CN111472039A - Preparation method of middle-high voltage electrode foil for aluminum electrolytic capacitor - Google Patents
Preparation method of middle-high voltage electrode foil for aluminum electrolytic capacitor Download PDFInfo
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- CN111472039A CN111472039A CN202010232202.4A CN202010232202A CN111472039A CN 111472039 A CN111472039 A CN 111472039A CN 202010232202 A CN202010232202 A CN 202010232202A CN 111472039 A CN111472039 A CN 111472039A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
Abstract
The invention provides a pore-forming corrosion liquid additive for an electrode foil and a method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor by using a pore-forming corrosion liquid containing the additive. The method comprises the following steps: the method comprises the following steps of pretreatment, primary pore-forming corrosion, secondary pore-expanding corrosion and post-treatment, wherein an additive is added into a primary pore-forming corrosion solution, and the additive is at least one of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof. The additive is beneficial to improving the uniformity of the holes and the consistency of the depth of the etched holes, and improving the appearance of the etched foil, so that the bending strength of the medium-high voltage electrode foil can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of electrode materials for capacitors, and particularly relates to a pore-forming corrosion liquid additive for an electrode foil and a method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor by using a pore-forming corrosion liquid containing the additive.
Background
With the development of miniaturization of the whole electronic equipment, urgent needs are provided for volume reduction and specific volume improvement of the aluminum electrolytic capacitor. The electrode foil is used as a core material in the aluminum electrolytic capacitor and plays a decisive role in various characteristics of the capacitor. An anode foil for an aluminum electrolytic capacitor is generally subjected to electrochemical etching to form a large number of vertical tunnel holes in the surface thereof so as to increase the effective surface area thereof, thereby increasing the capacity of the electrode foil; and then a layer of compact aluminum oxide film is generated on the surface of the etched hole through formation. The voltage resistance of the aluminum electrolytic capacitor is determined by the thickness of the oxide film, but the capacity, tensile strength and bending property thereof depend on the etching technique.
When the conventional corrosion process is used for carrying out the holing corrosion, the distribution of corrosion holes is not uniform, a large number of combined holes are formed in the subsequent reaming corrosion, and the combined holes lead to the thinning of the aluminum foil, so that the mechanical strength of the electrode foil is reduced. Especially, in the production process of a medium-high voltage corrosion foil production line, initial current of the open-pore corrosion is crucial to the uniformity of the open-pore germination, when the open-pore corrosion is carried out by the conventional process, a large amount of gas is generated on the cathode plate and the anode plate, and the gas is collected on the surface layer of the corrosion liquid, so that the efficiency of the initial current is easily reduced, the uniform germination of the open-pore is not facilitated, and the uniformity of the open-pore length is further influenced. And a large amount of gas in the corrosion tank liquid is easy to block an electric field, so that the growth of corrosion holes is influenced, branch holes are formed, and the improvement of the performance of the corrosion foil is not facilitated.
Disclosure of Invention
The invention provides a pore-forming corrosive liquid additive and a method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor by using a pore-forming corrosive liquid containing the additive, aiming at the problems that in the production process of a medium-high voltage corrosive foil production line, due to the fact that a large amount of gas is generated, etched pores are uneven, branch pores are easily generated, and the performance of a corrosive foil is affected.
Specifically, in a first aspect, the invention provides a pore-forming corrosion liquid additive for electrode foils, wherein the additive is at least one of ammonium diethyl fatty acid, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof.
Preferably, the additive is any one or two of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof.
According to the embodiment provided by the invention, the additive can change the liquid film structure of bubbles generated in the corrosion process, reduce the surface tension of the bubbles, promote the bubbles to break, and prevent a large amount of gas from blocking electric field lines, so that the initial current efficiency in the holing corrosion process is improved, the holing uniformity and the holing depth consistency are improved, the appearance of the corrosion foil is improved, and the bending strength of the medium-high voltage electrode foil can be effectively improved.
In another aspect, the invention provides a method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor, which comprises pretreatment, primary pitting corrosion, secondary reaming corrosion and post-treatment, wherein an additive is added into a corrosion solution of the primary pitting corrosion, and the additive is at least one of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof.
According to the embodiment provided by the invention, the content of the additive in the corrosion liquid for the primary open pore corrosion is 0.1-500 ppm, preferably 2-200 ppm.
According to an embodiment provided by the present invention, the additive is any one or two of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof.
