CN114164481B - Hole forming corrosion method, medium-high pressure corrosion foil and preparation method thereof - Google Patents
Hole forming corrosion method, medium-high pressure corrosion foil and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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Abstract
The invention discloses a hole forming corrosion method, a medium-high voltage corrosion foil and a preparation method thereof, wherein the hole forming corrosion method comprises the steps of placing an aluminum foil in corrosive liquid to sequentially perform first high-current corrosion and first low-current corrosion; the current density of the first large current corrosion is 0.4-0.8A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The current density of the first small current corrosion is 0.05-0.25A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The total time of the hole forming corrosion is 95-170 s, wherein the time of the first small current corrosion is 15-50 s; the concentration of hydrochloric acid in the corrosive liquid is 2-5 wt%, the concentration of sulfuric acid is 25-35 wt%, the concentration of aluminum ions is 0.3-0.6 mol/L, and the temperature of the corrosive liquid is 65-75 ℃. According to the invention, after or during high-current corrosion, small-current corrosion is added, so that the hole can be expanded and penetrated into the hole under the condition that the point corrosion hole is not newly increased basically, the penetration and the uniformity of reaming corrosion holes are facilitated, the adverse effect of invalid pinholes on the electrostatic capacity of the high-voltage corrosion foil is reduced, and the electrostatic capacity of the prepared corrosion foil is improved.
Description
Technical Field
The invention relates to the technical field of preparation of medium-high voltage corrosion foils, in particular to a hole forming corrosion method, a medium-high voltage corrosion foil and a preparation method thereof.
Background
The rapid development and iteration of electronic information technology and equipment promote miniaturization and sheet-type of aluminum electrolytic capacitors, which puts higher demands on the performances of static electricity and the like of anode foils for aluminum electrolytic capacitors.
Currently, the electrolytic corrosion process of the medium-high voltage aluminum foil generally comprises four main steps of pretreatment, hole forming corrosion, reaming corrosion and post-treatment. The pretreatment is mainly that an aluminum foil is placed in a mixed solution of hydrochloric acid and sulfuric acid, oil stains, impurities and oxide films on the surface of the aluminum foil are removed, the surface state is improved, and tunnel holes which are uniformly distributed are formed when the aluminum foil is subjected to hole forming corrosion in the next step; the pore-forming corrosion is mainly that the pretreated aluminum foil is placed in a mixed solution of sulfuric acid and hydrochloric acid to be subjected to direct current corrosion, and an initial tunnel pore with a certain length and a certain pore diameter is formed on the surface of the aluminum foil; the reaming corrosion is mainly to put the aluminum foil which is subjected to the pore-forming corrosion into nitric acid solution for electrifying corrosion, so that the aperture of the tunnel hole is further enlarged to the required size, the tunnel hole is prevented from being blocked by an oxide film during formation, and the high electrostatic capacity is obtained; the post-treatment is mainly to put the aluminum foil subjected to reaming corrosion into a nitric acid solution to eliminate residual metal impurities, foil ash and chloride ions in tunnel holes on the surface of the aluminum foil.
In practical production, the density of the etched holes, the shape of the holes and the uniformity of the holes depth are key to achieving high electrostatic capacity. In order to control the shape of holes and the deep uniformity of holes and further improve the electrostatic capacity, the prior art discloses a method for improving the electrostatic capacity by immersing an aluminum foil subjected to hole forming corrosion in nitric acid or hydrochloric acid solution, but the corrosion foil prepared by the method has the problem of a plurality of invalid pinholes.
Disclosure of Invention
The primary purpose of the invention is to overcome the problem of a large number of invalid pinholes of the corrosion foil prepared by the existing medium-high pressure corrosion foil preparation method, and provide a pore-forming corrosion method.
Another object of the invention is to provide a method for producing a medium and high voltage etched foil.
It is a further object of the invention to provide a medium and high voltage corrosion foil.
It is a further object of the invention to provide the use of said medium and high voltage corrosion foil.
The above object of the present invention is achieved by the following technical solutions:
a hole etching method comprises the following steps:
placing aluminum foil in corrosive liquidPerforming first high-current corrosion and first low-current corrosion for the second time; the current density of the first large current corrosion is 0.4-0.8A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The current density of the first small current corrosion is 0.05-0.25A/cm 2 ；
The total time of the hole forming corrosion is 95-170 s, wherein the time of the first small current corrosion is 15-50 s;
the concentration of hydrochloric acid in the corrosive liquid is 2-5 wt%, the concentration of sulfuric acid is 25-35 wt%, the concentration of aluminum ions is 0.3-0.6 mol/L, and the temperature of the corrosive liquid is 65-75 ℃.
