CN108456916B - Corrosion method of medium-high voltage electronic aluminum foil - Google Patents
Corrosion method of medium-high voltage electronic aluminum foil Download PDFInfo
- Publication number
- CN108456916B CN108456916B CN201711477367.2A CN201711477367A CN108456916B CN 108456916 B CN108456916 B CN 108456916B CN 201711477367 A CN201711477367 A CN 201711477367A CN 108456916 B CN108456916 B CN 108456916B
- Authority
- CN
- China
- Prior art keywords
- corrosion
- aluminum foil
- temperature
- solution
- reaming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 179
- 230000007797 corrosion Effects 0.000 title claims abstract description 179
- 239000011888 foil Substances 0.000 title claims abstract description 152
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 129
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 86
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 109
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 62
- 239000011259 mixed solution Substances 0.000 claims description 27
- 238000002791 soaking Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a corrosion method of a medium-high voltage electronic aluminum foil, which comprises four steps of pre-treatment, primary hole forming corrosion, secondary hole expanding corrosion and post-treatment of a high-purity aluminum foil, wherein a middle treatment step is added between the primary hole forming corrosion and the secondary hole expanding corrosion, and the middle treatment step is to immerse the aluminum foil subjected to the primary hole forming corrosion into a nitric acid or hydrochloric acid solution at the temperature of 40-75 ℃ for reaction for 30-200 s. The method has the advantages that the sulfate radicals remained in the tiny tunnel holes in the aluminum foil in the holing corrosion can be obviously reduced, and the specific volume of the corroded foil is improved.
Description
Technical Field
The invention relates to the technical field of anode foil corrosion for aluminum electrolytic capacitors, in particular to a corrosion method for a medium-high voltage electronic aluminum foil.
Background
Miniaturization is a necessary trend in the development of aluminum electrolytic capacitors, and the aluminum foil with high purity of {100} texture is subjected to electrolytic corrosion to enlarge the specific surface area and improve the specific capacitance, so that the aluminum electrolytic capacitor is the most effective technical approach for miniaturization.
At present, the electrolytic corrosion process of medium-high voltage aluminum foil generally comprises four main steps of pretreatment, primary holing corrosion, secondary reaming corrosion and post-treatment (namely chemical washing). The formation of uniformly distributed high-density tunnel holes with reasonable size (aperture and hole length) on the surface of the high-pressure aluminum foil is the key for obtaining high specific capacitance. The pretreatment mainly has the effects of removing oil stains, impurities and oxidation films on the surface of the plain foil, improving the surface state and promoting the formation of evenly distributed tunnel holes when the aluminum foil is subjected to hole-forming corrosion in the next step; the function of the pitting corrosion is to form an initial tunnel hole with a certain length and a certain aperture on the surface of the aluminum foil by applying direct current; the reaming corrosion is used for further electrifying corrosion on the basis of the initial tunnel hole, 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 high specific capacitance is obtained; the main function of the post-treatment is to eliminate metal impurities and foil ash remained on the surface of the aluminum foil and chloride ions in the tunnel holes.
In each step of the treatment, the components of the solution to be treated have large differences, particularly the primary pore-forming corrosion solution and the secondary pore-expanding corrosion solution. The primary pore-forming corrosion solution is mainly a mixed acid solution of hydrochloric acid and sulfuric acid, and the mixed acid solution is favorable for forming a large number of uniform fine tunnel pores on the surface of the aluminum foil. The secondary reaming corrosion solution is generally hydrochloric acid solution or nitric acid solution, and the solution is favorable for reaming on the basis of fine tunnel holes without continuous holes on the surface of the aluminum foil. However, when a small amount, even a very small amount, of sulfuric acid is mixed into the secondary reaming corrosive acid solution, the tunnel hole reaming is significantly affected. This effect is mainly manifested in: 1. holes are easy to form on the surface of the aluminum foil, so that the hole density is too high, and the hole merging is serious; 2. the hole reaming of the hole orifice of the tunnel hole is inhibited, and the hole reaming is serious, so that the inner and outer hole diameters of the tunnel hole are inconsistent. Thus, the specific volume of the etched foil is significantly reduced. Therefore, the mixing of sulfuric acid into the secondary pore-enlarging etching solution needs to be strictly controlled. Because the aluminum foil contains a large amount of sulfuric acid in the first-stage pore-forming corrosion solution, the aluminum foil needs to be cleaned when entering the second-stage pore-forming corrosion solution so as to remove sulfate radicals as much as possible.