According to an embodiment provided by the present invention, the additive is a combination of fatty acid diethyl ammonium or a salt thereof and tributyl phosphate or a salt thereof, a C12 alcohol phosphate ester or a salt thereof, or a C18 alcohol phosphate ester or a salt thereof. According to the embodiment provided by the invention, the content of hydrochloric acid in the corrosion solution for primary pore corrosion is 2-5 wt.%, and the content of sulfuric acid is 30-40 wt.%; when the hole is corroded, the current density is 0.1-2A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 60-360 s.
According to an embodiment of the present invention, the pre-processing comprises: the aluminum foil is placed into 0.5-3 wt.% NaOH aqueous solution at 40-60 ℃ to be soaked for 60-180 s, and then washed with water.
According to an embodiment of the present invention, the secondary counterbore corrosion comprises: will pass through the first-class hairThe aluminum foil with the corroded holes is placed in 1.5-4 wt.% nitric acid water solution for reaming corrosion, and the current density is 0.1-0.2A/cm2And (3) carrying out water washing at the corrosion temperature of 65-75 ℃ for 400-700 s.
According to an embodiment of the invention, the post-processing comprises: and (3) immersing the aluminum foil subjected to the secondary reaming corrosion into 3-6 wt.% nitric acid water solution for treatment at 60-80 ℃ for 30-120 s, and then washing and drying.
On the other hand, the invention also provides the medium-high voltage electrode foil obtained by the preparation method and the aluminum electrolytic capacitor comprising the medium-high voltage electrode foil.
Compared with the prior art, the invention has the following technical effects:
according to the invention, the additive with a specific structure is added during primary hole forming, so that the liquid film structure of bubbles generated in the corrosion process is changed, the surface tension of the bubbles is reduced, the bubble breakage is promoted, and a large amount of gas is prevented from blocking electric field lines, thus the initial current efficiency in the hole forming corrosion process is improved, the uniformity of the holes and the depth consistency of the etched holes are improved, the appearance of the corrosion foil is improved, and the bending strength of the medium-high voltage electrode foil can be effectively improved.
Drawings
FIG. 1: etching hole morphology pattern of the primary holed etched foil in the comparative example;
FIG. 2: etching hole topography for the primary holed etched foil in example 4.
Detailed Description
According to an embodiment provided by the present invention, the method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor includes:
1) pretreatment: soaking the aluminum foil in 0.5-3 wt.% NaOH aqueous solution at 40-60 ℃ for 60-180 s, and then washing with water;
2) primary pitting corrosion: placing the pretreated aluminum foil in an aqueous solution containing 2-5 wt.% of hydrochloric acid, 30-40 wt.% of sulfuric acid and 0.1-500 ppm of additive for pore-forming corrosion, wherein the current density is 0.1-2A/cm2The corrosion temperature is 60-80 ℃, the corrosion time is 60-360 s, and then washing is carried out; the additive is fatty acid ammonium diethyl ester and phosphoric acid trisAt least one of butyl ester, C12 alcohol phosphate, C18 alcohol phosphate or salt thereof;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in 1.5-4 wt.% nitric acid water solution for reaming corrosion, wherein the current density is 0.1-0.2A/cm2The corrosion temperature is 65-75 ℃, the corrosion time is 400-700 s, and then washing is carried out;
4) and (3) post-treatment: and (3) immersing the aluminum foil subjected to the secondary reaming corrosion into 3-6 wt.% nitric acid water solution for treatment at 60-80 ℃ for 30-120 s, and then washing and drying.
Specifically, the process conditions of the steps are as follows:
1) and pretreatment
Before pitting corrosion, the aluminum foil generally needs to be subjected to cleaning pretreatment, aiming at removing oil stains and oxidation layers on the surface of the aluminum foil. The pretreatment may be performed in an alkali solution or/and an acid solution.
In an embodiment of the present invention, the pretreatment includes: the aluminum foil is placed into 0.5-3 wt.% NaOH aqueous solution at 40-60 ℃ to be soaked for 60-180 s, and then the aluminum foil is washed with water at room temperature.
Non-limiting examples of the concentration of the aqueous NaOH solution include: 0.5 wt.%, 0.8 wt.%, 1 wt.%, 1.2 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.3 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, and the like.
Non-limiting examples of the soaking temperature in the NaOH solution include: 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, etc.
Non-limiting examples of such soaking times in NaOH solutions include: 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s, and so forth.
