CN112038098B - Pretreatment method of electrode foil - Google Patents
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- CN112038098B CN112038098B CN202010825673.6A CN202010825673A CN112038098B CN 112038098 B CN112038098 B CN 112038098B CN 202010825673 A CN202010825673 A CN 202010825673A CN 112038098 B CN112038098 B CN 112038098B
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- 238000002203 pretreatment Methods 0.000 title claims abstract description 29
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- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
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- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
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- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 45
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a pretreatment method of an electrode foil, which comprises the following steps: and (3) activation: dipping the etched foil in a polyol solution, and activating the surface of the etched foil; electro-deposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil; and (3) heat treatment: carrying out heat treatment on the electrodeposited corrosion foil to convert the aluminum hydroxide film into an aluminum oxide film; and (3) perfecting the membrane: repeating the steps of electrodepositing and heat treatment for at least 2 times to densify the aluminum oxide film. The pretreated etched foil is subjected to four-stage formation, depolarization, and compensation to obtain an electrode foil. Compared with the traditional water boiling pretreatment process, the preparation process of the electrode foil can reduce the energy consumption by 40 percent, and greatly reduce the production cost of the electrode foil.
Description
Technical Field
The invention belongs to the technical field of electrode materials for capacitors, and particularly relates to a pretreatment method of an electrode foil.
Background
The electrode foil is a novel electronic functional material encouraged and supported by the nation as a key raw material for manufacturing the aluminum electrolytic capacitor. The production of the electrode foil for the aluminum electrolytic capacitor is a process of increasing the surface area of the electronic optical foil after electrochemical or chemical corrosion and forming an aluminum oxide dielectric layer on the surface of the aluminum foil through electrochemical anodic oxidation, and relates to the technology and related industries of multiple subjects such as machinery, chemical engineering, electronics, metal materials and the like. In the production process of the electrode foil, the highest energy consumption is the formation process, and the electric charge in the medium-high pressure formation foil production accounts for 50-70% of the production cost of the electrode foil. With the development of the aluminum electrolytic capacitor market, the voltage demand on the electrode foil is higher and higher, and the electric energy required in the production of the electrode foil is further increased due to the increase of the voltage of the electrode foil, so that the reduction of the preparation energy consumption of the electrode foil is a difficult problem to be solved in the production.
In order to reduce the energy consumption of the electrode foil in the formation process, the existing method mainly comprises the following steps: first, hydration treatment, increasing the number of stages in the electrode foil formation process, e.g. US 2859148A; secondly, the device is improved, for example, CN209555389U improves the feeding device, for example, CN109737721A improves the drying device; third, improvements to the feed tank solution in turn reduce tank solution pressure drops, such as CN109628990A and CN 103397367B.
The conventional method for reducing the production energy consumption in the electrode foil formation process can reduce the energy consumption, but still has the following problems.
(1) The hydration pretreatment of the electrode foil before formation is to form a hydrated oxide film by means of dehydration. On one hand, the rate of forming the hydrated oxide film is slowed down along with the prolonging of the hydration treatment time, the thickness of the hydrated oxide film is not increased after a certain time, and a large number of holes are blocked along with the increase of the thickness of the hydrated oxide film, so that the final capacity of the electrode foil is influenced; on the other hand, an oxide film formed by dehydration of a hydrated oxide film has a large number of defects, which affect the performance of the electrode foil, resulting in large leakage current, poor hydration resistance, and the like.
(2) The number of stages of formation is increased, and the energy consumption of electrode foil formation can be effectively reduced theoretically, but in actual production, the more the number of stages is, the lower the energy consumption is, and when the number of stages of formation reaches 6, the phenomenon that the energy consumption of the number-of-stages formation production is not reduced or even increased is caused by increasing the number of stages.