At present, only a water washing method is generally adopted in the industry, but the effect of the method is difficult to completely clean sulfate radicals in pores in the rapid production. Patent application No. 201610601355.5 points out that after the first-order corrosion in the ultrahigh pressure corrosion process, the aluminum foil is put into sodium carbonate, sodium bicarbonate or dilute phosphoric acid solution with the pH value of 5.0-9.0 for soaking treatment, so that the aperture of the tunnel hole can be remarkably expanded, and the ultrahigh pressure performance can be remarkably improved. For secondary reaming corrosion, the method should have a certain sulfate radical cleaning effect, but only has certain limitation in the aspect of medium-high pressure or even lower pressure corrosion process, and is embodied in that: 1. sodium carbonate, sodium bicarbonate carry out that solution corrodes for acid solution more intensely to the aluminium foil surface, it is comparatively violent to tunnel hole reaming, it is bigger to make tunnel hole reaming easily, do not too do benefit to the promotion of well high pressure corrosion foil specific volume, in addition, because the aluminium foil goes out once to send out and remains a large amount of sulfate radicals after the hole, and have stronger reaming effect to tunnel hole itself when carrying out this one-step processing, therefore because the influence of sulfate radical can exist certain hindrance to the promotion of corroding the foil performance. 2. After the aluminum foil is soaked by using a sodium carbonate, sodium bicarbonate or dilute phosphoric acid solution, although the aluminum foil has a certain cleaning effect on sulfate radicals, substances such as sodium carbonate, sodium bicarbonate or dilute phosphoric acid remained in the aluminum foil and the tunnel hole can also influence the subsequent reaming effect, and further influence the performance of the corrosion foil, so that before entering the next reaming corrosion step, strict cleaning is required, and the production process is complex. Therefore, developing a practical middle-processing cleaning method with simple flow is a development direction for further improving the performance of middle-high pressure etched foil.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for etching medium and high voltage electronic aluminum foil, which can obviously reduce sulfate radicals remained in small tunnel holes in aluminum foil during pore etching, thereby improving specific volume of the etched foil.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a corrosion method of a medium-high voltage electronic aluminum foil comprises four steps of pre-treatment, primary hole forming corrosion, secondary hole expanding corrosion and post-treatment of a high-purity aluminum foil, wherein a middle treatment step is added between the primary hole forming corrosion and the secondary hole expanding corrosion, and the middle treatment step is to immerse the aluminum foil subjected to the primary hole forming corrosion into a nitric acid or hydrochloric acid solution at the temperature of 40-75 ℃ for reaction for 30-200 s.
As a further technical scheme, the concentration of the nitric acid solution is 30-120 g/L.
As a further technical scheme, the concentration of the hydrochloric acid solution is 10-70 g/L.
As a further technical scheme, the pretreatment comprises the step of soaking the high-purity aluminum foil in a mixed solution containing 1-10 mass percent of hydrochloric acid and 20-40 mass percent of sulfuric acid at the temperature of 60-80 ℃ for 60-200 s.
As a further technical scheme, the first-stage pore forming corrosion is to place the pretreated aluminum foil in pore forming corrosion liquid at the temperature of 65-80 ℃, and apply current density of 200-1000 mA/cm2The direct current is used for carrying out pore-forming corrosion for 60-120 s, and the pore-forming corrosion solution is a mixed solution containing 1-10% of hydrochloric acid and 20-40% of sulfuric acid in percentage by mass.
As a further technical scheme, the secondary reaming corrosion is to place the aluminum foil after the secondary reaming corrosion at the temperature of 60-80 DEG CIn the reaming corrosive liquid, the applied current density is 50-200 mA/cm2The direct current is used for reaming corrosion for 400-1000 s, and the reaming corrosion solution is a solution containing 1-10% by mass of nitric acid.