In some embodiments, the pre-treatment is: the aluminum foil is soaked in a sodium hydroxide aqueous solution containing 0.5-1.5 wt.% at 45-60 ℃ for 60-120 s, and then washed with water at room temperature.
2) Primary pitting corrosion
The primary pitting corrosion is performed in an aqueous solution containing 2-5 wt.% hydrochloric acid, 30-40 wt.% sulfuric acid, and 0.1-500 ppm of an additive.
Non-limiting examples of the concentration of hydrochloric acid include: 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, and so forth.
Non-limiting examples of the concentration of sulfuric acid include: 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, and so forth.
The additive is at least one of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salt thereof.
In some embodiments, the additive is any one or two of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate, or salts thereof.
In some embodiments, the additive is a combination of fatty acid diethyl ammonium or a salt thereof and tributyl phosphate or a salt thereof, a C12 alcohol phosphate ester or a salt thereof, or a C18 alcohol phosphate ester or a salt thereof. The combination of the two can greatly reduce the surface tension and viscosity of the liquid film through the synergistic effect, and effectively promote the bubble rupture.
In some embodiments, the additive is a combination of ammonium diethyl fatty acid and tributyl phosphate.
The content of the additives can be adjusted according to the selection of the specific additives. Preferred ranges for the additive content include, but are not limited to: 0.1 to 10ppm, 10 to 50ppm, 50 to 100ppm, 10 to 100ppm, 100 to 200ppm, 200 to 300ppm, 2 to 200ppm, 10 to 200ppm, 200 to 500 ppm.
In some embodiments, the additive is present in an amount of 2 to 200ppm, for example: 2ppm, 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, 200ppm, and the like.
In some embodiments, the primary pore etching is performed in an aqueous solution containing 3 to 4.5 wt.% hydrochloric acid, 32 to 38 wt.% sulfuric acid, and 10 to 200ppm of an additive.
The current density of the first-stage pore formation corrosion is 0.1-2A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 60-360 s.
Non-limiting examples of the current density include: 0.1A/cm2、0.2A/cm2、0.3A/cm2、0.4A/cm2、0.5A/cm2、0.6A/cm2、0.7A/cm2、0.8A/cm2、0.9A/cm2、1A/cm2、1.1A/cm2、1.2A/cm2、1.3A/cm2、1.4A/cm2、1.5A/cm2、1.6A/cm2、1.7A/cm2、1.8A/cm2、1.9A/cm2、2A/cm2And so on.
Non-limiting examples of the corrosion temperature include: 60 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 73 deg.C, 75 deg.C, 80 deg.C, etc.
Non-limiting examples of the corrosion time include: 60s, 80s, 100s, 120s, 150s, 180s, 200s, 240s, 260s, 280s, 300s, 320s, 360s, and so on.
In some embodiments, the primary pitting corrosion comprises: placing the pretreated aluminum foil in a corrosive liquid containing 3-4.5 wt.% of hydrochloric acid, 32-38 wt.% of sulfuric acid and 2-200 ppm of additives for pore-forming corrosion, wherein the current density is 0.25-1.5A/cm2The corrosion temperature is 65-75 ℃, the corrosion time is 80-300 s, and then washing is carried out at room temperature.
3) Second stage of counterboring corrosion
The secondary reaming corrosion is carried out in 1.5-4 wt.% nitric acid water solution, and the current density is 0.1-0.2A/cm2The corrosion temperature is 65-75 ℃, the corrosion time is 400-700 s, and then washing is carried out at room temperature.
Non-limiting examples of the concentration of the aqueous nitric acid solution include: 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, 3.5 wt.%, 3.8 wt.%, 4 wt.%, and so forth.
Non-limiting examples of the current density include: 0.1A/cm2、0.12A/cm2、0.13A/cm2、0.14A/cm2、0.15A/cm2、0.16A/cm2、0.17A/cm2、0.18A/cm2、0.19A/cm2、0.2A/cm2And so on.
Non-limiting examples of the corrosion temperature include: 65 deg.C, 68 deg.C, 70 deg.C, 73 deg.C, 75 deg.C, etc.
Non-limiting examples of the corrosion time include: 400s, 420s, 450s, 480s, 500s, 520s, 550s, 580s, 600s, 620s, 650s, 680s, 700s, and so on.
