CN112038102B - Preparation method of ultrahigh-pressure corrosion foil - Google Patents

Preparation method of ultrahigh-pressure corrosion foil Download PDF

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CN112038102B
CN112038102B CN202010858129.1A CN202010858129A CN112038102B CN 112038102 B CN112038102 B CN 112038102B CN 202010858129 A CN202010858129 A CN 202010858129A CN 112038102 B CN112038102 B CN 112038102B
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corrosion
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etched foil
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CN112038102A (en
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徐健
肖远龙
龙文祥
何凤荣
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Dongguan HEC Tech R&D Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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

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Abstract

The invention provides a preparation method of an ultrahigh-pressure etched foil. The preparation 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 the pretreatment is carried out in sulfamic acid aqueous solution, and the secondary pore-expanding corrosion is carried out in corrosive liquid containing a 5-diisopropyl amino pentylamine corrosion inhibitor. The corrosion action of the sulfamic acid aqueous solution on the surface of the aluminum foil is lower than that of strong alkali, the thickness of the aluminum foil can be effectively ensured, and the 5-diisopropylaminopentylamine can improve the activation energy of corrosion reaction, inhibit the corrosion reaction and play a role in inhibiting corrosion.

Description

Preparation method of ultrahigh-pressure corrosion foil
Technical Field
The invention belongs to the technical field of electrode materials for capacitors, and particularly relates to a preparation method of an ultrahigh-pressure corrosion foil.
Background
With the development of miniaturization of the whole electronic equipment, urgent needs are put forward for the miniaturization of the volume and the high specific volume of the aluminum electrolytic capacitor. The electrode foil is used as the core material of 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.
The existing preparation of the ultrahigh-pressure corrosion foil generally has the following defects: on one hand, in the ultrahigh pressure corrosion process, the aluminum foil surface is cleaned by using a strong alkali (such as sodium hydroxide) or strong acid (such as hydrochloric acid, sulfuric acid or nitric acid) aqueous solution in the pretreatment process, but the aluminum foil surface is seriously thinned due to high denudation strength and violent reaction of the sodium hydroxide, the subsequent corrosion and capacity and other performances of the aluminum foil are influenced, and the sulfuric acid has a passivation effect, the hydrochloric acid is volatile, and the toxicity of the nitric acid is strong; on the other hand, chemical substances containing phosphorus exist in the corrosive solution, and the existence of phosphorus causes pollution to natural water in the treatment process, causes water eutrophication and harms the environment.
Disclosure of Invention
In a first aspect, the invention provides a pretreatment solution for an ultrahigh-pressure etched foil, which uses an sulfamic acid aqueous solution to replace a general strong acid or strong alkali aqueous solution, wherein the sulfamic acid aqueous solution has strong acidity equal to that of hydrochloric acid and sulfuric acid, has good stability, is characterized by non-volatility, no odor and low toxicity to human bodies, can remove impurities on the surface of an aluminum foil, has a lower corrosion effect on the surface of the aluminum foil than strong alkali, can ensure the uniformity of the thickness and the surface state of the aluminum foil, and can improve the capacity of the etched foil.
In the second aspect, the corrosion solution for reaming corrosion is added with the corrosion inhibitor 5-diisopropylamino pentylamine, so that the problem of environmental pollution caused by the phosphorus-containing corrosion inhibitor is solved. The 5-diisopropyl amino pentylamine simultaneously has polar groups and nonpolar groups, N elements in the polar groups contain lone pair electrons, the electronegativity is large, the N elements are firmly adsorbed on the surface of the metal aluminum foil, and the nonpolar groups are arranged in a corrosive medium, so that on one hand, the contact between the metal aluminum foil and the corrosive medium is effectively isolated, the diffusion of corrosion reaction products is hindered, simultaneously, the structure of a double electric layer is changed, the activation energy of the corrosion reaction is improved, the corrosion reaction is finally inhibited, and the corrosion inhibition effect is achieved.
In order to achieve the above object, the present invention adopts the following technical solutions.
Specifically, in a first aspect, the invention provides a pretreatment solution for ultrahigh pressure etched foil, wherein the pretreatment solution is an aqueous sulfamic acid solution, and the content of sulfamic acid is 1 to 50 wt.%, preferably 5 to 50 wt.%, and more preferably 5 to 30 wt.%.
In a more preferred embodiment, copper ions are added to the sulfamic acid aqueous solution. The sulfamic acid contains amino, so that the adhesion of copper ions on the surface of the aluminum foil can be increased, the surface of the aluminum foil can be better activated, and the subsequent pore corrosion is facilitated.