(3) Through the transformation of relevant machine tank liquor or machine equipment, the tank liquor voltage drop in the formation liquor or the contact resistance of a circuit is reduced, the use efficiency of electric energy is improved, and the energy consumption in formation production is reduced to a certain extent. However, since the oxide film forming mechanism is not changed, a large amount of electricity is still required to be supplied for growing alumina, and the electric energy required for oxidation in the formation process cannot be reduced.
Therefore, the existing electrode foil preparation process still needs to be improved.
Disclosure of Invention
Aiming at the technical problem of high energy consumption of the preparation method of the electrode foil in the prior art, the invention provides a pretreatment method of the electrode foil, which is used for directly compounding an aluminum oxide layer on the surface of a corrosion foil, thereby effectively reducing the production energy consumption of the electrode foil.
Specifically, in a first aspect, the present invention provides a pretreatment method of an electrode foil, comprising:
s1 activation: dipping the etched foil in a polyol solution, and activating the surface of the etched foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil;
s3 heat treatment: carrying out heat treatment on the electrodeposited corrosion foil to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for at least 2 times to densify the aluminum oxide film.
The following describes each step in detail according to an embodiment of the present invention.
S1 activation
The surface of the electrode foil is negatively charged by the adsorption of the polyhydric alcohol on the surface of the electrode foil, and the like, so that the surface of the electrode foil is activated, and the effect of electrodeposition is improved.
According to an embodiment of the present invention, the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, butylene glycol, glycerol, and pentaerythritol.
According to some embodiments of the invention, the polyol is one or two of ethylene glycol, propylene glycol, butylene glycol, glycerol, pentaerythritol. Preferably, when the polyol is a combination of two alcohols, the volume ratio is 1: 1.
In some embodiments, the polyol solution is an ethylene glycol solution; in some embodiments, the polyol solution is a mixed solution of propylene glycol and butylene glycol; in some embodiments, the polyol solution is a mixed solution of glycerol and pentaerythritol.
As a further preferred embodiment, the mass fraction of the polyol solution is 10-30%, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, and the like.
According to the embodiment provided by the invention, the dipping temperature is 20-40 ℃, and the dipping time is 5-10 min.
Specifically, the temperature of the impregnation may be exemplified by: 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, etc.
The time of the impregnation may be exemplified by: 5min, 6min, 7min, 8min, 9min, 10min, and so on.
S2 electrodeposition
The function of electrodeposition is to form an aluminum hydroxide film on the surface of the etched foil. Since the particle surface of the aluminum hydroxide sol gel is positively charged, the aluminum hydroxide sol gel particles can be deposited on the surface of the electrode foil by corroding the foil as a cathode.
According to an embodiment of the present invention, the aluminum hydroxide sol gel contains 30 to 50% by mass of aluminum hydroxide, such as 30%, 35%, 40%, 45%, 50%, and the like.
According to an embodiment of the present invention, the pH of the aluminum hydroxide sol gel is controlled to be 6 to 10, for example: 6. 7, 8, 9, 10, etc.
According to the embodiment provided by the invention, the particle size of the aluminum hydroxide sol-gel particles is 5-30nm, and the aluminum hydroxide sol-gel with proper particle size is beneficial to the stability of the sol-gel and the entry of the sol into the holes in the corrosion foil, so that the formed aluminum hydroxide film layer is more uniform.
Specifically, the particle diameter of the aluminum hydroxide sol-gel particles may be: 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, and the like.
According to an embodiment of the present invention, the power-up process includes: performing electrodeposition at 15-35 deg.C for 0.5-2min under 10-20V DC voltage. Within this range, the aluminum hydroxide film formed has a desired compactness and thickness.
Specifically, the dc voltage includes: 10V, 11V, 12V, 13V, 14V, 15V, 16V, 17V, 18V, 19V, 20V, and so forth.
The electrodeposition temperature may be exemplified by: 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, etc.
The electrodeposition time may be exemplified by: 0.5min, 1min, 1.5min, 2min, and so on.