In some embodiments, the secondary counterbore corrosion comprises: putting the aluminum foil subjected to the first-level pore forming corrosion into 2-3.5 wt.% nitric acid water solution, wherein the current density is 0.1-0.2A/cm2The corrosion temperature is 68-73 ℃, the corrosion time is 450-700 s, and then the room temperature water washing is carried out.
6) Post-treatment
And (3) immersing the aluminum foil subjected to secondary hole expansion corrosion into 3-6 wt.% nitric acid water solution, treating for 30-120 s at 60-80 ℃, washing with room-temperature water, and drying for 120-600 s at 60-100 ℃.
Non-limiting examples of the concentration of the aqueous nitric acid solution include: 3 wt.%, 3.2 wt.%, 3.5 wt.%, 3.8 wt.%, 4 wt.%, 4.2 wt.%, 4.5 wt.%, 4.8 wt.%, 5 wt.%, 5.2 wt.%, 5.5 wt.%, 5.8 wt.%, 6 wt.%, and the like.
Non-limiting examples of the soaking temperature include: 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, etc.
Non-limiting examples of the soaking time include: 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s, 120s, and so forth.
Non-limiting examples of the drying temperature include: 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, etc.
Non-limiting examples of such drying times include: 120s, 180s, 200s, 240s, 300s, 360s, 400s, 420s, 480s, 500s, 540s, 600s, and so forth.
In some embodiments, the post-processing comprises: and (3) immersing the aluminum foil subjected to secondary reaming corrosion into 3.5-5 wt.% nitric acid water solution for treatment at 60-70 ℃ for 60-90 s, washing with room-temperature water, and drying at 75-95 ℃ for 300-480 s.
In the present invention, "which" in "or a salt thereof means fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate ester, or C18 alcohol phosphate ester. That is, the additive according to the present invention is at least one of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or a salt thereof, and is understood to be: the additive is at least one of fatty acid diethyl ammonium or salt thereof, tributyl phosphate or salt thereof, C12 alcohol phosphate or salt thereof, and C18 alcohol phosphate or salt thereof.
The room temperature in the invention is 20-35 ℃.
Unless otherwise specified, the solution referred to in the present invention means an aqueous solution.
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications based on the inventive concept herein will occur to those skilled in the art and are intended to be included within the scope of the present invention.
Example 1
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2Performing electrochemical pore-forming corrosion in aqueous solution of SO4 and 80ppm tributyl phosphate, wherein the current density is 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning at room temperature.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3The water solution of (2) is subjected to secondary reaming corrosion, and the current density is 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and then the substrate is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3Treating with water solution at 60 deg.C for 60s, cleaning with deionized water at room temperature, and drying at 75 deg.C for 300s。
Example 2
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2SO4And electrochemical pitting corrosion is carried out in 80ppm aqueous solution of ammonium diethyl fatty acid with current density of 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning at room temperature.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3The water solution of (2) is subjected to secondary reaming corrosion, and the current density is 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and then the substrate is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3Treating in water solution at 60 deg.C for 60s, cleaning with deionized water at room temperature, and drying at 75 deg.C for 300 s.
Example 3
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2SO46.5ppm ammonium diethyl fatty acid, 2.5ppm tributyl phosphate, and current density of 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning at room temperature.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3The water solution of (2) is subjected to secondary reaming corrosion, and the current density is 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and then the substrate is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3Treating in solution at 60 deg.C for 60s, and cleaning with deionized water at room temperatureAfter washing, the mixture was dried at 75 ℃ for 300 seconds.
Example 4
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2SO460ppm of fatty acid diethyl ammonium and 20ppm of tributyl phosphate in water solution, and performing electrochemical pitting corrosion with current density of 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning at room temperature.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3The water solution of (2) is subjected to secondary reaming corrosion, and the current density is 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and then the substrate is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3Treating in water solution at 60 deg.C for 60s, cleaning with deionized water at room temperature, and drying at 75 deg.C for 300 s.
Example 5
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2SO4150ppm of ammonium diethyl fatty acid and 50ppm of tributyl phosphate in water solution, and performing electrochemical pitting corrosion with current density of 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning at room temperature.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3The water solution of (2) is subjected to secondary reaming corrosion, and the current density is 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and then the substrate is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3Treating in water solution at 60 deg.C for 60s, cleaning with deionized water at room temperature, and drying at 75 deg.C for 300 s.
Comparative example 1
(1) Pretreatment: the aluminum foil is soaked in 1 wt% NaOH aqueous solution at 60 ℃ for 60s and then is cleaned by deionized water at room temperature.