According to an embodiment of the present invention, the content of the copper ion in the sulfamic acid aqueous solution is 1 to 1000ppm, preferably 100 to 1000ppm, more preferably 100 to 800ppm, and particularly preferably 100 to 500 ppm.
On the other hand, the invention provides a preparation method of the ultrahigh-pressure etched foil, which comprises pretreatment, primary pore-forming corrosion, secondary pore-expanding corrosion and post-treatment, wherein the pretreatment is carried out in an aqueous solution of sulfamic acid, and the content of the sulfamic acid is 1-50 wt.%, preferably 5-50 wt.%, and more preferably 5-30 wt.%.
In a more preferred embodiment, copper ions are added to the sulfamic acid aqueous solution, and the content of the copper ions is 1 to 1000ppm, preferably 100 to 1000ppm, more preferably 100 to 800ppm, and particularly preferably 100 to 500 ppm.
According to the embodiment provided by the invention, the temperature of the pretreatment is 40-65 ℃, and the time of the pretreatment is 30-60 s.
In a preferred embodiment, the secondary pore-enlarging etching is performed in an etching solution containing a 5-diisopropylaminopentylamine corrosion inhibitor.
According to some embodiments of the invention, the 5-diisopropylaminopentylamine is present in an amount of 0.1 to 1 wt.%.
According to an embodiment of the present invention, the secondary pore-enlarging etching is performed in a mixed aqueous solution containing aluminum ions, 5-diisopropylaminopentylamine and nitric acid.
According to some embodiments of the invention, the nitric acid is present in an amount of 3 to 10 wt.%.
According to some embodiments of the invention, the aluminum ion is present in an amount of 0.5 to 2 wt.%.
According to an embodiment provided by the present invention, the secondary pore-enlarging etching is performed in a mixed aqueous solution containing aluminum ions, 5-diisopropylaminopentylamine and nitric acid; preferably, the nitric acid is contained in an amount of 3 to 10 wt.%, the aluminum ion is contained in an amount of 0.5 to 2 wt.%, and the 5-diisopropylaminopentylamine is contained in an amount of 0.1 to 1 wt.%.
According to the embodiment provided by the invention, the current density is 0.1-0.25A/cm during the secondary reaming corrosion2The corrosion temperature is 60-70 ℃, and the corrosion time is 400-500 s.
According to the embodiment provided by the invention, the primary pore-forming etching solution is carried out in a mixed aqueous solution containing aluminum ions, hydrochloric acid and sulfuric acid, preferably, the content of the aluminum ions is 0.5-1 wt.%, the content of the hydrochloric acid is 5-10 wt.%, and the content of the sulfuric acid is 30-50 wt.%.
According to the embodiment provided by the invention, the current density is 0.5-0.7A/cm when the primary hole is corroded2The corrosion temperature is 60-80 ℃, and the corrosion time is 50-100 s.
According to an embodiment provided by the present invention, the post-treatment is performed in a mixed aqueous solution containing aluminum ions and nitric acid; preferably, the content of the nitric acid is 5-15 wt.%, and the content of the aluminum ions is 0.2-2 wt.%.
According to the embodiment provided by the invention, the post-treatment temperature is 50-60 ℃, and the treatment time is 40-120 s.
In another aspect, the present invention provides the extra-high pressure etched foil obtained by the above-described production method, and an electrode foil obtained by chemical conversion of the extra-high pressure etched foil.
In another aspect, the present invention also provides an aluminum electrolytic capacitor comprising the electrode foil.
Compared with the prior art, the invention has the following technical effects:
(1) the invention uses sulfamic acid aqueous solution to replace general strong acid or strong alkaline aqueous solution, the sulfamic acid aqueous solution has the same strong acid as hydrochloric acid and sulfuric acid, has good stability, has the characteristics of non-volatility, no odor, small toxicity to human bodies and the like, has lower corrosion action on the surface of the aluminum foil than strong alkali, can effectively ensure the thickness of the aluminum foil, and reduces the thinning of the aluminum foil by about 2 mu m when the aluminum foil is treated by the strong alkali in the pretreatment process.
(2) According to the invention, copper ions are added into the sulfamic acid aqueous solution, and the sulfamic acid contains amino, so that the adhesion of the copper ions on the surface of the aluminum foil can be increased, the pore-forming sites on the surface of the corrosion foil can be effectively improved, the corrosion pore diameter is increased, and the capacity of the corrosion foil is improved.