S3 Heat treatment
And (3) dehydrating the aluminum hydroxide film under a high-temperature condition through heat treatment, and realizing the transformation of the crystal form to obtain the finally required crystal form aluminum oxide film of the electrode foil.
According to an embodiment of the invention, the heat treatment comprises: drying at 150 ℃ and 200 ℃ for 1-2min, and then performing heat treatment at 500 ℃ and 600 ℃ for 2-5 min.
Specifically, the drying temperature may be exemplified by: 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, etc.
The heat treatment temperature may be, for example: 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, and the like.
Perfection of S4 film
After the heat treatment, as the crystal transformation causes defects such as more gaps, the treatment needs to be carried out for many times to ensure the compactness and the required thickness of the deposited film. Preferably, the electrodeposition-heat treatment is repeated at least 2 times, and may be, for example, 2 to 4 times.
Pretreatment of S0
As a preferred embodiment, the activation further comprises a pretreatment of the etched foil before the activation. The effect is that the impurity in the corrosion foil is removed, and the oxide film on the surface of the corrosion foil is removed, so that the surface activity of the corrosion foil is higher, and the subsequent treatment is easier to perform.
According to an embodiment of the present invention, the pre-processing comprises: the etched foil was immersed in an acid solution and then washed with pure water.
According to some embodiments provided herein, the acid solution is a nitric acid solution with a mass fraction of 3-10% (e.g., 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.).
According to some embodiments of the present invention, the dipping temperature is 30 to 65 ℃ and the dipping time is 1 to 5 min.
Specifically, the impregnation temperature may be exemplified by: 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, etc.
The impregnation time may be exemplified by: 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, and so on.
S5 post-processing
As a preferred embodiment, the membrane after completion further comprises a post-treatment, in particular the post-treatment comprises: and immersing the etched foil subjected to film improvement in acid liquor.
Due to the fact that the thin film layer formed by electrodeposition still has an unconverted aluminum hydroxide structure even after heat treatment and multiple times of composite treatment, the structure causes the blockage of holes to weaken the capacity on one hand, and the aluminum hydroxide is in a loose structure and easily influences the performance of the final electrode foil on the other hand. The relevant aluminum hydroxide structure is removed through acid liquor dipping treatment, and then the subsequent formation treatment of the formation liquid is carried out, so that the defect number of the electrode foil oxide film can be greatly reduced.
According to some embodiments provided herein, the acid solution is a nitric acid solution with a mass fraction of 2-5% (e.g., 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.).
According to some embodiments of the present invention, the dipping temperature is 30 to 50 ℃ and the dipping time is 2 to 5 min.
Specifically, the impregnation temperature may be exemplified by: 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, etc.
The impregnation time may be exemplified by: 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, and so on.
In a second aspect, the present invention provides a method for producing an electrode foil, comprising the step of pretreating an etched foil using the above pretreatment method.
Specifically, the preparation method of the electrode foil comprises the following steps: and carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil. The depolarization and complementary formation treatment can further reduce the defects of the composite aluminum oxide film and ensure that the electrode foil reaches the required reaching voltage.
According to an embodiment provided by the present invention, the method for preparing the electrode foil includes:
carrying out four-stage formation: carrying out four-stage formation on the pretreated corrosion foil;
first depolarization processing: carrying out first depolarization processing on the formed foil after the quaternary formation;
first complementary forming treatment: carrying out first compensation forming treatment on the formed foil after the first depolarization;
a second depolarization process: performing second depolarization processing on the formed foil after the first complementary forming processing;
second complementary forming treatment: performing second compensation forming treatment on the formed foil subjected to the second depolarization treatment;
and (3) drying: and drying the formed foil after the second complementary formation treatment to obtain the electrode foil.
The quaternization, depolarization, complementary formation and drying may be performed according to any method known in the art, without particular limitation.
In a third aspect, the present invention provides an electrode foil obtained by the above-mentioned production method
In a fourth aspect, the present invention provides an aluminum electrolytic capacitor comprising the above electrode foil.