According to the pore-forming corrosion method, small current corrosion is added after large current corrosion, and the pore-forming holes can be enlarged and penetrated into small amplitude under the condition that the point corrosion holes are not newly increased basically by controlling the current density and the corrosion time of the small current corrosion, so that the resistance of aluminum ions to outwards diffuse in the reaming process during the preparation of the medium-high voltage corrosion foil is reduced, the penetration and reaming consistency of the subsequent reaming corrosion holes is facilitated, the adverse effect of invalid pores on the electrostatic capacity of the medium-high voltage corrosion foil is reduced, and the electrostatic capacity of the prepared corrosion foil is improved.
Preferably, the first low current corrosion current density is 0.1-0.2A/cm 2 。
Preferably, the total time of the hole forming corrosion is 110-130 s, wherein the time of the first small current corrosion is 20-40 s.
Preferably, the concentration of hydrochloric acid in the corrosive liquid is 4wt.%, the concentration of sulfuric acid is 32wt.%, the concentration of aluminum ions is 0.43mol/L, and the temperature of the corrosive liquid is 70 ℃.
Preferably, the first high-current corrosion is performed in 2 or more sections, and the first low-current corrosion is performed between two adjacent sections of high-current corrosion.
Preferably, the first low-current corrosion is followed by a second high-current corrosion, wherein the first high-current corrosion time is 50-70 s, and the first low-current corrosion time is 20-40 s;
the second high current corrosion time is 20-40 s, and the current density is 0.5-0.6A/cm 2 。
More preferably, the process is carried out,the second heavy current corrosion is followed by a second low current corrosion, the second low current corrosion time is 20-40 s, and the current density is 0.1-0.2A/cm 2 。
The invention also provides a preparation method of the medium-high voltage corrosion foil, which comprises four steps of pretreatment, pore-forming corrosion, reaming corrosion and post-treatment of the aluminum foil in sequence, wherein the pore-forming corrosion is carried out according to the pore-forming corrosion method.
Preferably, the pretreatment is to treat the aluminum foil in a mixed solution of sulfuric acid and hydrochloric acid, wherein the solution temperature is 55-70 ℃ and the treatment time is 20-30 s.
More preferably, the pretreatment is to treat the aluminum foil in a mixed solution of 4wt.% hydrochloric acid and 32wt.% sulfuric acid at a solution temperature of 60 ℃ for 20s.
Preferably, the reaming corrosion is to wash the aluminum foil, then put the aluminum foil into a solution with the nitric acid concentration of 5 to 10wt.% for electrifying corrosion, and the current density is 0.15 to 0.25A/cm 2 The electric corrosion time is 400-480 s, and the solution temperature is 65-80 ℃.
More preferably, the reaming corrosion is to wash the aluminum foil with water and then put the aluminum foil into a solution with a nitric acid concentration of 8wt.% for electrifying corrosion, and the current density is 0.2A/cm 2 The electrical corrosion time was 450s and the solution temperature was 70 ℃.
Preferably, the post-treatment is to wash the aluminum foil subjected to reaming corrosion, then put the aluminum foil into a solution with nitric acid concentration of 5-10 wt.% for 40-80 s, and the solution temperature is 60-80 ℃ and then dried.
More preferably, the post-treatment is to wash the aluminum foil subjected to reaming corrosion with water, then treat the aluminum foil in a solution with a nitric acid concentration of 6wt.% for 60 seconds, with the solution temperature being 65 ℃, and then dry the aluminum foil.
Preferably, the drying temperature is 150-200 ℃ and the time is 60-120 s.
The invention also provides the medium-high pressure corrosion foil prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a hole forming corrosion method, which is characterized in that small current corrosion is added after or during the large current corrosion, and the hole forming corrosion method can be used for expanding and penetrating into a hole forming hole in a small scale under the condition of basically not newly increasing a point corrosion hole, thereby being beneficial to the penetration of a hole of a subsequent reaming corrosion hole and the consistency of reaming, reducing the adverse effect of invalid pinholes on the electrostatic capacity of a medium-high voltage corrosion foil, and improving the electrostatic capacity of the prepared medium-high voltage corrosion foil.
Drawings
FIG. 1 is a surface SEM image of a etched foil obtained in example 12.