(3) The corrosion inhibitor 5-diisopropylamino pentylamine is added into the corrosive liquid for reaming corrosion, so that the problem of environmental pollution caused by the phosphorus-containing corrosion inhibitor is solved.
Drawings
FIG. 1: etching hole morphology pattern of the etched foil obtained in example 3;
FIG. 2: etching hole morphology pattern of the etched foil obtained in comparative example 1;
FIG. 3: etching hole morphology pattern of the etched foil obtained in comparative example 2; and
FIG. 4: etching hole morphology pattern of the etched foil obtained in comparative example 3;
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
Unless otherwise specified, the solution referred to in the present invention means an aqueous solution.
The ultrahigh voltage is a voltage of 700v or more.
The process for preparing the ultra-high pressure etched foil will be described in detail below with reference to specific examples.
1) Pretreatment of the mixture
Before pitting corrosion, the aluminum foil generally needs to be cleaned and pretreated, aiming at removing oil stains and oxide layers on the surface of the aluminum foil.
According to an embodiment provided by the present invention, the pre-treatment is performed in an aqueous solution of sulfamic acid, the content of sulfamic acid is 1 to 50 wt.%, preferably 5 to 50 wt.%, more preferably 5 to 30 wt.%.
Specifically, the content of the sulfamic acid may be exemplified by: 1wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, and so forth.
In some embodiments, the sulfamic acid is present in an amount of 5 to 15 wt.%.
As a more preferred embodiment, copper ions are added to the sulfamic acid solution and the pretreatment is carried out in an aqueous sulfamic acid solution containing copper ions.
According to an embodiment of the present invention, the content of the copper ion is 1 to 1000ppm, preferably 100 to 1000ppm, more preferably 100 to 800ppm, and particularly preferably 100 to 500 ppm.
Specifically, the content of the copper ion may be: 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, and so forth.
In some embodiments, the copper ion content is 100 to 300 ppm; in other embodiments, the copper ion is present in an amount of 100 to 250 ppm.
According to the embodiment provided by the invention, the temperature of the pretreatment is 40-65 ℃, and the time of the pretreatment is 30-60 s.
Specifically, the temperature of the pretreatment may be exemplified by: 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, etc.
The pretreatment time may be exemplified by: 30s, 35s, 40s, 45s, 50s, 55s, 60s, etc.
2) Primary pitting corrosion
The primary pore etching is carried out in a mixed aqueous solution containing aluminum ions, hydrochloric acid and sulfuric acid.
According to an embodiment of the present invention, the content of aluminum ions is 0.5 to 1wt.%, the content of hydrochloric acid is 5 to 10 wt.%, and the content of sulfuric acid is 30 to 50 wt.%.
The content of the aluminum ions may be exemplified by: 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1wt.%, and so forth.
The content of the hydrochloric acid may be exemplified by: 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, and so forth.
The content of the sulfuric acid may be exemplified by: 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 43 wt.%, 44 wt.%, 45 wt.%, 46 wt.%, 47 wt.%, 48 wt.%, 49 wt.%, 50 wt.%, and so forth.
The current density of the primary hole corrosion is 0.5-0.7A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 50-100 s.
Specifically, the current density may be exemplified by: 0.5A/cm2、0.51A/cm2、0.52A/cm2、0.53A/cm2、0.54A/cm2、0.55A/cm2、0.56A/cm2、0.57A/cm2、0.58A/cm2、0.59A/cm2、0.6A/cm2、0.61A/cm2、0.62A/cm2、0.63A/cm2、0.64A/cm2、0.65A/cm2、0.66A/cm2、0.67A/cm2、0.68A/cm2、0.69A/cm2、0.7A/cm2And so on.
The corrosion temperature may be exemplified by: 60 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, 73 deg.C, 75 deg.C, 80 deg.C, etc.
The etching time may be exemplified by: 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, and so forth.
3) Second stage of counterboring corrosion
The secondary reaming corrosion is carried out in a mixed aqueous solution containing aluminum ions, 5-diisopropylaminopentylamine and nitric acid.
According to an embodiment of the present invention, the nitric acid is contained in an amount of 3 to 10 wt.%, the aluminum ion is contained in an amount of 0.5 to 2 wt.%, and the 5-diisopropylaminopentylamine is contained in an amount of 0.1 to 1 wt.%.
Specifically, the content of the nitric acid may be exemplified by: 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, and so forth.
The content of the aluminum ions may be exemplified by: 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2 wt.%, etc.