Compared with the prior art, the invention has the following technical effects:
before formation treatment, the surface of a corrosion foil is pretreated, an aluminum hydroxide film is electrodeposited in aluminum hydroxide sol-gel, then the aluminum hydroxide film is dehydrated through high-temperature heat treatment, crystal form conversion is realized, an aluminum oxide film of a crystal form finally required by an electrode foil is obtained, electrodeposition and heat treatment steps are alternately carried out for multiple times, a relatively compact aluminum oxide composite film is formed on the surface of the corrosion foil, and electric energy required to be provided in subsequent oxidation is reduced.
Drawings
FIG. 1: the embodiment of the invention provides a flow chart of a pretreatment method of an electrode foil.
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.
According to an embodiment of the present invention, there is provided a method for pretreating an electrode foil, as shown in fig. 1, including:
s0 pretreatment: immersing the etched foil in a nitric acid solution, and then cleaning with pure water;
s1 activation: dipping the pretreated etched foil in a polyol solution, and activating the surface of the etched foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil;
s3 heat treatment: carrying out heat treatment on the electrodeposited corrosion foil to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for at least 2 times to densify the aluminum oxide film;
and S5 post-processing: dipping the etched foil treated by the S4 in a nitric acid solution;
wherein the polyalcohol is at least one of ethylene glycol, propylene glycol, butanediol, glycerol and pentaerythritol.
In another aspect, the present invention provides a method for preparing an electrode foil, comprising the step of pretreating a corrosion foil using the above pretreatment method.
Specifically, the preparation method of the electrode foil comprises the following steps: and carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil.
According to an embodiment of the present invention, the method for preparing the electrode foil further includes:
carrying out four-stage formation: carrying out four-stage formation on the pretreated corrosion foil;
first depolarization processing: carrying out first depolarization processing on the formed foil after the quaternary formation;
first complementary forming treatment: carrying out first compensation forming treatment on the formed foil after the first depolarization;
a second depolarization process: performing second depolarization processing on the formed foil after the first complementary forming processing;
second complementary forming treatment: performing second compensation forming treatment on the formed foil subjected to the second depolarization treatment;
and (3) drying: and drying the formed foil after the second complementary formation treatment to obtain the electrode foil.
The quaternization, depolarization, complementary formation and drying may be performed according to any method known in the art, without particular limitation.
This can be done, for example, in the following manner:
carrying out four-stage formation on the pretreated corrosion foil in a formation liquid of boric acid and ammonium pentaborate;
first depolarization processing: carrying out first depolarization processing on the formed foil after the quaternization in a phosphoric acid solution;
first complementary forming treatment: carrying out first forming supplement treatment on the depolarized formed foil in a forming solution of boric acid and ammonium pentaborate;
a second depolarization process: carrying out second depolarization processing on the formed foil after the first complementary forming processing at high temperature (for example, 500 ℃);
second complementary forming treatment: carrying out second compensation forming treatment on the formed foil subjected to the second depolarization treatment in a forming solution of boric acid and ammonium pentaborate;
and (3) drying: and drying the formed foil after the second complementary formation treatment to obtain the electrode foil.
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
The pretreatment method of the electrode foil provided in this embodiment includes:
s0 pretreatment: putting the etched foil into a nitric acid solution with the mass fraction of 3%, soaking for 5min at 65 ℃, and then cleaning with pure water;
s1 activation: placing the pretreated etched foil in 10% glycol solution by mass, soaking at 20 ℃ for 10min, and activating the surface of the etched foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil, wherein the aluminum hydroxide sol-gel comprises 50% of aluminum hydroxide by mass, the pH value of the aluminum hydroxide sol-gel is controlled to be 6, and the particle size of aluminum hydroxide sol-gel particles is 5 nm; controlling the reaction temperature to be 15 ℃, and reacting for 2min under the condition of applying 10V direct current voltage;
s3 heat treatment: drying the electrodeposited corrosion foil at 150 ℃ for 2min, and then carrying out heat treatment at 500 ℃ for 5min to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for 4 times to densify the aluminum oxide film;
and S5 post-processing: and (3) soaking the etched foil treated by the S4 in a nitric acid solution with the mass fraction of 2% for 5min at 50 ℃.
And carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil.
Example 2
The pretreatment method of the electrode foil provided in this embodiment includes:
s0 pretreatment: placing the etched foil in a nitric acid solution with the mass fraction of 7%, soaking for 3min at 50 ℃, and then cleaning with pure water;
s1 activation: placing the pretreated etched foil in a mixed solution of 20% by mass, propylene glycol and butanediol (volume ratio of 1:1), soaking at 30 deg.C for 8min, and activating the surface of the etched foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil, wherein the aluminum hydroxide sol-gel comprises 40% of aluminum hydroxide by mass, the pH value of the aluminum hydroxide sol-gel is controlled to be 8, and the particle size of aluminum hydroxide sol-gel particles is 15 nm; controlling the reaction temperature to be 15 ℃, and reacting for 2min under the condition of applying 10V direct current voltage;
s3 heat treatment: drying the electrodeposited etched foil at 200 ℃ for 1min, and then carrying out heat treatment at 550 ℃ for 4min to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for 3 times to densify the aluminum oxide film;
and S5 post-processing: and (3) soaking the etched foil treated by the S4 in a nitric acid solution with the mass fraction of 4% for 4min at 40 ℃.
And carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil.
Example 3
The pretreatment method of the electrode foil provided in this embodiment includes:
s0 pretreatment: placing the etched foil in a nitric acid solution with the mass fraction of 10%, soaking for 5min at 40 ℃, and then cleaning with pure water;
s1 activation: placing the pretreated corrosion foil in a mixed solution of 30% by mass and glycerol and pentaerythritol (volume ratio of 1:1), soaking at 40 ℃ for 5min, and activating the surface of the corrosion foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil, wherein the aluminum hydroxide sol-gel comprises 30 mass percent of aluminum hydroxide, the pH value of the aluminum hydroxide sol-gel is controlled to be 10, and the particle size of aluminum hydroxide sol-gel particles is 30 nm; controlling the reaction temperature to be 35 ℃, and reacting for 0.5min under the condition of applying 20V direct current voltage;
s3 heat treatment: drying the electrodeposited corrosion foil at 200 ℃ for 2min, and then carrying out heat treatment at 600 ℃ for 2min to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for 2 times to densify the aluminum oxide film;
and S5 post-processing: and (3) soaking the etched foil treated by the S4 in a nitric acid solution with the mass fraction of 5% for 2min at the temperature of 30 ℃.
And carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil.
Comparative example 1
The pretreatment method of the electrode foil provided in this comparative example included: the etched foil was placed in pure water and boiled in water at 97 deg.C for 10 min.
And carrying out four-stage formation, depolarization and compensation formation treatment on the pretreated corrosion foil to obtain the electrode foil.
Comparative example 2
In the pretreatment method of the electrode foil provided in this comparative example, the difference from example 1 is that: step S4 is omitted.
Performance testing
The energy consumption ratios required in each group of electrode foils are shown in table 1 by monitoring the energy consumption during the preparation process of the above examples and comparative examples, and the data in the table are the data obtained by comparing with the data in comparative example 1.
