treatment: under the conditions that the temperature is 30 ℃ and the applied voltage is 1V, carrying out current supplementing treatment on the secondary aluminum foil in a liquid power supply tank;
third stage formation treatment (F3): placing the secondary formation aluminum foil subjected to the in-liquid power supply treatment into an ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20% for three-level formation treatment, wherein the time is 30 minutes, the current is 600A, and the voltage is applied to the solution to obtain the three-level formation aluminum foil;
fourth stage formation process (F4): placing the tertiary aluminum foil into ammonium adipate preparation solution with the temperature of 82 ℃ and the concentration of 20 percent for tertiary formation treatment for 30 minutes, wherein the current is 500A, and the voltage is 5V to obtain a quaternary aluminum foil;
phosphoric acid treatment (P treatment): placing the four-stage formed aluminum foil into phosphoric acid preparation solution with the temperature of 60 ℃ and the concentration of 5 percent for P treatment for 5 minutes to obtain P-treated formed aluminum foil;
primary repair treatment: placing the P-treated aluminum foil into an ammonium adipate solution with the temperature of 82 ℃ and the concentration of 3 percent for 10 minutes and the voltage of 4V to obtain a primary repaired aluminum foil;
and (3) final repairing: placing the primary repair formation aluminum foil into ammonium dihydrogen phosphate preparation solution with the temperature of 85 ℃ and the concentration of 3 percent for final repair treatment for 10 minutes and with the voltage of 4V to obtain final repair formation aluminum foil;
and (3) drying: and (3) drying the final-stage repaired formed aluminum foil at 170 ℃ to obtain the low-pressure formed foil.
Experimental example 1 high temperature Placement test
The formed foils of examples and comparative examples were subjected to a high temperature standing test at 105.+ -. 3 ℃. Various performance parameters of the formed foil before high temperature (0 hours) were recorded, and the performance parameters of the formed foil after 1000 hours of high temperature. Tables 1 and 2 show test results, wherein cap. Is the capacitance, and Δ% is the capacitance change value, and Δ% = (capacitance measured after 1000 hours at high temperature-capacitance measured after 0 hours at high temperature)/capacitance measured after 0 hours at high temperature×100%.
TABLE 1 high temperature placement test results (0 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm 2 ) | 206.6 | 207.8 | 198.5 | 202.2 | 197.2 |
| Δ％ | 0 | 0 | 0 | 0 | 0 |
TABLE 2 high temperature placement test results (1000 hours)
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Cap.(μf/cm 2 ) | 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 capacitance change value of comparative example 1 is significantly higher than that of examples 1 to 4 after 1000 hours of high temperature standing, and it can be demonstrated that the high acid resistance low pressure formed foil provided by the application has high temperature stability and life.
Experimental example 2 high temperature load Life test
The test pieces of the examples and the comparative examples were subjected to a high-temperature load life test, and the performance parameters of the test pieces were recorded at a temperature of 105.+ -. 3 ℃ for each of the test pieces after the high-temperature load life test for 0 hours, 1000 hours, 2000 hours, 5000 hours and 10000 hours, respectively, and the results are shown in the following table, wherein cap is the electrostatic capacity, Δ% is the electrostatic capacity change value, Δ% = (electrostatic capacity measured after the high-temperature load life test for x hours-electrostatic capacity measured after the high-temperature load life test for 0 hours)/electrostatic capacity measured after the high-temperature load life test for 0 hours x 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/cm 2 ) | 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/cm 2 ) | 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/cm 2 ) | 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/cm 2 ) | 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/cm 2 ) | 195.9 | 197.0 | 188.4 | 191.0 | 174.1 |
| Δ％ | -5.08 | -5.15 | -5.04 | -5.49 | -11.62 |
From the data, it can be seen that, at the front end of the formation procedure, the high temperature resistance of the low-voltage formation foil can be effectively improved by performing the formation treatment twice, the storage life is also improved, and the performance after the high-temperature load test at high temperature for 10000 hours can be still suitable for the aluminum electrolytic capacitor.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (8)
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, pretreatment: the pretreatment comprises a first-stage pretreatment and a second-stage pretreatment in sequence;
the specific steps of the first-stage pretreatment are as follows: the aluminum foil is placed in phosphoric acid solution with the mass concentration of 0.5-15% for treatment, the temperature of the phosphoric acid solution is controlled to be 60+/-5 ℃, and the voltage is controlled to be 2+/-0.5V; then carrying out first-stage compound tablet treatment in ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and then carrying out high-temperature heat treatment at 460 ℃ to finish first-stage pretreatment; the control temperature of the ammonium dihydrogen phosphate aqueous solution is 82+/-5 ℃, and the control voltage is 2+/-0.5V;
the specific steps of the second-stage pretreatment are as follows: carrying out second-stage compound treatment on the aluminum foil subjected to the first-stage pretreatment in an ammonium dihydrogen phosphate aqueous solution with the mass concentration of 0.02-2%, and cleaning and drying to finish the second-stage pretreatment; 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;
s2, multistage formation treatment: carrying out multistage 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-resistant low-pressure formation foil.
2. The method for producing a high acid-resistant low-pressure formed foil according to claim 1, wherein the multi-stage formation process is a four-stage formation process, comprising a first-stage formation process, a second-stage formation process, a third-stage formation process, and a fourth-stage formation process in this order; wherein the formation liquid of the first, second, third and fourth stage formation treatments is hexamethylenediamine solution, and the temperature is controlled to be 82+/-5 ℃.
3. The method for producing a high acid resistance low pressure formed foil according to claim 2, wherein an in-liquid power feeding treatment is provided between the second and third formation treatments, the control temperature of the in-liquid power feeding treatment being 30±3 ℃ and the applied voltage being 1±0.1V.
4. The method for producing a high acid resistance low pressure formed foil according to claim 3, wherein a phosphoric acid treatment is provided at the rear end of the fourth stage forming treatment, and the control temperature of the phosphoric acid treatment is 60.+ -. 6 ℃.
5. The method for producing a high acid resistance low pressure formed foil according to claim 1, further comprising a primary repair treatment and a final repair treatment, wherein the forming liquid of the primary repair treatment is a hexamethylenediamine solution, and the temperature is controlled to be 82+ -5 ℃; the formation liquid of the final repair treatment is ammonium dihydrogen phosphate aqueous solution, and the temperature is controlled to be 85+/-5 ℃.
6. The method for producing a high acid resistance low pressure formed foil according to claim 5, wherein a heat treatment is provided between the primary repair treatment and the final repair treatment, and the temperature of the heat treatment is 460±40 ℃.
7. A high acid resistance low pressure formed foil, characterized in that the high acid resistance low pressure formed foil is produced according to the production method of any one of claims 1-6.
8. Use of the high acid resistance low voltage formed foil according to claim 7 in high acid resistance low voltage aluminum electrolytic capacitors.
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