FIG. 2 is a surface SEM image of the etched foil obtained in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
Example 1
The embodiment provides a preparation method of a medium-high pressure corrosion foil, which comprises the following steps:
s1, pretreatment: soft electronic aluminum foil with the purity of more than or equal to 99.99 percent HEC130 mu m is taken and treated in a mixed solution of 4wt.% hydrochloric acid and 32wt.% sulfuric acid, wherein the treatment temperature is 60 ℃, and the treatment time is 20s;
s2, hole forming corrosion:
s21, placing the pretreated aluminum foil into an etching solution with the hydrochloric acid concentration of 4 wt%, the sulfuric acid concentration of 32 wt%, and the aluminum ion concentration of 0.43mol/L for the first time, wherein the etching condition is that the current density is 0.55A/cm 2 The temperature of the corrosive liquid is 72 ℃ and the corrosion time is 90s;
s22, carrying out first low-current corrosion after the step S21 is finished, wherein the corrosion condition is that the current density is 0.05A/cm 2 The temperature of the corrosive liquid is 70 ℃ and the corrosion time is 15s; the concentration of hydrochloric acid in the low-current corrosion solution is 4wt.%, the concentration of sulfuric acid is 32wt.%, and the concentration of aluminum ions is 0.43mol/L;
s3, reaming and corrosion: s2, after finishing, washing and cleaning, and placingIn 8% nitric acid solution at 70deg.C with current density of 0.2A/cm 2 Is subjected to power-on corrosion for 450s under the corrosion condition;
s4, post-treatment: the aluminum foil after reaming corrosion and water washing is placed in 6% nitric acid solution for treatment at 65 ℃ for 60 seconds, and then is dried at 160 ℃ to obtain the medium-high pressure corrosion foil.
Example 2
This example provides another method for producing a medium-high voltage etched foil, which differs from example 1 only in that in step S22, the current density is 0.1A/cm 2 The etching time was 20s.
Example 3
This example provides another method for preparing a medium-high voltage etched foil, which differs from example 2 only in that in step S22, the etching solution temperature is 73 ℃.
Example 4
This example provides another method for producing a medium-high pressure etched foil, which differs from example 2 only in that in step S22, the etching solution temperature is 67 ℃.
Example 5
This example provides another method for producing a medium-high voltage etched foil, which differs from example 1 only in that in step S22, the current density is 0.15A/cm 2 The etching time was 25s.
Example 6
This example provides another method for producing a medium-high voltage etched foil, which differs from example 1 only in that in step S22, the current density is 0.20A/cm 2 The etching time was 40s.
Example 7
This example provides another method for producing a medium-high voltage etched foil, which differs from example 1 only in that in step S22, the current density is 0.25A/cm 2 The etching time was 50s.
Example 8
The embodiment provides another method for preparing a medium-high pressure corrosion foil, which comprises the following steps:
s1, pretreatment: step S1 is the same as in example 1;
s2, hole forming corrosion:
s21, placing the pretreated aluminum foil into an etching solution with the hydrochloric acid concentration of 4 wt%, the sulfuric acid concentration of 32 wt%, and the aluminum ion concentration of 0.43mol/L for the first time, wherein the etching condition is that the current density is 0.55A/cm 2 The temperature of the corrosive liquid is 72 ℃ and the corrosion time is 70s;
s22, carrying out first low-current corrosion after the step S21 is finished, wherein the corrosion condition is that the current density is 0.1A/cm 2 The temperature of the corrosive liquid is 70 ℃ and the corrosion time is 20s; the concentration of hydrochloric acid in the low-current corrosion solution is 4wt.%, the concentration of sulfuric acid is 32wt.%, and the concentration of aluminum ions is 0.43mol/L;
s23, after the step S22 is finished, placing the aluminum foil into an etching solution with the hydrochloric acid concentration of 4 wt%, the sulfuric acid concentration of 32 wt%, and the aluminum ion concentration of 0.43mol/L for secondary heavy current etching under the etching condition that the current density is 0.55A/cm 2 The temperature is 72 ℃ and the corrosion time is 20s;
s3, reaming and corrosion: s2, washing with water, placing in 8% nitric acid solution, and measuring current density at 70deg.C and 0.2A/cm 2 Is subjected to power-on corrosion for 450s under the corrosion condition;
s4, post-treatment: step S4 is the same as in example 1.
Example 9
This example provides another method for producing a medium-high voltage etched foil, which differs from example 8 only in that the etching time is 50S in step S21 and 40S in step S23.