As a further technical scheme, the post-treatment comprises the steps of soaking the aluminum foil subjected to the secondary reaming corrosion in a 1-10% nitric acid solution at the temperature of 50-80 ℃ for 50-120 s, and then washing with water.
The high-purity aluminum foil adopted by the invention has the purity of 99.99 percent, the thickness of 120 mu m and the cubic texture occupancy rate of more than 95 percent.
The medium processing principle of the invention is as follows: immersing the aluminum foil corroded by the primary hair holes into a nitric acid or hydrochloric acid solution, wherein the surface of the aluminum foil, including the inside of the tunnel hole, reacts with acid to generate a large amount of bubbles, and sulfate radicals attached to the surface of the aluminum foil and the inner wall of the tunnel hole are largely separated from the surface of the aluminum foil in the reaction and bubble stirring processes so as to be cleaned; meanwhile, a small amount of nitric acid or hydrochloric acid is mixed into the secondary reaming corrosion liquid, so that the reaming corrosion performance is not influenced, and therefore, the aluminum foil can directly enter the secondary reaming corrosion liquid for secondary reaming corrosion without being cleaned after the treatment method is used, so that the production flow is simplified.
Compared with the prior art, the invention has the beneficial effects that: after the high-purity aluminum foil is corroded by the open pores, the high-purity aluminum foil is immersed into a nitric acid or hydrochloric acid solution with a certain concentration and temperature for reaction, and then subsequent steps of reaming corrosion, post-treatment and the like are directly performed, compared with the traditional corrosion process, after the treatment in the step is added, the consistency inside and outside the tunnel holes of the corroded foil is good, and the specific volume of the corroded foil is relatively improved by 1-2%. The method has the advantages of simple process, convenient operation, easy realization in industrial production and good application value.
Detailed Description
The present invention will be described in further detail with reference to examples.
A corrosion method of a medium-high voltage electronic aluminum foil comprises four steps of pretreatment, primary holing corrosion, secondary reaming corrosion and post-treatment of a high-purity aluminum foil, and specifically comprises the following operations:
(1) pretreatment: soaking the high-purity aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s;
(2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2Carrying out pore-forming corrosion for 80 s by direct current, wherein a pore-forming corrosion solution is a mixed solution containing 3% of hydrochloric acid and 35% of sulfuric acid in percentage by mass;
(3) and (3) performing intermediate treatment, namely immersing the aluminum foil subjected to primary pore corrosion into a nitric acid or hydrochloric acid solution at the temperature of 40-75 ℃ for reaction for 30-200 s, wherein the concentration of the nitric acid solution is 30-120 g/L, and the concentration of the hydrochloric acid solution is 10-70 g/L.
(4) Secondary reaming corrosion: directly placing the aluminum foil after the intermediate treatment in a reaming corrosive liquid at the temperature of 70 ℃, and applying a current with the density of 100 mA/cm2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid;
(5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water.