(2) Primary pitting corrosion: pre-treated aluminum foil containing 3 wt.% HCl and 35 wt.% H2SO4The current density is 0.6A/cm2The etching time is 80s, the temperature is 73 ℃, and then deionized water is used for cleaning.
(3) Secondary reaming corrosion: subjecting the aluminum foil subjected to primary holing corrosion to a solution containing 3.5 wt.% of HNO3Performing secondary reaming corrosion in water solution with current density of 0.1A/cm2And the etching temperature is 70 ℃, the etching time is 700s, and the glass is cleaned by deionized water at room temperature.
(4) And (3) post-treatment: immersing the aluminum foil subjected to the secondary reaming corrosion in 5 wt.% HNO3The solution was treated at 60 ℃ for 60s, then rinsed with deionized water at room temperature and dried at 75 ℃ for 300 s.
Performance testing
The electrostatic capacity and the number of times of bending were measured after forming the electrode foils of the examples and comparative examples, and the test results are shown in table 1, and the forming conditions were as follows: 10% boric acid at 90 deg.C and current density of 25A/dm2The formation voltage is Vfe-520V. The detection method was carried out according to the standard described in national Standard "SJ/T11140-.
TABLE 1
From the data in the table, it can be seen that the anti-bending performance of the electrode foil can be effectively improved by adopting the etching process of the invention under the condition of keeping the electrostatic capacity not to be greatly reduced.
As can be seen from the figures 1 and 2, after the additive is added into the primary hair hole corrosion liquid, the hair hole corrosion foil appearance is obviously improved, the transverse branch holes are obviously reduced, and the hole depth consistency is improved.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes in the method can be made without departing from the spirit of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Claims (11)
1. The additive is characterized in that the additive is at least one of ammonium diethyl fatty acid, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salt thereof.
2. A preparation method of a medium-high voltage electrode foil for an aluminum electrolytic capacitor comprises pretreatment, primary hole forming corrosion, secondary hole expanding corrosion and post-treatment, and is characterized in that an additive is added into a corrosion solution of the primary hole forming corrosion, and the additive is at least one of fatty acid diethyl ammonium, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate or salts thereof.
3. The method for preparing a medium-high voltage electrode foil for an aluminum electrolytic capacitor according to claim 2, wherein the additive is contained in the primary pore-forming corrosion solution in an amount of 0.1 to 500ppm, preferably 2 to 200 ppm.
4. The method for manufacturing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in claim 3, wherein the additive is one or two of ammonium diethyl fatty acid, tributyl phosphate, C12 alcohol phosphate, C18 alcohol phosphate, or a salt thereof.
5. The method for producing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in claim 3, wherein the additive is a combination of ammonium diethyl fatty acid or a salt thereof with tributyl phosphate or a salt thereof, C12 alcohol phosphate or a salt thereof, or C18 alcohol phosphate or a salt thereof.
6. The method for producing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in any one of claims 2 to 5, wherein the primary pore-forming etching solution contains 2 to 5 wt.% of hydrochloric acid and 30 to 40 wt.% of sulfuric acid; when the hole is corroded, the current density is 0.1-2A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 60-360 s.
7. The method for producing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in claim 2, wherein the pretreatment comprises: the aluminum foil is placed into 0.5-3 wt.% NaOH aqueous solution at 40-60 ℃ to be soaked for 60-180 s, and then washed with water.
8. The method for producing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in claim 2, wherein the secondary pore-enlarging etching comprises: will be provided withThe aluminum foil subjected to the first-stage holing corrosion is placed in 1.5-4 wt.% nitric acid water solution for reaming corrosion, and the current density is 0.1-0.2A/cm2And (3) carrying out water washing at the corrosion temperature of 65-75 ℃ for 400-700 s.
9. The method for producing a medium-high voltage electrode foil for an aluminum electrolytic capacitor as recited in claim 2, wherein the post-treatment comprises: and (3) immersing the aluminum foil subjected to the secondary reaming corrosion into 3-6 wt.% nitric acid water solution for treatment at 60-80 ℃ for 30-120 s, and then washing and drying.
10. A medium-high voltage electrode foil for aluminum electrolytic capacitors obtained by the production method according to any one of claims 2 to 9.
11. An aluminum electrolytic capacitor comprising the medium-high voltage electrode foil for an aluminum electrolytic capacitor according to claim 10.
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