Example 10
This example provides another method for producing a medium-high voltage etched foil, which differs from example 8 only in that the etching time is 20S in step S21 and 70S in step S23.
Example 11
This example provides another method for producing a medium-high voltage etched foil, which differs from example 8 only in that in step S22, the etching time is 40S.
Example 12
The embodiment provides another method for preparing a medium-high pressure corrosion foil, which comprises the following steps:
s1, pretreatment: step S1 is the same as in example 1;
s2, hole forming corrosion:
s21, placing the pretreated aluminum foil into an etching solution with the hydrochloric acid concentration of 4 wt%, the sulfuric acid concentration of 32 wt%, and the aluminum ion concentration of 0.43mol/L for the first time, wherein the etching condition is that the current density is 0.55A/cm 2 The corrosion temperature is 72 ℃ and the corrosion time is 70s;
s22, carrying out first low-current corrosion after the step S21 is finished, wherein the corrosion condition is that the current density is 0.1A/cm 2 The corrosion temperature is 70 ℃ and the corrosion time is 20s; the concentration of hydrochloric acid in the low-current corrosion solution is 4wt.%, the concentration of sulfuric acid is 32wt.%, and the concentration of aluminum ions is 0.43mol/L;
s23, after the step S22 is finished, placing the aluminum foil into an etching solution with the hydrochloric acid concentration of 4 wt%, the sulfuric acid concentration of 32 wt%, and the aluminum ion concentration of 0.43mol/L for secondary heavy current etching under the etching condition that the current density is 0.55A/cm 2 Etching temperature 72 ℃ and etching time 20s;
s24, carrying out secondary low-current corrosion after the step S23 is finished, wherein the corrosion condition is that the current density is 0.1A/cm 2 The temperature is 70 ℃ and the corrosion time is 20s; the concentration of hydrochloric acid in the second low-current corrosion solution is 4 wt%, the concentration of sulfuric acid is 32 wt%, and the concentration of aluminum ions is 0.43mol/L;
s3, reaming and corrosion: step S3 is the same as in example 1;
s4, post-treatment: step S4 is the same as in example 1.
Example 13
The present example provides another method for producing a medium-high voltage etched foil, which differs from example 12 only in that in step S24, the etching time is 40S, and the current density is 0.2A/cm 2 。
Example 14
The embodiment provides a preparation method of a medium-high pressure corrosion foil, which comprises the following steps:
s1, pretreatment: soft electronic aluminum foil with the purity of more than or equal to 99.99 percent HEC130 mu m is taken and treated in a mixed solution of 4wt.% hydrochloric acid and 32wt.% sulfuric acid, wherein the treatment temperature is 55 ℃, and the treatment time is 30s;
s2, hole forming corrosion:
s21, placing the pretreated aluminum foil into an etching solution with the hydrochloric acid concentration of 2 wt%, the sulfuric acid concentration of 25 wt%, and the aluminum ion concentration of 0.3mol/L for the first time, wherein the etching condition is that the current density is 0.8A/cm 2 The temperature of the corrosive liquid is 65 ℃ and the corrosion time is 80s;
s22, carrying out first low-current corrosion after the step S21 is finished, wherein the corrosion condition is that the current density is 0.25A/cm 2 The temperature of the corrosive liquid is 65 ℃ and the corrosion time is 15s; the concentration of hydrochloric acid in the low-current corrosion solution is 2 wt%, the concentration of sulfuric acid is 25 wt%, and the concentration of aluminum ions is 0.3mol/L;
s3, reaming and corrosion: s2, washing with water, placing in 5% nitric acid solution, and measuring current density at 65deg.C and 0.15A/cm 2 Is subjected to electric corrosion for 480 seconds under the corrosion condition;
s4, post-treatment: the aluminum foil after reaming corrosion and water washing is placed in 6% nitric acid solution for treatment at 65 ℃ for 60 seconds, and then is dried at 160 ℃ to obtain the medium-high pressure corrosion foil.