The content of the 5-diisopropylaminopentylamine may be exemplified by: 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1wt.%, and the like.
According to the embodiment provided by the invention, the current density is 0.1-0.25A/cm during the secondary reaming corrosion2The corrosion temperature is 60-70 ℃, and the corrosion time is 400-500 s
Specifically, the current density may be exemplified by: 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/cm2、0.21A/cm2、0.22A/cm2、0.23A/cm2、0.24A/cm2、0.25A/cm2And so on.
The corrosion temperature may be exemplified by: 60 ℃, 65 ℃, 68 ℃, 70 ℃, etc.
The etching time may be exemplified by: 400s, 410s, 420s, 430s, 440s, 450s, 460s, 470s, 480s, 490s, 500s, and so on.
4) Post-treatment
The post-treatment is carried out in a mixed aqueous solution containing aluminum ions and nitric acid, wherein the content of the nitric acid is 5-15 wt.%, and the content of the aluminum ions is 0.2-2 wt.%.
Specifically, the content of the nitric acid may be exemplified by: 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 7.5 wt.%, 8 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%, 10.5 wt.%, 11 wt.%, 11.5 wt.%, 12 wt.%, 12.5 wt.%, 13 wt.%, 13.5 wt.%, 14 wt.%, 14.5 wt.%, 15 wt.%, and the like.
The content of the aluminum ions may be exemplified by: 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2 wt.%, and so forth.
According to the embodiment provided by the invention, the post-treatment temperature is 50-60 ℃, and the treatment time is 40-120 s.
The post-treatment temperature may be exemplified by: 50 deg.C, 55 deg.C, 60 deg.C, etc.
The post-treatment time may be exemplified by: 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s, 120s, and so forth.
According to some embodiments of the present invention, the method for preparing the ultra-high pressure etched foil comprises:
1) pretreatment: soaking the aluminum foil in sulfamic acid aqueous solution containing copper ions at 40-65 ℃ for 30-60 s, wherein the content of sulfamic acid is 1-50 wt.%, and the content of copper ions is 1-1000 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5-1 wt.% of aluminum ions, 5-10 wt.% of hydrochloric acid and 30-50 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5-0.7A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 50-100 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to primary holing corrosion in a mixed aqueous solution containing 0.5-2 wt.% of aluminum ions, 0.1-1 wt.% of 5-diisopropylamino pentylamine and 3-10 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.1-0.25A/cm2The corrosion temperature is 60-70 ℃, and the corrosion time is 400-500 s;
4) and (3) post-treatment: and (3) placing the aluminum foil subjected to the secondary hole expanding corrosion in a mixed aqueous solution containing 0.2-2 wt.% of aluminum ions and 5-15 wt.% of nitric acid, and treating for 40-120 s at 50-60 ℃.
According to other embodiments provided by the present invention, the method for preparing the ultra-high pressure etched foil includes:
1) pretreatment: soaking the aluminum foil in 1-50 wt.% of sulfamic acid aqueous solution at 40-65 ℃ for 30-60 s;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5-1 wt.% of aluminum ions, 5-10 wt.% of hydrochloric acid and 30-50 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5-0.7A/cm2The corrosion temperature is 60-80 ℃, and the corrosion time is 50-100 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to primary holing corrosion in a mixed aqueous solution containing 0.5-2 wt.% of aluminum ions, 0.1-1 wt.% of 5-diisopropylamino pentylamine and 3-10 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.1-0.25A/cm2The corrosion temperature is 60-70 ℃, and the corrosion time is 400-500 s;
4) and (3) post-treatment: and (3) placing the aluminum foil subjected to the secondary hole expanding corrosion in a mixed aqueous solution containing 0.2-2 wt.% of aluminum ions and 5-15 wt.% of nitric acid, and treating for 40-120 s at 50-60 ℃.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 5 wt.%, and the content of copper ions is 100 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
Example 2
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 10 wt.%, and the content of copper ions is 150 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density isIs 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
Example 3
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 15 wt.%, and the content of copper ions is 200 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
SEM test of the etched foil obtained in this example is shown in FIG. 1, which shows that the cross-section of the pore channel in the picture is relatively regular, the overall cross-sectional thickness is 123-.