The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Comparative example 1
A conventional etching process is used. (1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2Carrying out pore corrosion for 80 s by direct current, wherein a pore corrosion solution is a mixed solution containing 3% of hydrochloric acid and 35% of sulfuric acid in percentage by mass, and then washing the mixed solution with water; (3) secondary reaming corrosion: placing the aluminum foil after the perforation in a reaming corrosive liquid at the temperature of 70 ℃, and applying a current with the density of 100 mA/cm2The direct current carries out hole expanding corrosion for 720s, and the hole expanding corrosion solution is a solution containing 3 mass percent of nitric acidLiquid; (4) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 1
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a nitric acid solution with the concentration of 60 g/L and the treatment temperature of 50 ℃ for treatment for 120s, (3) the secondary reaming corrosion is carried out, the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 2
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2Performing primary pore-forming corrosion on the aluminum foil for 80 seconds by direct current, wherein the primary pore-forming corrosion solution is a mixed solution containing 3 mass percent of hydrochloric acid and 35 mass percent of sulfuric acid, and (3) performing secondary pore-forming corrosion by immersing the aluminum foil subjected to primary pore-forming corrosion into a nitric acid solution with the concentration of 60 g/L and the treatment temperature of 50 ℃ for 60 seconds, and (4) directly placing the aluminum foil subjected to primary pore-forming corrosion in a pore-forming corrosion solution with the temperature of 70 ℃,applied current density was 100 mA/cm2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 3
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a nitric acid solution with the concentration of 60 g/L and the treatment temperature of 50 ℃ for treatment for 200s, (3) the secondary reaming corrosion is carried out, the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 4
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the pore-forming corrosion for 80 s, the pore-forming corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, and the treatment in the step (3) is carried out, namely, the aluminum foil after the first-level pore-forming corrosion is immersed into the solution with the concentration of 30 g/L and the treatment temperature of 50 DEG CTreating in nitric acid solution for 120 s. (4) Secondary reaming corrosion: directly placing the aluminum foil after the intermediate treatment in a reaming corrosive liquid at the temperature of 70 ℃, and applying a current with the density of 100 mA/cm2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 5
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a nitric acid solution with the concentration of 100 g/L and the treatment temperature of 50 ℃ for treatment for 120s, (3) the secondary reaming corrosion is carried out, the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 6
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the pore-forming corrosion for 80 s, and the pore-forming corrosion solution contains 3 percent of hydrochloric acid by massAnd (3) treating, namely immersing the aluminum foil subjected to primary pore forming corrosion into a nitric acid solution with the concentration of 60 g/L and the treatment temperature of 40 ℃ for 120s, (4) performing secondary pore-forming corrosion, namely directly placing the aluminum foil subjected to the primary pore forming corrosion into a pore-forming corrosion solution with the temperature of 70 ℃, and applying a current density of 100 mA/cm2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 7
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a nitric acid solution with the concentration of 60 g/L and the treatment temperature of 65 ℃ for treatment for 120s, (3) the secondary reaming corrosion is carried out, the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 8
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 DEG CApplied current density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a hydrochloric acid solution with the concentration of 30 g/L and the treatment temperature of 50 ℃ for treatment for 120s, and the secondary reaming corrosion is carried out, wherein the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 9
(1) Pretreatment: soaking the aluminum foil in a mixed solution containing 3% by mass of hydrochloric acid and 35% by mass of sulfuric acid at the temperature of 80 ℃ for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a hydrochloric acid solution with the concentration of 10 g/L and the treatment temperature of 50 ℃ for treatment for 120s, and the secondary reaming corrosion is carried out, wherein the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
Example 10
(1) Pretreatment: placing the aluminum foil at the temperature of 80 ℃, wherein the aluminum foil contains 3 mass percent of hydrochloric acid andsoaking in 35% sulfuric acid solution for 120 s; (2) primary pitting corrosion: placing the pretreated aluminum foil in a pore-forming corrosive liquid at the temperature of 75 ℃, and applying a current with the density of 600 mA/cm2The direct current is used for carrying out the perforation corrosion for 80 s, the perforation corrosion solution is a mixed solution containing 3 percent of hydrochloric acid and 35 percent of sulfuric acid by mass percent, the aluminum foil after the primary perforation corrosion is immersed into a hydrochloric acid solution with the concentration of 70 g/L and the treatment temperature of 50 ℃ for treatment for 120s, and the secondary reaming corrosion is carried out, wherein the aluminum foil after the primary perforation corrosion is directly placed into a reaming corrosion solution with the temperature of 70 ℃, and the current density of 100 mA/cm is applied2Carrying out reaming corrosion for 720s by direct current, wherein the reaming corrosion solution is a solution containing 3 mass percent of nitric acid; (5) and (3) post-treatment: and (3) soaking the etched foil subjected to the secondary hole expansion in a 5% nitric acid solution at the temperature of 70 ℃ for 100s, and then washing with water. The obtained aluminum foil is based on the standard SJ/T11140-: the aluminum electrolytic capacitor was subjected to 520V formation using an electrode foil ".
TABLE 1 comparative examples and specific values of aluminum foil obtained using the treatment method in Corrosion according to the invention
As can be seen from the data in Table 1, the specific volume of the etched foil obtained by the intermediate treatment method is relatively higher than that obtained by the traditional etching process, and the specific volume of the etched foil can be relatively improved by 0.26-2.18% by selecting reasonable process parameters. The method has the advantages of simple process, easy production realization and low investment cost, so the method still has stronger application value for practical production.