Example 15
The embodiment provides a preparation method of a medium-high pressure corrosion foil, which comprises the following steps:
s1, pretreatment: soft electronic aluminum foil with the purity of more than or equal to 99.99 percent HEC130 mu m is taken and treated in a mixed solution of 4wt.% hydrochloric acid and 32wt.% sulfuric acid, wherein the treatment temperature is 70 ℃ and the treatment time is 20s;
s2, hole forming corrosion:
s21, placing the pretreated aluminum foil into an etching solution with 5wt.% of hydrochloric acid, 35wt.% of sulfuric acid and 0.6mol/L of aluminum ion for first heavy current etching under the current density of 0.4A/cm 2 The temperature of the corrosive liquid is 75 ℃ and the corrosion time is 120s;
s22, carrying out first low-current corrosion after the step S21 is finished, wherein the corrosion condition is that the current density is 0.05A/cm 2 The temperature of the corrosive liquid is 75 ℃ and the corrosion time is 50s; the concentration of hydrochloric acid in the low-current corrosion solution is 5 wt%, and the concentration of sulfuric acid is35wt.%, aluminum ion concentration 0.6mol/L;
s3, reaming and corrosion: s2, washing with water, placing in 10% nitric acid solution, and measuring current density at 80deg.C to 0.25A/cm 2 Is subjected to electric corrosion for 400s under the corrosion condition;
s4, post-treatment: the aluminum foil after reaming corrosion and water washing is placed in 6% nitric acid solution for treatment at 65 ℃ for 60 seconds, and then is dried at 160 ℃ to obtain the medium-high pressure corrosion foil.
Comparative example 1
This comparative example provides a method for producing a medium-high pressure etched foil, which differs from example 1 only in that this comparative example does not perform step S22.
Comparative example 2
The comparative example provides a method for preparing a medium-high pressure corrosion foil, comprising the following steps:
s1, pretreatment: soaking aluminum foil in a mixed solution containing 3 mass percent of hydrochloric acid and 35 mass percent of sulfuric acid at 80 ℃ for 120 seconds;
s2, primary hole forming corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid with the temperature of 75 ℃ and applying a current density of 600mA/cm 2 The direct current of the water-based paint is subjected to pore-forming corrosion for 80 seconds, wherein the pore-forming corrosive liquid is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent;
s3, medium processing: immersing the aluminum foil subjected to primary pore formation corrosion into hydrochloric acid solution with the concentration of 30g/L and the treatment temperature of 50 ℃ for 120s.
S4, secondary reaming corrosion: directly placing the aluminum foil after the medium treatment in reaming corrosive liquid with the temperature of 70 ℃ and applying current with the density of 100mA/cm 2 The direct current of the steel is subjected to reaming corrosion for 72s, and reaming corrosion liquid is a solution containing 3 mass percent of nitric acid;
s5, post-treatment: and (3) immersing the etched foil subjected to secondary reaming in a 5% nitric acid solution at the temperature of 70 ℃ for 100 seconds, and then washing the etched foil with water to obtain the medium-high pressure etched foil.
Comparative example 3
This comparative example provides a method for preparing a medium-high pressure etched foil, as compared with the examples1 is different only in that the etching current density in step S22 is 0.30A/cm 2 。
Comparative example 4
This comparative example provides a method for producing a medium-high pressure etched foil, which differs from example 1 only in that the etching time in step S22 is 60S.
Performance detection
The medium-high pressure etched aluminum foils obtained in examples 1 to 15 and comparative examples 1 to 4 were tested for 520V electrostatic capacity, bending strength and sample thickness, and were subjected to reduction by the EIAJ method, and the results are shown in Table 1 below.
TABLE 1
As is clear from Table 1, the thickness of the corrosion samples was not substantially different, the flexural strength was also within the product requirement range (65 cycles or more), and it was found that the low-current corrosion treatment had no significant effect on the thickness reduction of the corrosion samples, and the flexural strength was not significantly reduced.
As can be seen from examples 8 to 10, the longer the first-stage galvanic corrosion time, the higher the electrostatic capacity of the corrosion foil in the cavitation corrosion.
In examples 8 and 12, the electrostatic capacity of the etched foil was further increased by performing the second low-current etching after the second high-current etching was completed in the hole etching.
From example 1 and comparative examples 3 to 4, increasing the low current etching current density or extending the low current etching time is disadvantageous for the improvement of electrostatic capacity because the excessive low current etching current density or the excessive time can produce more new pitting holes instead of effectively enlarging and penetrating into the original pitting holes, resulting in an increase in the proportion of invalid pinholes in the subsequent reaming etching.
In contrast, the method of the present invention can increase the electrostatic capacity of the prepared corrosion foil in all of examples 1 to 15 and comparative examples 1 to 4.
SEM analysis was performed on the etched foils described in example 12 and comparative example 1, respectively, and fig. 1 and 2 are SEM images of the surfaces of the etched foils obtained in example 12 and comparative example 1, respectively, and the results of statistics are shown in table 2 below.