Example 4
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 15 wt.%, and the content of copper ions is 200 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.5 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
Example 5
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 15 wt.%, and the content of copper ions is 200 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 1wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for hole expanding corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
Example 6
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 15 wt.% sulfamic acid aqueous solution at 50 ℃ for 50 s;
2) primary pitting corrosion: the pretreated aluminum foil was placed in a container containing 0.5 wt.% aluminum ions, 5 wt.% hydrochloric acid and 30wt.% sulfuric acid mixed aqueous solution for pitting corrosion, the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
Comparative example 1
1) Pretreatment: placing a 125-micron high-purity aluminum foil in a 15 wt.% sodium hydroxide solution at 50 ℃ to soak for 50 s;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of 5-diisopropylamino pentylamine and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
SEM test of the corrosion foil obtained in the comparative example is carried out, as shown in FIG. 2, it can be seen that a part of long holes appear, and the thickness of the cross section of the corrosion foil is measured to be 121-122 μm by using picture analysis software, namely the thickness of the corrosion foil is reduced and increased after the treatment of sodium hydroxide.
Comparative example 2
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 15 wt.%, and the content of copper ions is 200 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
SEM test is carried out on the corrosion foil obtained by the comparative example, as shown in figure 3, the cross section end of the integral appearance of the pore channel is obviously changed, a large number of long and short pores are generated, and the cross section appearance thickness of the corrosion foil is measured by using picture analysis software, so that the cross section thickness is slightly reduced.
Comparative example 3
1) Pretreatment: soaking a 125-micron high-purity aluminum foil in 50 ℃ sulfamic acid aqueous solution containing copper ions for 50s, wherein the content of sulfamic acid is 15 wt.%, and the content of copper ions is 200 ppm;
2) primary pitting corrosion: placing the pretreated aluminum foil in a mixed aqueous solution containing 0.5 wt.% of aluminum ions, 5 wt.% of hydrochloric acid and 30 wt.% of sulfuric acid for pore-forming corrosion, wherein the current density is 0.5A/cm2The corrosion temperature is 65 ℃, and the corrosion time is 80 s;
3) secondary reaming corrosion: placing the aluminum foil subjected to the primary holing corrosion in a mixed aqueous solution containing 1wt.% of aluminum ions, 0.1 wt.% of p-phenylthiourea and 5 wt.% of nitric acid for reaming corrosion, wherein the current density is 0.18A/cm2The corrosion temperature is 70 ℃, and the corrosion time is 500 s;
4) and (3) post-treatment: the aluminum foil subjected to the secondary hole expansion etching was placed in an aqueous solution containing 1wt.% of aluminum ions and 10 wt.% of nitric acid, and treated at 55 ℃ for 60 seconds.
The etched foil obtained in the comparative example is subjected to SEM test, as shown in FIG. 4, it can be seen that the shapes of the long and short holes at the cross section end of the etched foil are relatively regular, and the length uniformity of the pore path of the etched foil is improved compared with the cross section picture of the comparative example 2.
Performance testing
The electrostatic capacity and the number of times of bending were measured after forming the corrosion foils of the examples and comparative examples, and the results are shown in Table 1, and the forming conditions were as follows: 7% boric acid at 90 deg.C and current density of 0.05A/cm2The formation voltage is Vfe-850V. The detection method was carried out according to the standard described in national Standard "SJ/T11140-.
TABLE 1
Test item Capacity (. mu.F/cm)2) Voltage (V) Bend (Hui) Pulling force (N/cm) Thickness (μm) Excess weight (mg)
Example 1 0.352 852 48 22.3 123-124 0.1587
Example 2 0.345 858 51 23.0 122-123 0.1550
Example 3 0.343 860 53 22.5 122-123 0.1507
Example 4 0.351 851 52 22.8 123-124 0.1605
Example 5 0.345 854 49 22.6 122-123 0.1623
Example 6 0.343 857 50 22.1 123-124 0.1645
Comparative example 1 0.320 850 50 22.0 120-121 0.1484
Comparative example 2 0.323 856 50 22.3 122-123 0.1495
Comparative example 3 0.321 852 51 22.7 121-122 0.1552
The data in the table show that the thickness of the corrosion foil can be effectively ensured by adopting the corrosion process of the invention, and the capacity and the mechanical property of the corrosion foil are improved while the bending is ensured. In the comparative example 1, the traditional alkali liquor pretreatment is adopted, the thickness of the corrosion foil is reduced more, the residual weight is obviously lightened, and the capacity is reduced more; in comparative example 2, since no corrosion inhibitor was used, and in comparative example 3, other corrosion inhibitors were used instead of 5-diisopropylaminopentylamine, the same etched foil was reduced in thickness by a relatively greater amount, had a relatively lighter residual weight, and had a relatively lower capacity.