Finally, it should be pointed out that: the pretreatment, the primary pore opening corrosion, the secondary pore expansion corrosion and the post-treatment of the invention are conventional treatment means in the field, and therefore, detailed description and examples are omitted in the embodiments. The above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. The corrosion method of the medium-high voltage electronic aluminum foil comprises four steps of pretreatment, first-stage pore-forming corrosion, second-stage pore-expanding corrosion and post-treatment of the high-purity aluminum foil, and is characterized in that: adding a middle treatment step between the first-stage pore-forming corrosion and the second-stage pore-expanding corrosion, wherein the middle treatment step is to immerse the aluminum foil subjected to the first-stage pore-forming corrosion into a nitric acid or hydrochloric acid solution at the temperature of 50 ℃ for reaction for 120 s;
the concentration of the hydrochloric acid solution is 10-70 g/L.
2. The corrosion method of the medium-high voltage electronic aluminum foil according to claim 1, characterized in that: the pretreatment is to soak the high-purity aluminum foil in a mixed solution containing 1-10 mass percent of hydrochloric acid and 20-40 mass percent of sulfuric acid at the temperature of 60-80 ℃ for 60-200 s.
3. The corrosion method of the medium-high voltage electronic aluminum foil according to claim 1, characterized in that: the first-stage pore-forming corrosion is to place the pretreated aluminum foil in pore-forming corrosion liquid at the temperature of 65-80 ℃, and apply current density of 200-1000 mA/cm2The direct current is used for carrying out pore-forming corrosion for 60-120 s, and the pore-forming corrosion solution is a mixed solution containing 1-10% of hydrochloric acid and 20-40% of sulfuric acid in percentage by mass.
4. The corrosion method of the medium-high voltage electronic aluminum foil according to claim 1, characterized in that: the second-stage reaming corrosion is to place the aluminum foil after the middle treatment in a reaming corrosion solution at the temperature of 60-80 ℃, and apply a current with the density of 50-200 mA/cm2The direct current is used for reaming corrosion for 400-1000 s, and the reaming corrosion solution is a solution containing 1-10% by mass of nitric acid.
5. The corrosion method of the medium-high voltage electronic aluminum foil according to claim 1, characterized in that: and the post-treatment comprises the steps of soaking the aluminum foil subjected to the secondary reaming corrosion in a 1-10% nitric acid solution at the temperature of 50-80 ℃ for 50-120 s, and then washing with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711477367.2A CN108456916B (en) | 2017-12-29 | 2017-12-29 | Corrosion method of medium-high voltage electronic aluminum foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711477367.2A CN108456916B (en) | 2017-12-29 | 2017-12-29 | Corrosion method of medium-high voltage electronic aluminum foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108456916A CN108456916A (en) | 2018-08-28 |
| CN108456916B true CN108456916B (en) | 2020-07-14 |
Family
ID=63220570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711477367.2A Active CN108456916B (en) | 2017-12-29 | 2017-12-29 | Corrosion method of medium-high voltage electronic aluminum foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108456916B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109797424B (en) * | 2018-12-28 | 2021-08-10 | 广西贺州市桂东电子科技有限责任公司 | Method for treating five-level pore formation corrosion of medium-high voltage anode aluminum foil |
| CN110289171B (en) * | 2019-05-14 | 2021-10-01 | 乳源瑶族自治县东阳光化成箔有限公司 | Method for manufacturing non-phosphorus hole-expanding aluminum electrolytic capacitor electrode foil |