TABLE 2
From SEM (scanning electron microscope) hole number and aperture statistical data, compared with comparative example 1, the hole number in the thickness of 5 μm is not obviously increased in example 12, but the attenuation trend of the hole number is slower along with the increase of the polishing depth, so that the hole diameter attenuation trend is also slower, which indicates that the hole etching method is favorable for improving the penetration and the uniformity of reaming of the subsequent reaming etching holes and reducing the adverse effect of ineffective pinholes on the electrostatic capacity of the etching foil. SEM images of the etched foils described in examples 1 to 11 and examples 13 to 15 are similar to example 12.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. A hole-forming corrosion method is characterized by comprising the following steps:
placing aluminum foil in corrosive liquid to sequentially perform first high-current corrosion and first low-current corrosionThe method comprises the steps of carrying out a first treatment on the surface of the The current density of the first large current corrosion is 0.4-0.8A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The current density of the first small current corrosion is 0.05-0.25A/cm 2 ；
The total time of the hole forming corrosion is 95-170 s, wherein the time of the first small current corrosion is 15-50 s;
the concentration of hydrochloric acid in the corrosive liquid is 2-5 wt%, the concentration of sulfuric acid is 25-35 wt%, the concentration of aluminum ions is 0.3-0.6 mol/L, and the temperature of the corrosive liquid is 65-75 ℃.
2. The method of hole etching according to claim 1, wherein the first low current etching current density is 0.1 to 0.2A/cm 2 。
3. The method of claim 1, wherein the total time of the hole etching is 110 to 130 seconds, and wherein the first low current etching time is 20 to 40 seconds.
4. The method of claim 1, wherein the first high current etching is performed in 2 or more sections, and the first low current etching is performed between two adjacent sections of high current etching.
5. The method of hole forming etching according to claim 1, wherein the first low-current etching is followed by a second high-current etching, the first high-current etching being performed for 50 to 70 seconds and the first low-current etching being performed for 20 to 40 seconds;
the second high current corrosion time is 20-40 s, and the current density is 0.5-0.6A/cm 2 。
6. The method of hole forming etching according to claim 5, wherein the second high current etching is followed by a second low current etching for 20 to 40 seconds with a current density of 0.1 to 0.2A/cm 2 。
7. A method for preparing a medium-high pressure corrosion foil, comprising four steps of pretreatment, pore-forming corrosion, reaming corrosion and post-treatment of an aluminum foil in sequence, wherein the pore-forming corrosion is carried out according to the pore-forming corrosion method of any one of claims 1 to 6.
8. The method for preparing a medium-high pressure etched foil according to claim 7, wherein the pretreatment is to treat the aluminum foil in a mixed solution of sulfuric acid and hydrochloric acid at a temperature of 55-70 ℃ for 20-30 s.
9. The method for preparing a medium-high pressure corrosion foil according to claim 7, wherein the reaming corrosion is to put an aluminum foil into a solution with a nitric acid concentration of 5-10 wt.% for electric corrosion after washing, and the current density is 0.15-0.25A/cm 2 The electric corrosion time is 400-480S, and the solution temperature is 65-80 ℃.
10. A medium-high pressure etched foil, characterized in that it is produced by the method according to any one of claims 7-9.
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| JP2692108B2 (en) * | 1988-02-19 | 1997-12-17 | 松下電器産業株式会社 | Manufacturing method of electrode foil for aluminum electrolytic capacitor |
| JP5170163B2 (en) * | 2010-06-07 | 2013-03-27 | パナソニック株式会社 | Manufacturing method of etching foil for aluminum electrolytic capacitor |
| CN107254707B (en) * | 2017-06-16 | 2020-06-26 | 李晓天 | Method for manufacturing multi-stage pore-forming rapid medium-high voltage electrode foil |
| CN110923779B (en) * | 2019-11-27 | 2021-09-14 | 东莞东阳光科研发有限公司 | Ultrahigh pressure etched foil and etching method thereof |
| CN111733443B (en) * | 2020-05-22 | 2021-07-16 | 东莞东阳光科研发有限公司 | Method for manufacturing electrode foil for aluminum electrolytic capacitor and electrode foil |
| CN111748839A (en) * | 2020-06-24 | 2020-10-09 | 东莞东阳光科研发有限公司 | Preparation method of medium-high voltage corrosion foil for aluminum electrolytic capacitor and anode foil |
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