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 (24)

1. The pretreatment solution for the ultrahigh-pressure etched foil is characterized by being an sulfamic acid aqueous solution, wherein the content of sulfamic acid is 1-50 wt.%, copper ions are added into the sulfamic acid aqueous solution, and the content of the copper ions is 1-1000 ppm.
2. The pretreatment solution for extra-high pressure etched foil according to claim 1, wherein the content of sulfamic acid is 5 to 50 wt.%.
3. The pretreatment solution for extra-high pressure etched foil according to claim 2, wherein the content of sulfamic acid is 5 to 30 wt.%.
4. The pretreatment solution for extra-high pressure etched foil according to claim 1, wherein the content of copper ions is 100 to 800 ppm.
5. The pretreatment solution for extra-high pressure etched foil according to claim 4, wherein the content of copper ions is 100 to 500 ppm.
6. The preparation method of the ultrahigh-pressure etched foil comprises pretreatment, primary pore-forming corrosion, secondary pore-expanding corrosion and post-treatment, and is characterized in that the pretreatment is carried out in sulfamic acid aqueous solution, the content of sulfamic acid is 1-50 wt.%, and the secondary pore-expanding corrosion is carried out in corrosive liquid containing a 5-diisopropyl amino pentylamine corrosion inhibitor.
7. The method of manufacturing an extra-high pressure etched foil according to claim 6, wherein the content of sulfamic acid is 5 to 50 wt.%.
8. The method for preparing an extra-high pressure etched foil according to claim 7, wherein the content of sulfamic acid is 5 to 30 wt.%.
9. The method for manufacturing an extra-high pressure etched foil according to claim 6, wherein copper ions are added to the sulfamic acid aqueous solution, and the content of the copper ions is 1 to 1000 ppm.
10. The method for producing an extra-high pressure etched foil according to claim 9, wherein the content of copper ions is 100 to 800 ppm.
11. The method for producing an extra-high pressure etched foil according to claim 10, wherein the content of copper ions is 100 to 500 ppm.
12. The method for preparing an extra-high pressure etched foil according to claim 6, wherein the temperature of the pretreatment is 40 to 65 ℃ and the time of the pretreatment is 30 to 60 seconds.
13. The method for producing extra-high pressure etched foil according to claim 6, wherein the content of the 5-diisopropylaminopentylamine is 0.1 to 1 wt.%.
14. The method for producing an extra-high pressure etched foil according to claim 13, wherein the secondary pore-enlarging etching is performed in a mixed aqueous solution containing aluminum ions, 5-diisopropylaminopentylamine, and nitric acid; the content of the nitric acid is 3-10 wt.%, and the content of the aluminum ions is 0.5-2 wt.%.
15. The method for preparing an extra-high pressure etched foil according to claim 13, wherein the current density during the secondary hole-expanding etching is 0.1 to 0.25A/cm2The corrosion temperature is 60-70 ℃, and the corrosion time is 400-500 s.
16. The method for producing extra-high pressure etched foil according to any one of claims 6 to 15, wherein the primary pitting is performed in a mixed aqueous solution containing aluminum ions, hydrochloric acid and sulfuric acid.
17. The method for preparing an extra-high pressure etched foil according to claim 16, wherein the first-stage pore-forming etching solution contains 0.5 to 1wt.% of aluminum ions, 5 to 10 wt.% of hydrochloric acid, and 30 to 50 wt.% of sulfuric acid.
18. According toThe method for producing an extra-high pressure etched foil according to claim 16, wherein the current density is 0.5 to 0.7A/cm in pitting corrosion2The corrosion temperature is 60-80 ℃, and the corrosion time is 50-100 s.
19. Method for producing an extra-high pressure etched foil according to any one of claims 6 to 15, characterized in that the post-treatment is carried out in a mixed aqueous solution containing aluminium ions and nitric acid.
20. The method of manufacturing an extra-high pressure etched foil according to claim 19, wherein the post-treatment solution contains 5 to 15 wt.% of nitric acid and 0.2 to 2 wt.% of aluminum ions.
21. The method for preparing an extra-high pressure etched foil according to claim 19, wherein the post-treatment temperature is 50 to 60 ℃ and the treatment time is 40 to 120 seconds.
22. An ultra-high pressure etched foil obtained by the production method according to any one of claims 6 to 21.
23. An electrode foil obtained by chemical conversion of the extra-high pressure etched foil according to claim 22.
24. An aluminum electrolytic capacitor comprising the electrode foil of claim 23.
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