| CN112117128B (en) * | 2020-08-05 | 2022-04-22 | 乳源瑶族自治县东阳光化成箔有限公司 | High-specific-volume and high-strength medium-high voltage corrosion electrode foil and preparation method and application thereof |
| CN112798508B (en) * | 2020-12-15 | 2022-11-29 | 乳源东阳光优艾希杰精箔有限公司 | Method for detecting corrosion solubility of low-voltage electronic foil |
| CN112853456B (en) * | 2021-01-07 | 2021-11-23 | 佛山科学技术学院 | Method for manufacturing high-pressure high-specific-volume corrosion foil |
| CN112863879B (en) * | 2021-01-22 | 2022-09-30 | 广西贺州市桂东电子科技有限责任公司 | Process method for processing and thinning in medium-high voltage anode aluminum foil |
| CN114032606A (en) * | 2021-12-22 | 2022-02-11 | 江苏立富电极箔有限公司 | Method for preparing medium-high pressure corrosion foil by using phosphoric acid as corrosion inhibitor in corrosion process |
| CN114487262A (en) * | 2021-12-29 | 2022-05-13 | 广西贺州市桂东电子科技有限责任公司 | Continuous titration method of medium-high voltage anode aluminum foil reaming corrosive liquid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029413A (en) * | 2006-12-19 | 2007-09-05 | 东莞市东阳光电容器有限公司 | Production of medium-high voltage anode corrosive foil |
| CN101225539A (en) * | 2007-09-28 | 2008-07-23 | 扬州宏远电子有限公司 | Multi-stage frequency-conversion eroding method for anode foil of aluminium electrolytic capacitor |
| CN101423946A (en) * | 2008-07-29 | 2009-05-06 | 东莞市东阳光电容器有限公司 | Technique for preparing etched foil of medium-high voltage anode foil for energy-saving lamp |
| CN105097286A (en) * | 2015-09-01 | 2015-11-25 | 广西贺州市桂东电子科技有限责任公司 | Etching method of ultra-high-pressure energy storage material |
| CN105551805A (en) * | 2016-01-18 | 2016-05-04 | 南通海星电子股份有限公司 | Intermediate processing method of electrode foil for middle-high voltage aluminium electrolytic capacitor |
| CN106098378A (en) * | 2016-06-27 | 2016-11-09 | 江苏荣生电子有限公司 | A kind of device manufacturing large aperture high-voltage high specific capacitance energy storage paper tinsel |
| CN106948000A (en) * | 2017-04-18 | 2017-07-14 | 扬州宏远电子有限公司 | A kind of etching process method for improving mesohigh etched foil corrosion layer intensity |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3453984B2 (en) * | 1996-02-05 | 2003-10-06 | 松下電器産業株式会社 | Manufacturing method of etching foil for aluminum electrolytic capacitor |
| CN104878441B (en) * | 2015-04-30 | 2017-07-04 | 聊城大学 | A kind of aluminium electrolutic capacitor etching process of the anode aluminium foil with tunnel branch hole |
| CN105006367B (en) * | 2015-05-25 | 2017-05-31 | 厦门大学 | Electrolytic capacitor low voltage anode aluminum foil ladder non-sinusoidal waveform frequency-conversion eroding method |
| CN105200509B (en) * | 2015-09-01 | 2018-04-10 | 广西贺州市桂东电子科技有限责任公司 | A kind of cleaning method of electron stored energy material |
| CN105420803A (en) * | 2015-11-27 | 2016-03-23 | 广西贺州市桂东电子科技有限责任公司 | Method for ultrasonic-assisted corrosion of middle-high voltage anode aluminum foil |
| CN105401209B (en) * | 2015-12-09 | 2018-03-30 | 广西贺州市桂东电子科技有限责任公司 | A kind of method of mesohigh anodic aluminum corrosion processing |
| CN106637380A (en) * | 2016-12-13 | 2017-05-10 | 广西贺州市桂东电子科技有限责任公司 | Middle and high voltage electronic aluminium foil corrosion method |
| CN107502948A (en) * | 2017-07-15 | 2017-12-22 | 江苏国瑞科技有限公司 | A kind of new etched foil counter-boring techniques |
-
2017
- 2017-12-29 CN CN201711477367.2A patent/CN108456916B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029413A (en) * | 2006-12-19 | 2007-09-05 | 东莞市东阳光电容器有限公司 | Production of medium-high voltage anode corrosive foil |
| CN101225539A (en) * | 2007-09-28 | 2008-07-23 | 扬州宏远电子有限公司 | Multi-stage frequency-conversion eroding method for anode foil of aluminium electrolytic capacitor |
| CN101423946A (en) * | 2008-07-29 | 2009-05-06 | 东莞市东阳光电容器有限公司 | Technique for preparing etched foil of medium-high voltage anode foil for energy-saving lamp |