TABLE 1
| Example one another | Electrode foil arrival voltage | Energy consumption for preparing electrode foil |
| Example 1 | 565.2V | 58.6％ |
| Example 2 | 565.7V | 57.7％ |
| Example 3 | 565.3V | 60.0％ |
| Comparative example 1 | 565.5V | 100％ |
| Comparative example 2 | 565.9V | 76.5％ |
As can be seen from the comparison of the preparation energy consumption of the electrode foil in the embodiment of the invention and the comparative example 1 (conventional pretreatment), the actual measurement of the voltage deviation of the electrode foil is less than 1V, the voltage deviation can be basically ignored, the preparation energy consumption of the electrode foil can be reduced by 40% to the lowest extent, and the production cost of the electrode foil is greatly reduced by performing the subsequent formation preparation after the electrodeposition of the composite aluminum hydroxide film on the surface of the electrode foil and the heat treatment conversion and the multiple treatments. In comparative example 2, since the film perfecting was not performed, the obtained oxide film had many defects, and the defect portion of the oxide film had to be repaired by aluminum oxide generated in the formation process, the energy consumption for preparing the electrode foil was increased by 17.9% compared to example 1.
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 (18)
1. A pretreatment method of an electrode foil is characterized in that: the method comprises the following steps:
s1 activation: dipping the etched foil in a polyol solution, and activating the surface of the etched foil;
s2 electrodeposition: placing the activated corrosion foil in aluminum hydroxide sol-gel as a cathode to perform electrification treatment, and depositing an aluminum hydroxide film on the surface of the corrosion foil;
s3 heat treatment: carrying out heat treatment on the electrodeposited corrosion foil to convert the aluminum hydroxide film into an aluminum oxide film;
and (3) completing an S4 film: repeating the steps S2 and S3 for at least 2 times to densify the aluminum oxide film.
2. The pretreatment method for electrode foil according to claim 1, characterized in that: in the activation of S1, the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, butylene glycol, glycerol and pentaerythritol.
3. The pretreatment method for electrode foil according to claim 2, characterized in that: the mass fraction of the polyalcohol solution is 10-30%.
4. The pretreatment method for electrode foil according to claim 1, characterized in that: in the S1 activation, the dipping temperature is 20-40 ℃, and the dipping time is 5-10 min.
5. The method for pretreating an electrode foil according to claim 1, wherein the aluminum hydroxide sol gel comprises 30 to 50 mass% of aluminum hydroxide in the electrodeposition in S2.
6. The pretreatment method for electrode foil according to claim 5, wherein the particle diameter of the aluminum hydroxide sol-gel particles is 5 to 30 nm.
7. The pretreatment method for electrode foil according to claim 5, wherein the pH of the aluminum hydroxide sol gel is controlled to 6 to 10.
8. The pretreatment method for electrode foil according to claim 1, wherein in the S2 electrodeposition, the electrification process comprises: performing electrodeposition at 15-35 deg.C for 0.5-2min under 10-20V DC voltage.
9. The pretreatment method for electrode foil according to claim 1, wherein in the S3 heat treatment, the heat treatment comprises: the electrodeposited corrosion foil is dried at the temperature of 150-.
10. The pretreatment method for electrode foil according to any one of claims 1 to 9, wherein the step of S1 activation further comprises a step of S0 pretreatment of the etched foil.
11. The pretreatment method for electrode foil according to claim 10, wherein the pretreatment comprises: the etched foil was immersed in an acid solution and then washed with pure water.
12. The pretreatment method for electrode foil according to claim 11, wherein the acid solution is a nitric acid solution with a mass fraction of 3 to 10%, the dipping temperature is 30 to 65 ℃, and the dipping time is 1 to 5 min.
13. The pretreatment method for electrode foil according to any one of claims 1 to 9, wherein the S4 film further comprises an S5 post-treatment after completion.
14. The pretreatment method for electrode foil according to claim 13, wherein the post-treatment comprises: and (4) immersing the etched foil treated by the S4 in acid liquor.
15. The pretreatment method for electrode foil according to claim 14, wherein the acid solution is a nitric acid solution having a mass fraction of 2 to 5%, the dipping temperature is 30 to 50 ℃, and the dipping time is 2 to 5 min.
16. A method for producing an electrode foil, characterized by comprising a step of pretreating an etched foil by the pretreatment method according to any one of claims 1 to 15.
17. An electrode foil obtained by the production method according to claim 16.
18. An aluminum electrolytic capacitor comprising the electrode foil of claim 17.
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