| CN105097286A (en) * | 2015-09-01 | 2015-11-25 | 广西贺州市桂东电子科技有限责任公司 | Etching method of ultra-high-pressure energy storage material |
| CN105551805A (en) * | 2016-01-18 | 2016-05-04 | 南通海星电子股份有限公司 | Intermediate processing method of electrode foil for middle-high voltage aluminium electrolytic capacitor |
| CN106098378A (en) * | 2016-06-27 | 2016-11-09 | 江苏荣生电子有限公司 | A kind of device manufacturing large aperture high-voltage high specific capacitance energy storage paper tinsel |
| CN106948000A (en) * | 2017-04-18 | 2017-07-14 | 扬州宏远电子有限公司 | A kind of etching process method for improving mesohigh etched foil corrosion layer intensity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108456916A (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108456916B (en) | Corrosion method of medium-high voltage electronic aluminum foil | |
| CN108538600B (en) | Hole-expanding corrosion method for high-voltage anode foil mixed acid in aluminum electrolysis | |
| JP6768088B2 (en) | Etching method of electrode foil for low-voltage aluminum electrolytic capacitors with low contact resistance | |
| CN101425390B (en) | Medium high voltage anode aluminum foil corrosion method | |
| CN105097286B (en) | A kind of caustic solution of super-pressure energy storage material | |
| KR102317276B1 (en) | Method for manufacturing electrode foil for surface mount aluminum electrolytic capacitors | |
| CN106653373A (en) | Formation foil for aluminium electrolytic capacitor and production process of formation foil | |
| CN110085455B (en) | Method for increasing specific volume of low-pressure corrosion aluminum foil | |
| CN110783108A (en) | Method for manufacturing corrosion foil | |
| CN110578163B (en) | Manufacturing method of medium-pressure corrosion foil | |
| CN112117128B (en) | High-specific-volume and high-strength medium-high voltage corrosion electrode foil and preparation method and application thereof | |
| CN107502948A (en) | A kind of new etched foil counter-boring techniques | |
| CN101345137A (en) | Anode foil corrosion technology of electrolytic capacitor | |
| KR20220160539A (en) | Manufacturing method of nano-microporous structure aluminum electrode foil for automotive electronics | |
| CN112899766A (en) | Manufacturing method of medium-pressure corrosion foil | |
| CN113628888A (en) | Preparation method of corrosion aluminum foil with high consistency of hole length | |
| CN109554746B (en) | Method for manufacturing high-pressure high-specific-volume corrosion foil | |
| CN110289171B (en) | Method for manufacturing non-phosphorus hole-expanding aluminum electrolytic capacitor electrode foil | |
| CN109797424B (en) | Method for treating five-level pore formation corrosion of medium-high voltage anode aluminum foil | |
| CN107254707A (en) | A kind of manufacture method of the quick middle-high voltage electrode foil of multistage hair engaging aperture | |
| JP2007103798A (en) | Method of forming aluminum electrode foil for electrolytic capacitor | |
| CN112853456A (en) | Method for manufacturing high-pressure high-specific-volume corrosion foil | |
| CN107699941A (en) | A kind of new aluminium corrosion foil pretreatment | |
| CN108754594B (en) | Method for power-on protection of semi-V cathode after medium-high voltage electronic aluminum foil hole corrosion | |
| CN113025961B (en) | Preparation method of electrode foil for aluminum electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220803 Address after: 834034 no.18-032, Industrial Avenue, huyanghe Industrial Park, Xinjiang Uygur Autonomous Region Patentee after: Xinjiang guangtou Guidong Electronic Technology Co.,Ltd. Address before: No. 39, Jiangbei East Road, Hezhou City, Guangxi Zhuang Autonomous Region Patentee before: GUANGXI HEZHOU GUIDONG ELECTRONIC TECHNOLOGY Co.,Ltd. |